Nos publications
Chen, Hong; Noirbent, Guillaume; Zhang, Yijun; Sun, Ke; Liu, Shaohui; Brunel, Damien; Gigmes, Didier; Graff, Bernadette; Morlet-Savary, Fabrice; Xiao, Pu; Dumur, Frederic; Lalevee, Jacques Photopolymerization and 3D/4D applications using newly developed dyes: Search around the natural chalcone scaffold in photoinitiating systems Article de journal Dyes and Pigments, 188 , p. 109213, 2021. @article{Chen2021c, title = {Photopolymerization and 3D/4D applications using newly developed dyes: Search around the natural chalcone scaffold in photoinitiating systems}, author = {Hong Chen and Guillaume Noirbent and Yijun Zhang and Ke Sun and Shaohui Liu and Damien Brunel and Didier Gigmes and Bernadette Graff and Fabrice Morlet-Savary and Pu Xiao and Frederic Dumur and Jacques Lalevee}, doi = {10.1016/j.dyepig.2021.109213}, year = {2021}, date = {2021-04-01}, journal = {Dyes and Pigments}, volume = {188}, pages = {109213}, abstract = {Chalcones are well-known natural dyes, 18 different derivatives selected from the rational molecular design (i.e. through molecular orbital calculations) were synthesized. If used in conjunction with an amine (i.e. ethyl 1, 4-(dimethylamino) benzoate, EDB) and an iodonium salt (bis(4-tert-butylphenyl) iodonium hexafluorophosphate, Iod) as photoinitiating systems (PISs), these dyes can initiate both the free radical polymerization of polyethylene glycol diacrylate (PEG-diacrylate) and the cationic polymerization of 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate (EPOX) via oxidation-reduction reaction mechanisms. Furthermore, among the 18 different suggested structures, except for dyes 9 and 10, which have been synthesized and used in other fields, the remaining 16 dyes have never been synthesized before. The photopolymerization efficiency of acrylates carried out under LED@405 nm are excellent both for thin films (the thickness is about 0.2 mm) and thick films (the thickness is about 2 mm). Furthermore, all of them can also boost the cationic polymerization of EPOX upon LED irradiation at 405 nm, in the presence of an iodonium salt and an amine. More interestingly, stereoscopic 3D patterns were successfully fabricated by the direct laser write (DLW) technique which demonstrated reversible swelling properties and reversible shape-memory effects induced via swelling and dehydration for the access to 4D printing.}, keywords = {}, pubstate = {published}, tppubtype = {article} } Chalcones are well-known natural dyes, 18 different derivatives selected from the rational molecular design (i.e. through molecular orbital calculations) were synthesized. If used in conjunction with an amine (i.e. ethyl 1, 4-(dimethylamino) benzoate, EDB) and an iodonium salt (bis(4-tert-butylphenyl) iodonium hexafluorophosphate, Iod) as photoinitiating systems (PISs), these dyes can initiate both the free radical polymerization of polyethylene glycol diacrylate (PEG-diacrylate) and the cationic polymerization of 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate (EPOX) via oxidation-reduction reaction mechanisms. Furthermore, among the 18 different suggested structures, except for dyes 9 and 10, which have been synthesized and used in other fields, the remaining 16 dyes have never been synthesized before. The photopolymerization efficiency of acrylates carried out under LED@405 nm are excellent both for thin films (the thickness is about 0.2 mm) and thick films (the thickness is about 2 mm). Furthermore, all of them can also boost the cationic polymerization of EPOX upon LED irradiation at 405 nm, in the presence of an iodonium salt and an amine. More interestingly, stereoscopic 3D patterns were successfully fabricated by the direct laser write (DLW) technique which demonstrated reversible swelling properties and reversible shape-memory effects induced via swelling and dehydration for the access to 4D printing. |
Jellali, Salah; Charabi, Yassine; Usman, Muhammad; Al-Badi, Abdullah; Jeguirim, Mejdi Investigations on Biogas Recovery from Anaerobic Digestion of Raw Sludge and Its Mixture with Agri-Food Wastes: Application to the Largest Industrial Estate in Oman Article de journal Sustainability, 13 (7), p. 3698, 2021. @article{Jellali2021a, title = {Investigations on Biogas Recovery from Anaerobic Digestion of Raw Sludge and Its Mixture with Agri-Food Wastes: Application to the Largest Industrial Estate in Oman}, author = {Salah Jellali and Yassine Charabi and Muhammad Usman and Abdullah Al-Badi and Mejdi Jeguirim}, doi = {10.3390/su13073698}, year = {2021}, date = {2021-04-01}, journal = {Sustainability}, volume = {13}, number = {7}, pages = {3698}, abstract = {This work is intended to evaluate the technical, environmental, and economic feasibility of converting the sludge produced at an industrial estate's wastewater treatment plant (WWTP) in Oman into energy through anaerobic digestion (AD). In this study, three different scenarios were analyzed. They concerned the digestion of the total amount of the produced sludge alone (240 m(3) day(-1)) (scenario 1), and its co-digestion with wet agri-food wastes (AFW) at rates of two tonnes day(-1) (scenario 2) and ten tonnes day(-1) (scenario 3). Based on the analyses of sludge samples, an intensive literature review regarding sludge and AFW Physico-chemical and energetic characteristics and the use of the cost-benefit analysis (CBA) approach, it was found that, for the overall duration of the project (20 years), the AD of the sludge alone (scenario 1) permitted the production of 43.9 GWh of electricity, the reduction of greenhouse gas (GHG) emissions (more than 37,000 tonnes equivalent CO2 (TCO2)) and exhibited positive net present value (NPV: $393,483) and an internal return rate (IRR) of 19.4%. Co-digesting sludge with AFW significantly increased all of these key performance indicators. For instance, scenario 3 results in the recovery of electrical energy of 82.2 GWh and avoids the emission of 70,602 tCO(2). Moreover, a higher NPV and IRR of $851,876 and 21.8%, respectively, and a payback period (PBP) of only seven years were calculated. The sensitivity analysis revealed that a decrease in total expenses by 15% results in a significant increase of the NPV and the IRR to $1,418,704 and 33.9%, respectively, for scenario 3. Considering a pessimistic assumption (an increase of the total expenses by 15%), all studied scenarios remain attractive. For instance, for scenario 3, the NPV, IRR, and PBP were evaluated to $285,047, 13.5%, and 9 years, respectively. Therefore, the co-digestion of sludge with agri-food wastes for energy recovery purposes could be considered a promising, eco-friendly, and economically viable approach in the Omani industrial estates.}, keywords = {}, pubstate = {published}, tppubtype = {article} } This work is intended to evaluate the technical, environmental, and economic feasibility of converting the sludge produced at an industrial estate's wastewater treatment plant (WWTP) in Oman into energy through anaerobic digestion (AD). In this study, three different scenarios were analyzed. They concerned the digestion of the total amount of the produced sludge alone (240 m(3) day(-1)) (scenario 1), and its co-digestion with wet agri-food wastes (AFW) at rates of two tonnes day(-1) (scenario 2) and ten tonnes day(-1) (scenario 3). Based on the analyses of sludge samples, an intensive literature review regarding sludge and AFW Physico-chemical and energetic characteristics and the use of the cost-benefit analysis (CBA) approach, it was found that, for the overall duration of the project (20 years), the AD of the sludge alone (scenario 1) permitted the production of 43.9 GWh of electricity, the reduction of greenhouse gas (GHG) emissions (more than 37,000 tonnes equivalent CO2 (TCO2)) and exhibited positive net present value (NPV: $393,483) and an internal return rate (IRR) of 19.4%. Co-digesting sludge with AFW significantly increased all of these key performance indicators. For instance, scenario 3 results in the recovery of electrical energy of 82.2 GWh and avoids the emission of 70,602 tCO(2). Moreover, a higher NPV and IRR of $851,876 and 21.8%, respectively, and a payback period (PBP) of only seven years were calculated. The sensitivity analysis revealed that a decrease in total expenses by 15% results in a significant increase of the NPV and the IRR to $1,418,704 and 33.9%, respectively, for scenario 3. Considering a pessimistic assumption (an increase of the total expenses by 15%), all studied scenarios remain attractive. For instance, for scenario 3, the NPV, IRR, and PBP were evaluated to $285,047, 13.5%, and 9 years, respectively. Therefore, the co-digestion of sludge with agri-food wastes for energy recovery purposes could be considered a promising, eco-friendly, and economically viable approach in the Omani industrial estates. |
Ng, Eng-Poh; Ahmad, Nur Hidayahni; Khoerunnisa, Fitri; Mintova, Svetlana; Ling, Tau Chuan; Daou, Jean T Offretite Zeolite Single Crystals Synthesized by Amphiphile-Templating Approach Article de journal Molecules, 26 (8), p. 2238, 2021. @article{Ng2021h, title = {Offretite Zeolite Single Crystals Synthesized by Amphiphile-Templating Approach}, author = {Eng-Poh Ng and Nur Hidayahni Ahmad and Fitri Khoerunnisa and Svetlana Mintova and Tau Chuan Ling and Jean T Daou}, doi = {10.3390/molecules26082238}, year = {2021}, date = {2021-04-01}, journal = {Molecules}, volume = {26}, number = {8}, pages = {2238}, abstract = {Offretite zeolite synthesis in the presence of cetyltrimethylammonium bromide (CTABr) is reported. The offretite crystals were synthesized with a high crystallinity and hexagonal prismatic shape after only 72 h of hydrothermal treatment at 180 degrees C. The CTABr has dual-functions during the crystallization of offretite, viz. as structure-directing agent and as mesoporogen. The resulting offretite crystals, with a Si/Al ratio of 4.1, possess more acid sites than the conventional offretite due to their high crystallinity and hierarchical structure. The synthesized offretite is also more reactive than its conventional counterpart in the acylation of 2-methylfuran for biofuel production under non-microwave instant heating condition, giving 83.5% conversion with 100% selectivity to the desired product 2-acetyl-5-methylfuran. Hence, this amphiphile synthesis approach offers another cost-effective and alternative route for crystallizing zeolite materials that require expensive organic templates.}, keywords = {}, pubstate = {published}, tppubtype = {article} } Offretite zeolite synthesis in the presence of cetyltrimethylammonium bromide (CTABr) is reported. The offretite crystals were synthesized with a high crystallinity and hexagonal prismatic shape after only 72 h of hydrothermal treatment at 180 degrees C. The CTABr has dual-functions during the crystallization of offretite, viz. as structure-directing agent and as mesoporogen. The resulting offretite crystals, with a Si/Al ratio of 4.1, possess more acid sites than the conventional offretite due to their high crystallinity and hierarchical structure. The synthesized offretite is also more reactive than its conventional counterpart in the acylation of 2-methylfuran for biofuel production under non-microwave instant heating condition, giving 83.5% conversion with 100% selectivity to the desired product 2-acetyl-5-methylfuran. Hence, this amphiphile synthesis approach offers another cost-effective and alternative route for crystallizing zeolite materials that require expensive organic templates. |
Lai, H; Zhu, D; Peng, X; Zhang, J; Lalevee, J; Xiao, P N-Aryl glycines as versatile initiators for various polymerizations Article de journal Polymer Chemistry, 12 (13), p. 1991–2000, 2021. @article{Lai2021, title = {N-Aryl glycines as versatile initiators for various polymerizations}, author = {H Lai and D Zhu and X Peng and J Zhang and J Lalevee and P Xiao}, doi = {10.1039/d1py00030f}, year = {2021}, date = {2021-04-01}, journal = {Polymer Chemistry}, volume = {12}, number = {13}, pages = {1991--2000}, abstract = {The design and development of versatile initiators for various types of polymerization reactions, i.e. thermal-/photo-crosslinked/controlled polymerizations, is highly interesting to fabricate high-performance polymer materials. Herein, we synthesized two N-aryl glycine-based initiators, N-(1-naphthyl)glycine (NNG) and N-(1-pyrenyl)glycine (NPYG), and investigated their ability to trigger thermal- or light-induced polymerizations. Relevant photochemical mechanisms to generate reactive species were studied by steady state photolysis, fluorescence, and electron paramagnetic resonance spin-trapping techniques. The synthesized N-aryl glycine-based initiators can act as monocomponent photoinitiators or be incorporated into multicomponent photoinitiating systems for free radical or cationic crosslinked photopolymerization under diverse blue LEDs. Moreover, NPYG was also capable of initiating reversible addition-fragmentation chain transfer polymerization under either thermal- or light-induced reaction.}, keywords = {}, pubstate = {published}, tppubtype = {article} } The design and development of versatile initiators for various types of polymerization reactions, i.e. thermal-/photo-crosslinked/controlled polymerizations, is highly interesting to fabricate high-performance polymer materials. Herein, we synthesized two N-aryl glycine-based initiators, N-(1-naphthyl)glycine (NNG) and N-(1-pyrenyl)glycine (NPYG), and investigated their ability to trigger thermal- or light-induced polymerizations. Relevant photochemical mechanisms to generate reactive species were studied by steady state photolysis, fluorescence, and electron paramagnetic resonance spin-trapping techniques. The synthesized N-aryl glycine-based initiators can act as monocomponent photoinitiators or be incorporated into multicomponent photoinitiating systems for free radical or cationic crosslinked photopolymerization under diverse blue LEDs. Moreover, NPYG was also capable of initiating reversible addition-fragmentation chain transfer polymerization under either thermal- or light-induced reaction. |
Bouzidi, Imen; Fkiri, Anis; Sellami, Badreddine; Harrath, Abdel Halim; Boufahja, Fehmi; Mezni, Amine; Vidal, Loic; Vaulot, Cyril; Josien, Ludovic; Beyrem, Hamouda; Mougin, Karine Does the photocatalytic activity of nanoparticles protect the marine mussel Mytilus galloprovincialis from polycyclic aromatic hydrocarbon toxicity? Article de journal Environmental science and pollution research international, 2021. @article{Bouzidi2021, title = {Does the photocatalytic activity of nanoparticles protect the marine mussel Mytilus galloprovincialis from polycyclic aromatic hydrocarbon toxicity?}, author = {Imen Bouzidi and Anis Fkiri and Badreddine Sellami and Abdel Halim Harrath and Fehmi Boufahja and Amine Mezni and Loic Vidal and Cyril Vaulot and Ludovic Josien and Hamouda Beyrem and Karine Mougin}, doi = {10.1007/s11356-021-13908-4}, year = {2021}, date = {2021-04-01}, journal = {Environmental science and pollution research international}, abstract = {In the present study, five NPs (containing ZnO, Au-ZnO, Cu-ZnO, TiO2, and Au-TiO2) were characterized using dynamic light scattering and transmission electron microscopy, in order to observe their behavior under environmental change. The applicability of NPs for degradation of three polycyclic aromatic hydrocarbons (PAHs), including benzo(a)pyrene, fluoranthene, and benzanthracene, using UV irradiation showed the high photocatalytic efficiency of doped NPs for the removal of the study pollutants. To predict the environmental impact and interaction between NPs and PAHs on marine organisms, Mytilus galloprovincialis mussels were exposed to concentrations of each chemical (50 and 100 mug/L) for 14 days. The mussel's response was determined using the oxidative stress biomarker approach. Measured biomarkers in the mussel's digestive gland showed possible oxidative mechanisms in a concentration-dependent manner occurring after exposure to PAHs and NPs separately. Overall, this finding provides an interesting combination to remove PAHs in water, and the incorporation of chemical element into the crystallographic structure of NPs and the combination of two different NPs to form a binary hybrid NPs are promising materials.}, keywords = {}, pubstate = {published}, tppubtype = {article} } In the present study, five NPs (containing ZnO, Au-ZnO, Cu-ZnO, TiO2, and Au-TiO2) were characterized using dynamic light scattering and transmission electron microscopy, in order to observe their behavior under environmental change. The applicability of NPs for degradation of three polycyclic aromatic hydrocarbons (PAHs), including benzo(a)pyrene, fluoranthene, and benzanthracene, using UV irradiation showed the high photocatalytic efficiency of doped NPs for the removal of the study pollutants. To predict the environmental impact and interaction between NPs and PAHs on marine organisms, Mytilus galloprovincialis mussels were exposed to concentrations of each chemical (50 and 100 mug/L) for 14 days. The mussel's response was determined using the oxidative stress biomarker approach. Measured biomarkers in the mussel's digestive gland showed possible oxidative mechanisms in a concentration-dependent manner occurring after exposure to PAHs and NPs separately. Overall, this finding provides an interesting combination to remove PAHs in water, and the incorporation of chemical element into the crystallographic structure of NPs and the combination of two different NPs to form a binary hybrid NPs are promising materials. |
Le, Cuong Minh Quoc; Vidal, Loic; Schmutz, Marc; Chemtob, Abraham Droplet nucleation in miniemulsion thiol-ene step photopolymerization Article de journal Polymer Chemistry, 12 (14), p. 2084–2094, 2021. @article{Le2021, title = {Droplet nucleation in miniemulsion thiol-ene step photopolymerization}, author = {Cuong Minh Quoc Le and Loic Vidal and Marc Schmutz and Abraham Chemtob}, doi = {10.1039/d1py00139f}, year = {2021}, date = {2021-04-01}, journal = {Polymer Chemistry}, volume = {12}, number = {14}, pages = {2084--2094}, abstract = {Complex and unique polymer colloids have been prepared by miniemulsion polymerization through particle nucleation confined to monomer droplets. Unlike radical chain polymerization, the reaction conditions for a predominant droplet nucleation have not been investigated in step polymerizations such as thiol-ene polymerization. To clarify this issue, an aqueous thiol-ene miniemulsion based on diallyl adipate and 2,2-(ethylenedioxy)diethanedithiol is prepared. Droplet stability is affected by Ostwald ripening due to the limited solubility of hexadecane (costabilizer) in the monomer phase. The control of chemical stability is also difficult, since a self-initiated polymerization is caused by adventitious radicals generated in the emulsification stage (ultrasonication). However, the addition of an appropriate concentration of a radical scavenger (quinone) can halt polymerization for several hours. Under these conditions, batch photopolymerization kinetics, molecular weight progress and particle size distribution have been determined with reproducible results. Emphasis is placed on understanding how initiator solubility, droplet size and monomer solubility affect droplet nucleation. For this purpose, a reliable measurement of droplet (particle) size distributions is achieved by combining size data from dynamic light scattering and transmission electron microscopy. When using a water-soluble photoinitiator, a substantial homogeneous nucleation is reported even for highly water-insoluble monomers. Only when the droplet diameter is low enough (about 100 nm), then droplet nucleation prevails. Conversely, a water-insoluble initiator drives a robust and complete droplet nucleation irrespective of the reaction conditions.}, keywords = {}, pubstate = {published}, tppubtype = {article} } Complex and unique polymer colloids have been prepared by miniemulsion polymerization through particle nucleation confined to monomer droplets. Unlike radical chain polymerization, the reaction conditions for a predominant droplet nucleation have not been investigated in step polymerizations such as thiol-ene polymerization. To clarify this issue, an aqueous thiol-ene miniemulsion based on diallyl adipate and 2,2-(ethylenedioxy)diethanedithiol is prepared. Droplet stability is affected by Ostwald ripening due to the limited solubility of hexadecane (costabilizer) in the monomer phase. The control of chemical stability is also difficult, since a self-initiated polymerization is caused by adventitious radicals generated in the emulsification stage (ultrasonication). However, the addition of an appropriate concentration of a radical scavenger (quinone) can halt polymerization for several hours. Under these conditions, batch photopolymerization kinetics, molecular weight progress and particle size distribution have been determined with reproducible results. Emphasis is placed on understanding how initiator solubility, droplet size and monomer solubility affect droplet nucleation. For this purpose, a reliable measurement of droplet (particle) size distributions is achieved by combining size data from dynamic light scattering and transmission electron microscopy. When using a water-soluble photoinitiator, a substantial homogeneous nucleation is reported even for highly water-insoluble monomers. Only when the droplet diameter is low enough (about 100 nm), then droplet nucleation prevails. Conversely, a water-insoluble initiator drives a robust and complete droplet nucleation irrespective of the reaction conditions. |
Lee, Zhong-Han; Hammoud, Fatima; Hijazi, Akram; Graff, Bernadette; Lalevee, Jacques; Chen, Yung-Chung Synthesis and free radical photopolymerization of triphenylamine-based oxime ester photoinitiators Article de journal Polymer Chemistry, 12 (9), p. 1286–1297, 2021. @article{Lee2021, title = {Synthesis and free radical photopolymerization of triphenylamine-based oxime ester photoinitiators}, author = {Zhong-Han Lee and Fatima Hammoud and Akram Hijazi and Bernadette Graff and Jacques Lalevee and Yung-Chung Chen}, doi = {10.1039/d0py01768j}, year = {2021}, date = {2021-03-01}, journal = {Polymer Chemistry}, volume = {12}, number = {9}, pages = {1286--1297}, abstract = {Four visible light triphenylamine-based oxime ester photoinitiators (TP-1-4) were synthesized and confirmed successfully through H-1 NMR, C-13 NMR, and electron impact mass spectrometry (EI-MS) measurements as well as elementary analyses (EA). The design strategy for triphenylamine substituted photoinitiators involved the use of hydrogen atoms only for TP-1, one methoxy group for TP-2, two methoxy groups for TP-3 and two methyl groups for TP-4. The incorporation of triphenylamine derivatives in oxime esters gives near UV and visible light absorption characters with maximum absorption peaks at around 360 nm. Upon using a UV lamp as an irradiation source, all the oxime esters showed good double bond conversion efficiency in a range of 72-92% in the free radical polymerization of trimethylolpropane triacrylate (TMPTA) through photo-DSC experiments. Among all, TP-1 displayed the highest final conversion efficiency. Accordingly, the photochemical reaction behavior was studied using photolysis, cyclic voltammograms (CV), electron spin resonance (ESR) and theoretical calculations. Additionally, selected photoinitiating systems exhibited outstanding 3D patterns with high resolution and good edge definition through direct laser write (DLW) experiments @405 nm. This work thus demonstrates a judicious chemical design to fine-tune the photopolymerization character in triphenylamine oxime ester analogues.}, keywords = {}, pubstate = {published}, tppubtype = {article} } Four visible light triphenylamine-based oxime ester photoinitiators (TP-1-4) were synthesized and confirmed successfully through H-1 NMR, C-13 NMR, and electron impact mass spectrometry (EI-MS) measurements as well as elementary analyses (EA). The design strategy for triphenylamine substituted photoinitiators involved the use of hydrogen atoms only for TP-1, one methoxy group for TP-2, two methoxy groups for TP-3 and two methyl groups for TP-4. The incorporation of triphenylamine derivatives in oxime esters gives near UV and visible light absorption characters with maximum absorption peaks at around 360 nm. Upon using a UV lamp as an irradiation source, all the oxime esters showed good double bond conversion efficiency in a range of 72-92% in the free radical polymerization of trimethylolpropane triacrylate (TMPTA) through photo-DSC experiments. Among all, TP-1 displayed the highest final conversion efficiency. Accordingly, the photochemical reaction behavior was studied using photolysis, cyclic voltammograms (CV), electron spin resonance (ESR) and theoretical calculations. Additionally, selected photoinitiating systems exhibited outstanding 3D patterns with high resolution and good edge definition through direct laser write (DLW) experiments @405 nm. This work thus demonstrates a judicious chemical design to fine-tune the photopolymerization character in triphenylamine oxime ester analogues. |
Liu, Shaohui; Zhang, Yijun; Sun, Ke; Graff, Bernadette; Xiao, Pu; Dumur, Frederic; Lalevee, Jacques Design of photoinitiating systems based on the chalcone-anthracene scaffold for LED cationic photopolymerization and application in 3D printing Article de journal European Polymer Journal, 147 , p. 110300, 2021. @article{Liu2021b, title = {Design of photoinitiating systems based on the chalcone-anthracene scaffold for LED cationic photopolymerization and application in 3D printing}, author = {Shaohui Liu and Yijun Zhang and Ke Sun and Bernadette Graff and Pu Xiao and Frederic Dumur and Jacques Lalevee}, doi = {10.1016/j.eurpolymj.2021.110300}, year = {2021}, date = {2021-03-01}, journal = {European Polymer Journal}, volume = {147}, pages = {110300}, abstract = {In this study, light-emitting diodes (LEDs) used as secure, low-cost and possessing long emission wavelengths irradiation sources were applied in photopolymerization. Seven novel anthracene derivatives (noted A1-A7) were proposed and evaluated in photosensitive systems. Three of them were never synthesized before (A1, A2 and A7) and the other derivatives were evaluated in other fields. Due to the in-silico design of molecular structure by molecular modeling, the proposed chalcone-anthracenes showed a broad absorption band in the visible region with favorable molar extinction coefficients. Photoinitiation abilities of the different photo-initiating systems were examined by the Real-Time Fourier Transformed Infrared Spectroscopy. The free radical polymerization of acrylates under LED@405 nm irradiation in laminate was evaluated and high final function conversions (FCs) were obtained in the presence of three-component photoinitiating systems based on chalcone-anthracenes/iodonium salt/amine. Meanwhile, the chalcone-anthracene derivatives exhibited high photoinitiation abilities in cationic photopolymerization of epoxides in combination with an iodonium salt under LED@405 nm irradiation. The final function conversions of epoxy using some anthracene/iodonium salt systems were even higher than the well-established dibutoxyanthracene (DBA)/iodonium salt benchmark system. In addition, due to the good light absorption properties, the cationic photopolymerization also was carried out in the presence of the chalcone-anthracene/iodonium salt systems under LED@470 nm or laser diode@447 nm irradiation (not possible to do with the reference DBA systems). Markedly, these derivatives were also able to sensitize sulfonium salts. The photochemical reactivity of anthracene derivatives was investigated through the steady state photolysis and fluorescence quenching experiments. Furthermore, the proposed interaction mechanisms of chalcone-anthracene derivatives and additives (iodonium salt and amine) were discussed using the free energy changes of electron transfer reactions. Interestingly, the cationic photopolymerization of A5/iodonium salt system was applied in 3D printing and the 3D patterns showed a good spatial resolution.}, keywords = {}, pubstate = {published}, tppubtype = {article} } In this study, light-emitting diodes (LEDs) used as secure, low-cost and possessing long emission wavelengths irradiation sources were applied in photopolymerization. Seven novel anthracene derivatives (noted A1-A7) were proposed and evaluated in photosensitive systems. Three of them were never synthesized before (A1, A2 and A7) and the other derivatives were evaluated in other fields. Due to the in-silico design of molecular structure by molecular modeling, the proposed chalcone-anthracenes showed a broad absorption band in the visible region with favorable molar extinction coefficients. Photoinitiation abilities of the different photo-initiating systems were examined by the Real-Time Fourier Transformed Infrared Spectroscopy. The free radical polymerization of acrylates under LED@405 nm irradiation in laminate was evaluated and high final function conversions (FCs) were obtained in the presence of three-component photoinitiating systems based on chalcone-anthracenes/iodonium salt/amine. Meanwhile, the chalcone-anthracene derivatives exhibited high photoinitiation abilities in cationic photopolymerization of epoxides in combination with an iodonium salt under LED@405 nm irradiation. The final function conversions of epoxy using some anthracene/iodonium salt systems were even higher than the well-established dibutoxyanthracene (DBA)/iodonium salt benchmark system. In addition, due to the good light absorption properties, the cationic photopolymerization also was carried out in the presence of the chalcone-anthracene/iodonium salt systems under LED@470 nm or laser diode@447 nm irradiation (not possible to do with the reference DBA systems). Markedly, these derivatives were also able to sensitize sulfonium salts. The photochemical reactivity of anthracene derivatives was investigated through the steady state photolysis and fluorescence quenching experiments. Furthermore, the proposed interaction mechanisms of chalcone-anthracene derivatives and additives (iodonium salt and amine) were discussed using the free energy changes of electron transfer reactions. Interestingly, the cationic photopolymerization of A5/iodonium salt system was applied in 3D printing and the 3D patterns showed a good spatial resolution. |
Blin, Jean-Luc; Michelin, Laure; Lebeau, Benedicte; Naydenov, Anton; Velinova, Ralitsa; Kolev, Hristo; Gaudin, Pierrick; Vidal, Loic; Dotzeva, Anna; Tenchev, Krasimir; Todorova, Silviya Co-Ce Oxides Supported on SBA-15 for VOCs Oxidation Article de journal Catalysts, 11 (3), p. 366, 2021. @article{Blin2021, title = {Co-Ce Oxides Supported on SBA-15 for VOCs Oxidation}, author = {Jean-Luc Blin and Laure Michelin and Benedicte Lebeau and Anton Naydenov and Ralitsa Velinova and Hristo Kolev and Pierrick Gaudin and Loic Vidal and Anna Dotzeva and Krasimir Tenchev and Silviya Todorova}, doi = {10.3390/catal11030366}, year = {2021}, date = {2021-03-01}, journal = {Catalysts}, volume = {11}, number = {3}, pages = {366}, abstract = {Reported here are new data on the structural and catalytic properties of a series of mono-component cobalt and bi-component Co-Ce catalysts supported on SBA-15 (Santa Barbara Amorphous-15)). The catalysts performance has been evaluated by tests on combustion of methane, propane, and n-hexane. It was established that the preparation of the Co-Ce catalysts by the 'two-solvent' technique does not significantly change the mesoporous structure, however, its pores are clogging with the Co and Ce guest species. Cobalt and cerium are uniformly distributed and preferentially fill up the channels of SBA-15, but oxide agglomerates located on the surface are observed as well. The highest activity of the mono-component cobalt sample is explained by its higher reducibility as a result of lower interaction of the cobalt oxide with the SBA-15. The fine dispersion of cobalt and cerium oxide and their strong interaction in the channels of the SBA-15 molecular sieve, leads to the formation of difficult-to-reduce oxide phases and, consequently, to lower catalytic activity compared to monocomponent cobalt oxide catalyst. The synthesised mesoporous structure can prevent the agglomeration of the oxide particles, thus leading to the successful development of a new and stable catalyst for decreasing greenhouse gas emissions.}, keywords = {}, pubstate = {published}, tppubtype = {article} } Reported here are new data on the structural and catalytic properties of a series of mono-component cobalt and bi-component Co-Ce catalysts supported on SBA-15 (Santa Barbara Amorphous-15)). The catalysts performance has been evaluated by tests on combustion of methane, propane, and n-hexane. It was established that the preparation of the Co-Ce catalysts by the 'two-solvent' technique does not significantly change the mesoporous structure, however, its pores are clogging with the Co and Ce guest species. Cobalt and cerium are uniformly distributed and preferentially fill up the channels of SBA-15, but oxide agglomerates located on the surface are observed as well. The highest activity of the mono-component cobalt sample is explained by its higher reducibility as a result of lower interaction of the cobalt oxide with the SBA-15. The fine dispersion of cobalt and cerium oxide and their strong interaction in the channels of the SBA-15 molecular sieve, leads to the formation of difficult-to-reduce oxide phases and, consequently, to lower catalytic activity compared to monocomponent cobalt oxide catalyst. The synthesised mesoporous structure can prevent the agglomeration of the oxide particles, thus leading to the successful development of a new and stable catalyst for decreasing greenhouse gas emissions. |
Ors, Taylan; Gouraud, Fanny; Michel, Vincent; Huger, Marc; Gey, Nathalie; Micha, Jean-Sebastien; Castelnau, Olivier; Guinebretiere, Rene Huge local elastic strains in bulk nanostructured pure zirconia materials Article de journal Materials Science and Engineering A-structural Materials Properties Microstructure and Processing, 806 , p. 140817, 2021. @article{Ors2021, title = {Huge local elastic strains in bulk nanostructured pure zirconia materials}, author = {Taylan Ors and Fanny Gouraud and Vincent Michel and Marc Huger and Nathalie Gey and Jean-Sebastien Micha and Olivier Castelnau and Rene Guinebretiere}, doi = {10.1016/j.msea.2021.140817}, year = {2021}, date = {2021-03-01}, journal = {Materials Science and Engineering A-structural Materials Properties Microstructure and Processing}, volume = {806}, pages = {140817}, abstract = {From the liquid state to room temperature, two successive solid-state phase transitions occur in pure zirconia. It is well-known that the last one (tetragonal to monoclinic) is martensitic and induces large volume variations and shear strains. Elastic and inelastic behaviors of zirconia-based materials are strongly influenced by this transition and the associated strain fields that it induces. Knowledge of strain and stress at the crystal scale is thus a crucial point. Using fully dense pure zirconia polycrystals obtained by a fuse casting process, we have determined at a sub-micrometric scale, by X-ray Laue microdiffraction, the strains map at room temperature in as-cast specimens and after a post elaboration high temperature thermal treatment. We observed that the fluctuation of deviatoric elastic strain is huge, the standard deviation of normal component being in the range of 1-2%. The heat treatment tends to even further increase this range of fluctuation, despite the development of a multiscale crack network formed during the cooling. Correspondingly, the associated stress level is also huge. It lies in the 5 GPa range with stress gradient amounting 1 GPa mu m(-1).}, keywords = {}, pubstate = {published}, tppubtype = {article} } From the liquid state to room temperature, two successive solid-state phase transitions occur in pure zirconia. It is well-known that the last one (tetragonal to monoclinic) is martensitic and induces large volume variations and shear strains. Elastic and inelastic behaviors of zirconia-based materials are strongly influenced by this transition and the associated strain fields that it induces. Knowledge of strain and stress at the crystal scale is thus a crucial point. Using fully dense pure zirconia polycrystals obtained by a fuse casting process, we have determined at a sub-micrometric scale, by X-ray Laue microdiffraction, the strains map at room temperature in as-cast specimens and after a post elaboration high temperature thermal treatment. We observed that the fluctuation of deviatoric elastic strain is huge, the standard deviation of normal component being in the range of 1-2%. The heat treatment tends to even further increase this range of fluctuation, despite the development of a multiscale crack network formed during the cooling. Correspondingly, the associated stress level is also huge. It lies in the 5 GPa range with stress gradient amounting 1 GPa mu m(-1). |
Subervie, Daniel; Quemener, Frederic Le; Canterel, Remi; Dugas, Pierre-Yves; Boyron, Olivier; Lalevee, Jacques; Bourgeat-Lami, Elodie; Lansalot, Muriel; Lacote, Emmanuel Visible-Light Emulsion Photopolymerization of Acrylates and Methacrylates: Mechanistic Insights and Introduction of a Simplified Sulfur-Based Photoinitiating System Article de journal Macromolecules, 54 (5), p. 2124–2133, 2021. @article{Subervie2021, title = {Visible-Light Emulsion Photopolymerization of Acrylates and Methacrylates: Mechanistic Insights and Introduction of a Simplified Sulfur-Based Photoinitiating System}, author = {Daniel Subervie and Frederic Le Quemener and Remi Canterel and Pierre-Yves Dugas and Olivier Boyron and Jacques Lalevee and Elodie Bourgeat-Lami and Muriel Lansalot and Emmanuel Lacote}, doi = {10.1021/acs.macromol.0c01692}, year = {2021}, date = {2021-03-01}, journal = {Macromolecules}, volume = {54}, number = {5}, pages = {2124--2133}, abstract = {The emulsion photopolymerization under visible light of acrylate and methacrylate monomers is reported. We previously introduced an NHC-borane-based system that was efficient for the emulsion photopolymerization of styrene [acridine orange (AO)/disulfide/NHC-borane]. This system relies on the disulfide photoreduction from the excited AO, followed by H-atom abstraction from the NHC-borane by the thiyl radical generated from the disulfide, eventually forming initiating NHC-boryl radicals. For the photopolymerization of (meth)acrylates, the boron-based photoinitiating system was simplified; as under LED illumination, the water-soluble disulfide alone is able to generate thiyl radicals that could initiate the polymerizations. With this disulfide/blue light system, MMA efficiently polymerized in emulsion, with solid contents up to 40%. The simplified system led to smaller particles than the full photoinitiating boron-based system, but the latter gave slightly better particle size distributions. Compared to styrene, the particle sizes attained for MMA were generally smaller. The disulfide photoinitiator gives access to a wide range of poly(meth)acrylic latexes, but it does not initiate the photopolymerization of styrene. We suggest that the propagation rate prevails on monomer solubility in the case of (meth)acrylates, which explains the efficiency of the photopolymerization with a much weaker initiating system. The method can also lead to the production of random copolymer latexes, such as P(MMA-co-St) and the film-forming P(MMA-co-BA). The fact that the disulfide is able to lead to the former further supports the predominant role of the propagation rate on the polymerization. Finally, the polymerization allows for temporal control. It proceeds under light and stops in the dark.}, keywords = {}, pubstate = {published}, tppubtype = {article} } The emulsion photopolymerization under visible light of acrylate and methacrylate monomers is reported. We previously introduced an NHC-borane-based system that was efficient for the emulsion photopolymerization of styrene [acridine orange (AO)/disulfide/NHC-borane]. This system relies on the disulfide photoreduction from the excited AO, followed by H-atom abstraction from the NHC-borane by the thiyl radical generated from the disulfide, eventually forming initiating NHC-boryl radicals. For the photopolymerization of (meth)acrylates, the boron-based photoinitiating system was simplified; as under LED illumination, the water-soluble disulfide alone is able to generate thiyl radicals that could initiate the polymerizations. With this disulfide/blue light system, MMA efficiently polymerized in emulsion, with solid contents up to 40%. The simplified system led to smaller particles than the full photoinitiating boron-based system, but the latter gave slightly better particle size distributions. Compared to styrene, the particle sizes attained for MMA were generally smaller. The disulfide photoinitiator gives access to a wide range of poly(meth)acrylic latexes, but it does not initiate the photopolymerization of styrene. We suggest that the propagation rate prevails on monomer solubility in the case of (meth)acrylates, which explains the efficiency of the photopolymerization with a much weaker initiating system. The method can also lead to the production of random copolymer latexes, such as P(MMA-co-St) and the film-forming P(MMA-co-BA). The fact that the disulfide is able to lead to the former further supports the predominant role of the propagation rate on the polymerization. Finally, the polymerization allows for temporal control. It proceeds under light and stops in the dark. |
Yatsui, Takashi; Brandenburg, Felix; Leuschel, Benjamin; Soppera, Olivier Synthesis of silver nanostructure on gold nanoparticle using near field assisted second harmonic generation. Article de journal Scientific reports, 11 (1), p. 5642–5642, 2021. @article{Yatsui2021, title = {Synthesis of silver nanostructure on gold nanoparticle using near field assisted second harmonic generation.}, author = {Takashi Yatsui and Felix Brandenburg and Benjamin Leuschel and Olivier Soppera}, doi = {10.1038/s41598-021-84944-w}, year = {2021}, date = {2021-03-01}, journal = {Scientific reports}, volume = {11}, number = {1}, pages = {5642--5642}, abstract = {By using gold (Au) nanoparticles (NPs) as an optical near-field source under far-field illumination in combination with a silver (Ag) ion solution containing a photoinitiator, we coated Ag on Au NPs using a near-field (NF)-assisted process. We evaluated the change in the size of the NPs using transmission electron microscopy. Evaluation of the synthesized Ag volume over illumination power confirmed the squared power dependence of the NP volume with illumination using 808nm light, i.e., a wavelength longer than the absorption edge wavelength of the photoinitiator molecules. The rate of volume increase was much lower than the plasmonic field enhancement effect. Therefore, the squared power dependency of the volume increase using a wavelength longer than the absorption edge wavelength originated from NF-assisted second-harmonic generation and the resulting excitation.}, keywords = {}, pubstate = {published}, tppubtype = {article} } By using gold (Au) nanoparticles (NPs) as an optical near-field source under far-field illumination in combination with a silver (Ag) ion solution containing a photoinitiator, we coated Ag on Au NPs using a near-field (NF)-assisted process. We evaluated the change in the size of the NPs using transmission electron microscopy. Evaluation of the synthesized Ag volume over illumination power confirmed the squared power dependence of the NP volume with illumination using 808nm light, i.e., a wavelength longer than the absorption edge wavelength of the photoinitiator molecules. The rate of volume increase was much lower than the plasmonic field enhancement effect. Therefore, the squared power dependency of the volume increase using a wavelength longer than the absorption edge wavelength originated from NF-assisted second-harmonic generation and the resulting excitation. |
Steciuk, Gwladys; Schaf, Oliver; Tortet, Laurence; Pizzala, Helene; Palatinus, Lukas; Hornfeck, Wolfgang; Paillaud, Jean-Louis A New Lithium-Rich Zeolitic 10-MR Zincolithosilicate MZS-1 Hydrothermally Synthesized under High Pressure and Characterized by 3D Electron Diffraction Article de journal European Journal of Inorganic Chemistry, 2021 (7), p. 628–638, 2021. @article{Steciuk2021, title = {A New Lithium-Rich Zeolitic 10-MR Zincolithosilicate MZS-1 Hydrothermally Synthesized under High Pressure and Characterized by 3D Electron Diffraction}, author = {Gwladys Steciuk and Oliver Schaf and Laurence Tortet and Helene Pizzala and Lukas Palatinus and Wolfgang Hornfeck and Jean-Louis Paillaud}, doi = {10.1002/ejic.202000939}, year = {2021}, date = {2021-02-01}, journal = {European Journal of Inorganic Chemistry}, volume = {2021}, number = {7}, pages = {628--638}, abstract = {We report the structure of a new high lithium content zincolithosilicate (MZS-1) obtained after hydrothermal treatment under high pressure from a glass precursor. After synthesis microcrystalline mixture of phases was obtained among which the main phase was unknown. Due to the sub micrometric size of the crystallites its structure was determined from precession-assisted 3D electron diffraction measured at 100 K and refined using the dynamical theory of diffraction. More accurate lattice parameters are obtained from Rietveld refinement of synchrotron powder data collected at the ambient temperature. The characteristic framework is described at the ambient temperature using an average unit cell a(0)=8.57999(5) angstrom, b(0)=14.12332(8) angstrom, c(0)=4.96827(3) angstrom in the space group Ccc2. The structure of the new zeolitic 10-membered ring zincosilicate with chemical formula per unit cell (SiO2)(2)Zn0.408LiO(OH)(2)(Li,H)(2.184) (Z=4) is composed of undulated silicate layers made of fused 6-membered rings connected via vertices of (Zn,Li)O-4 tetrahedra. A weak superstructure doubling the a(0) parameter is observed and is explained by a Zn/Li ordering within the (Zn,Li)O-4 layers.}, keywords = {}, pubstate = {published}, tppubtype = {article} } We report the structure of a new high lithium content zincolithosilicate (MZS-1) obtained after hydrothermal treatment under high pressure from a glass precursor. After synthesis microcrystalline mixture of phases was obtained among which the main phase was unknown. Due to the sub micrometric size of the crystallites its structure was determined from precession-assisted 3D electron diffraction measured at 100 K and refined using the dynamical theory of diffraction. More accurate lattice parameters are obtained from Rietveld refinement of synchrotron powder data collected at the ambient temperature. The characteristic framework is described at the ambient temperature using an average unit cell a(0)=8.57999(5) angstrom, b(0)=14.12332(8) angstrom, c(0)=4.96827(3) angstrom in the space group Ccc2. The structure of the new zeolitic 10-membered ring zincosilicate with chemical formula per unit cell (SiO2)(2)Zn0.408LiO(OH)(2)(Li,H)(2.184) (Z=4) is composed of undulated silicate layers made of fused 6-membered rings connected via vertices of (Zn,Li)O-4 tetrahedra. A weak superstructure doubling the a(0) parameter is observed and is explained by a Zn/Li ordering within the (Zn,Li)O-4 layers. |
Mouafo, Louis Donald Notemgnou; Godel, Florian; Simon, Laurent; Dappe, Yannick J; Baaziz, Walid; Noumbe, Ulrich Nguetchuissi; Lorchat, Etienne; Martin, Marie-Blandine; Berciaud, Stephane; Doudin, Bernard; Ersen, Ovidiu; Dlubak, Bruno; Seneor, Pierre; Dayen, Jean-Francois 0D/2D Heterostructures Vertical Single Electron Transistor Article de journal Advanced Functional Materials, 31 (9), p. 2008255, 2021. @article{Mouafo2021, title = {0D/2D Heterostructures Vertical Single Electron Transistor}, author = {Louis Donald Notemgnou Mouafo and Florian Godel and Laurent Simon and Yannick J Dappe and Walid Baaziz and Ulrich Nguetchuissi Noumbe and Etienne Lorchat and Marie-Blandine Martin and Stephane Berciaud and Bernard Doudin and Ovidiu Ersen and Bruno Dlubak and Pierre Seneor and Jean-Francois Dayen}, doi = {10.1002/adfm.202008255}, year = {2021}, date = {2021-02-01}, journal = {Advanced Functional Materials}, volume = {31}, number = {9}, pages = {2008255}, abstract = {Mixed-dimensional heterostructures formed by the stacking of 2D materials with nanostructures of distinct dimensionality constitute a new class of nanomaterials that offers multifunctionality that goes beyond those of single dimensional systems. An unexplored architecture of single electron transistor (SET) is developed that employs heterostructures made of nanoclusters (0D) grown on a 2D molybdenum disulfide (MoS2) channel. Combining the large Coulomb energy of the nanoclusters with the electronic capabilities of the 2D layer, the concept of 0D-2D vertical SET is unveiled. The MoS2 underneath serves both as a charge tunable channel interconnecting the electrode, and as bottom electrode for each v-SET cell. In addition, its atomic thickness makes it thinner than the Debye screening length, providing electric field transparency functionality that allows for an efficient electric back gate control of the nanoclusters charge state. The Coulomb diamond pattern characteristics of SET are reported, with specific doping dependent nonlinear features arising from the 0D/2D geometry that are elucidated by theoretical modeling. These results hold promise for multifunctional single electron device taking advantage of the versatility of the 2D materials library, with as example envisioned spintronics applications while coupling quantum dots to magnetic 2D material, or to ferroelectric layers for neuromorphic devices.}, keywords = {}, pubstate = {published}, tppubtype = {article} } Mixed-dimensional heterostructures formed by the stacking of 2D materials with nanostructures of distinct dimensionality constitute a new class of nanomaterials that offers multifunctionality that goes beyond those of single dimensional systems. An unexplored architecture of single electron transistor (SET) is developed that employs heterostructures made of nanoclusters (0D) grown on a 2D molybdenum disulfide (MoS2) channel. Combining the large Coulomb energy of the nanoclusters with the electronic capabilities of the 2D layer, the concept of 0D-2D vertical SET is unveiled. The MoS2 underneath serves both as a charge tunable channel interconnecting the electrode, and as bottom electrode for each v-SET cell. In addition, its atomic thickness makes it thinner than the Debye screening length, providing electric field transparency functionality that allows for an efficient electric back gate control of the nanoclusters charge state. The Coulomb diamond pattern characteristics of SET are reported, with specific doping dependent nonlinear features arising from the 0D/2D geometry that are elucidated by theoretical modeling. These results hold promise for multifunctional single electron device taking advantage of the versatility of the 2D materials library, with as example envisioned spintronics applications while coupling quantum dots to magnetic 2D material, or to ferroelectric layers for neuromorphic devices. |
Jeguirim, Mejdi; Jellali, Salah Wastewater Treatment, Valorization, and Reuse Article de journal Water, 13 (4), p. 548, 2021. @article{Jeguirim2021, title = {Wastewater Treatment, Valorization, and Reuse}, author = {Mejdi Jeguirim and Salah Jellali}, doi = {10.3390/w13040548}, year = {2021}, date = {2021-02-01}, journal = {Water}, volume = {13}, number = {4}, pages = {548}, keywords = {}, pubstate = {published}, tppubtype = {article} } |
Rougerie, Pablo; dos Santos, Rafaela Silva; Farina, Marcos; Anselme, Karine Molecular Mechanisms of Topography Sensing by Osteoblasts: An Update Article de journal Applied Sciences-basel, 11 (4), p. 1791, 2021. @article{Rougerie2021, title = {Molecular Mechanisms of Topography Sensing by Osteoblasts: An Update}, author = {Pablo Rougerie and Rafaela Silva dos Santos and Marcos Farina and Karine Anselme}, doi = {10.3390/app11041791}, year = {2021}, date = {2021-02-01}, journal = {Applied Sciences-basel}, volume = {11}, number = {4}, pages = {1791}, abstract = {Featured Application The evaluation of the behavior of cultured cells on substrates with controlled topographies can contribute significantly to the optimization of biomaterials for bioengineering, due to the fact that cells are able to recognize topographies at different length scales and can be influenced by them. This review aims to bring together studies in the field that identify important molecular factors involved in this mechanism. In the case of osteoblasts, specific surface topographies of biomaterials used as bone grafts could lead to a fast recovery of bone defects associated with expected tissue homeostasis. In this review we have brought up the present knowledge on the interaction of osteoblasts with different substrates and we expect that its content can help in the future design of the next generation of materials for bone engineering. Bone is a specialized tissue formed by different cell types and a multiscale, complex mineralized matrix. The architecture and the surface chemistry of this microenvironment can be factors of considerable influence on cell biology, and can affect cell proliferation, commitment to differentiation, gene expression, matrix production and/or composition. It has been shown that osteoblasts encounter natural motifs in vivo, with various topographies (shapes, sizes, organization), and that cell cultures on flat surfaces do not reflect the total potential of the tissue. Therefore, studies investigating the role of topographies on cell behavior are important in order to better understand the interaction between cells and surfaces, to improve osseointegration processes in vivo between tissues and biomaterials, and to find a better topographic surface to enhance bone repair. In this review, we evaluate the main available data about surface topographies, techniques for topographies' production, mechanical signal transduction from surfaces to cells and the impact of cell-surface interactions on osteoblasts or preosteoblasts' behavior.}, keywords = {}, pubstate = {published}, tppubtype = {article} } Featured Application The evaluation of the behavior of cultured cells on substrates with controlled topographies can contribute significantly to the optimization of biomaterials for bioengineering, due to the fact that cells are able to recognize topographies at different length scales and can be influenced by them. This review aims to bring together studies in the field that identify important molecular factors involved in this mechanism. In the case of osteoblasts, specific surface topographies of biomaterials used as bone grafts could lead to a fast recovery of bone defects associated with expected tissue homeostasis. In this review we have brought up the present knowledge on the interaction of osteoblasts with different substrates and we expect that its content can help in the future design of the next generation of materials for bone engineering. Bone is a specialized tissue formed by different cell types and a multiscale, complex mineralized matrix. The architecture and the surface chemistry of this microenvironment can be factors of considerable influence on cell biology, and can affect cell proliferation, commitment to differentiation, gene expression, matrix production and/or composition. It has been shown that osteoblasts encounter natural motifs in vivo, with various topographies (shapes, sizes, organization), and that cell cultures on flat surfaces do not reflect the total potential of the tissue. Therefore, studies investigating the role of topographies on cell behavior are important in order to better understand the interaction between cells and surfaces, to improve osseointegration processes in vivo between tissues and biomaterials, and to find a better topographic surface to enhance bone repair. In this review, we evaluate the main available data about surface topographies, techniques for topographies' production, mechanical signal transduction from surfaces to cells and the impact of cell-surface interactions on osteoblasts or preosteoblasts' behavior. |
Anfar, Zakaria; Fakir, Abdellah Ait El; Zbair, Mohamed; Hafidi, Zakaria; Amedlous, Abdallah; Majdoub, Mohammed; Farsad, Salaheddine; Amjlef, Asma; Jada, Amane; Alem, Noureddine El Chemical Engineering Journal, 405 , p. 126660, 2021. @article{Anfar2021, title = {New functionalization approach synthesis of Sulfur doped, Nitrogen doped and Co-doped porous carbon: Superior metal-free Carbocatalyst for the catalytic oxidation of aqueous organics pollutants}, author = {Zakaria Anfar and Abdellah Ait El Fakir and Mohamed Zbair and Zakaria Hafidi and Abdallah Amedlous and Mohammed Majdoub and Salaheddine Farsad and Asma Amjlef and Amane Jada and Noureddine El Alem}, doi = {10.1016/j.cej.2020.126660}, year = {2021}, date = {2021-02-01}, journal = {Chemical Engineering Journal}, volume = {405}, pages = {126660}, abstract = {New green synthesis methods of novel commercially applicable carbocatalysts suitable for the catalytic oxidation of organic pollutants, remain a challenge. Herein, Nitrogen doped (N-PC), Sulfur doped (S-PC) and Co-doped (N, S-PC) porous carbon, were synthesized via a new facile environmentally functionalization approach followed by pyrolysis. Thus, Almond Shell (AS) as Bio-sourced material was used for porous carbon (PC) preparation as support. Thereafter, the introduction of Melamine, Diphenyl Disulfide and Thiourea on the PC matrix with high-COCl- and -CCl- groups facilitated the surface functionalization, and allowed us the introduction of high N and S heteroatoms contents in the PC networks surface. It was found that the optimized carbocatalysts could effectively activate PS, and exhibited excellent catalytic performances for the organic pollutants degradation, with an exceptionally low activation energy and fast kinetic reaction. Based on a systematic comparison, it was found that the N-PC exhibited the superior catalytic activity for activating the PS and degrading various organic pollutants. Such superior catalytic activity of the N-PC Carbocatalyst resulted from its high surface area, its low defect degree with the higher content of Graphitic-N. In addition, all experimental and theoretical investigations demonstrated the critical role of graphitic-N for the PS activation. It is expected that the doping process by N will significantly break the chemical inertness of the PC network and will make the N-PC surface more positively charged accelerating hence its interaction with the negatively charged S2O82-. Furthermore, the O-1(2) was found to be the predominant reactive oxygen species (ROS) as assessed by radical scavenging tests and EPR experi-ments. The carbocatalysts were not easily influenced by the water aqueous phase, which give us more obvious advantages over the PS activation.}, keywords = {}, pubstate = {published}, tppubtype = {article} } New green synthesis methods of novel commercially applicable carbocatalysts suitable for the catalytic oxidation of organic pollutants, remain a challenge. Herein, Nitrogen doped (N-PC), Sulfur doped (S-PC) and Co-doped (N, S-PC) porous carbon, were synthesized via a new facile environmentally functionalization approach followed by pyrolysis. Thus, Almond Shell (AS) as Bio-sourced material was used for porous carbon (PC) preparation as support. Thereafter, the introduction of Melamine, Diphenyl Disulfide and Thiourea on the PC matrix with high-COCl- and -CCl- groups facilitated the surface functionalization, and allowed us the introduction of high N and S heteroatoms contents in the PC networks surface. It was found that the optimized carbocatalysts could effectively activate PS, and exhibited excellent catalytic performances for the organic pollutants degradation, with an exceptionally low activation energy and fast kinetic reaction. Based on a systematic comparison, it was found that the N-PC exhibited the superior catalytic activity for activating the PS and degrading various organic pollutants. Such superior catalytic activity of the N-PC Carbocatalyst resulted from its high surface area, its low defect degree with the higher content of Graphitic-N. In addition, all experimental and theoretical investigations demonstrated the critical role of graphitic-N for the PS activation. It is expected that the doping process by N will significantly break the chemical inertness of the PC network and will make the N-PC surface more positively charged accelerating hence its interaction with the negatively charged S2O82-. Furthermore, the O-1(2) was found to be the predominant reactive oxygen species (ROS) as assessed by radical scavenging tests and EPR experi-ments. The carbocatalysts were not easily influenced by the water aqueous phase, which give us more obvious advantages over the PS activation. |
Liu, Shaohui; Brunel, Damien; Noirbent, Guillaume; Mau, Alexandre; Chen, Hong; Morlet-Savary, Fabrice; Graff, Bernadette; Gigmes, Didier; Xiao, Pu; Dumur, Frederic; Lalevee, Jacques New multifunctional benzophenone-based photoinitiators with high migration stability and their applications in 3D printing Article de journal Materials Chemistry Frontiers, 5 (4), p. 1982–1994, 2021. @article{Liu2021, title = {New multifunctional benzophenone-based photoinitiators with high migration stability and their applications in 3D printing}, author = {Shaohui Liu and Damien Brunel and Guillaume Noirbent and Alexandre Mau and Hong Chen and Fabrice Morlet-Savary and Bernadette Graff and Didier Gigmes and Pu Xiao and Frederic Dumur and Jacques Lalevee}, doi = {10.1039/d0qm00885k}, year = {2021}, date = {2021-02-01}, journal = {Materials Chemistry Frontiers}, volume = {5}, number = {4}, pages = {1982--1994}, abstract = {In this paper, seven new photoinitiators based on the benzophenone scaffold are specifically designed for photopolymerization under mild conditions upon light-emitting diode (LED) irradiation, i.e. four benzophenone-triphenylamine photoinitiators (denoted as BT1-BT4) and three benzophenone-carbazole photoinitiators (denoted as BC1-BC3). Noticeably, these structures have never been reported in the literature except for BT4, so these molecules have been specifically designed for photopolymerization applications. Remarkably, various combinations of chemical groups were investigated in this work to determine the effects of the substitution patterns on their photoinitiation abilities. The formation of benzophenone-triphenylamine and benzophenone-carbazole hybrid structures not only contributes to red-shift of the absorption maxima but also strongly enhances their molar extinction coefficients. The different compounds showed high photoinitiation abilities upon irradiation with an LED@405 nm, and the free radical photopolymerization of acrylates and the cationic polymerization of epoxides could be promoted with high final function conversions (e.g. 77% for the BT3/iodonium salt/amine system in free radical photopolymerization). Remarkably, these new PIs are also able to sensitize sulfonium salts upon irradiation @405 nm. Markedly, because of the benzophenone moiety, a monocomponent Type II PI behavior could be observed, e.g. these compounds could initiate the polymerization alone. Remarkably, benzophenone-triphenylamine compounds BT2, BT3 and BT4 exhibited better hydrogen abstraction abilities as Type II photoinitiators than the benchmark and commercial photoinitiator 2-isopropylthioxanthone in the absence of amines as well as in the presence of amines. Furthermore, the interaction between the photoinitiators and the different additives was investigated by steady state photolysis and fluorescence quenching experiments. The free radical generation in the BT3/amine system was confirmed by the electron spin resonance-spin trapping technique, and the chemical mechanisms related to the polymerization efficiency are discussed. In addition, the migration stability of BT3 was investigated, which was excellent due to its high molecular weight and its trifunctional character. Finally, the three-component photoinitiating system based on BT3 was successfully applied in 3D printing and the 3D patterns showed a good spatial resolution.}, keywords = {}, pubstate = {published}, tppubtype = {article} } In this paper, seven new photoinitiators based on the benzophenone scaffold are specifically designed for photopolymerization under mild conditions upon light-emitting diode (LED) irradiation, i.e. four benzophenone-triphenylamine photoinitiators (denoted as BT1-BT4) and three benzophenone-carbazole photoinitiators (denoted as BC1-BC3). Noticeably, these structures have never been reported in the literature except for BT4, so these molecules have been specifically designed for photopolymerization applications. Remarkably, various combinations of chemical groups were investigated in this work to determine the effects of the substitution patterns on their photoinitiation abilities. The formation of benzophenone-triphenylamine and benzophenone-carbazole hybrid structures not only contributes to red-shift of the absorption maxima but also strongly enhances their molar extinction coefficients. The different compounds showed high photoinitiation abilities upon irradiation with an LED@405 nm, and the free radical photopolymerization of acrylates and the cationic polymerization of epoxides could be promoted with high final function conversions (e.g. 77% for the BT3/iodonium salt/amine system in free radical photopolymerization). Remarkably, these new PIs are also able to sensitize sulfonium salts upon irradiation @405 nm. Markedly, because of the benzophenone moiety, a monocomponent Type II PI behavior could be observed, e.g. these compounds could initiate the polymerization alone. Remarkably, benzophenone-triphenylamine compounds BT2, BT3 and BT4 exhibited better hydrogen abstraction abilities as Type II photoinitiators than the benchmark and commercial photoinitiator 2-isopropylthioxanthone in the absence of amines as well as in the presence of amines. Furthermore, the interaction between the photoinitiators and the different additives was investigated by steady state photolysis and fluorescence quenching experiments. The free radical generation in the BT3/amine system was confirmed by the electron spin resonance-spin trapping technique, and the chemical mechanisms related to the polymerization efficiency are discussed. In addition, the migration stability of BT3 was investigated, which was excellent due to its high molecular weight and its trifunctional character. Finally, the three-component photoinitiating system based on BT3 was successfully applied in 3D printing and the 3D patterns showed a good spatial resolution. |
Rahal, Mahmoud; Mokbel, Haifaa; Graff, Bernadette; Pertici, Vincent; Gigmes, Didier; Toufaily, Joumana; Hamieh, Tayssir; Dumur, Frederic; Lalevee, Jacques Naphthalimide-Based Dyes as Photoinitiators under Visible Light Irradiation and their Applications: Photocomposite Synthesis, 3D printing and Polymerization in Water Article de journal Chemphotochem, 2021. @article{Rahal2021, title = {Naphthalimide-Based Dyes as Photoinitiators under Visible Light Irradiation and their Applications: Photocomposite Synthesis, 3D printing and Polymerization in Water}, author = {Mahmoud Rahal and Haifaa Mokbel and Bernadette Graff and Vincent Pertici and Didier Gigmes and Joumana Toufaily and Tayssir Hamieh and Frederic Dumur and Jacques Lalevee}, doi = {10.1002/cptc.202000306}, year = {2021}, date = {2021-02-01}, journal = {Chemphotochem}, publisher = {Wiley}, abstract = {In this work, six new fluorescent dyes derived from the naphthalimide scaffold (Napht1-Napht6) were synthesized and used as high-performance photoinitiating systems (PISs) in two and three-component systems (combined with iodonium salt (Iod) and/or an electron donor amine (such as N-phenylglycine[NPG])) for the radical photopolymerization of acrylate and methacrylate monomers under visible light using a light-emitting diode at 405 nm. Markedly, these dyes were never synthesized before. In fact, these PISs showed high initiation efficiency with both demonstrating high final reactive function conversions and high polymerization rates. A further interest of our study is to determine the effect of the different substituents (chromophoric group) on the naphthalimide function, concerning the efficiency of initiation of the free radical polymerization. In order to improve the mechanical properties of the obtained polymers, these derivatives were also tested for the photopolymerization of a blend of acrylate/epoxy monomers (TA/EPOX); these latter properties were characterized by traction tests. To demonstrate the initiation efficiency of these dyes, several methods and characterization techniques were used, including steady state photolysis, real-time Fourier transform infrared spectroscopy, emission spectroscopy as well as cyclic voltammetry. In our study, these naphthalimides were used for the synthesis of photocomposites (one and multiple layers of glass fibres) using a UV@395 nm (4 W/cm(2)) conveyor, as well as in the preparation of 3D printed polymers. Markedly, one of the naphthalimide derivatives (Napht-4) can be used as a new high-performance water soluble photoinitiator for photopolymerization in water and hydrogel synthesis.}, keywords = {}, pubstate = {published}, tppubtype = {article} } In this work, six new fluorescent dyes derived from the naphthalimide scaffold (Napht1-Napht6) were synthesized and used as high-performance photoinitiating systems (PISs) in two and three-component systems (combined with iodonium salt (Iod) and/or an electron donor amine (such as N-phenylglycine[NPG])) for the radical photopolymerization of acrylate and methacrylate monomers under visible light using a light-emitting diode at 405 nm. Markedly, these dyes were never synthesized before. In fact, these PISs showed high initiation efficiency with both demonstrating high final reactive function conversions and high polymerization rates. A further interest of our study is to determine the effect of the different substituents (chromophoric group) on the naphthalimide function, concerning the efficiency of initiation of the free radical polymerization. In order to improve the mechanical properties of the obtained polymers, these derivatives were also tested for the photopolymerization of a blend of acrylate/epoxy monomers (TA/EPOX); these latter properties were characterized by traction tests. To demonstrate the initiation efficiency of these dyes, several methods and characterization techniques were used, including steady state photolysis, real-time Fourier transform infrared spectroscopy, emission spectroscopy as well as cyclic voltammetry. In our study, these naphthalimides were used for the synthesis of photocomposites (one and multiple layers of glass fibres) using a UV@395 nm (4 W/cm(2)) conveyor, as well as in the preparation of 3D printed polymers. Markedly, one of the naphthalimide derivatives (Napht-4) can be used as a new high-performance water soluble photoinitiator for photopolymerization in water and hydrogel synthesis. |
Ma, Yik-Ken; Rigolet, Severinne; Michelin, Laure; Paillaud, Jean-Louis; Mintova, Svetlana; Khoerunnisa, Fitri; Daou, Jean T; Ng, Eng-Poh Facile and fast determination of Si/Al ratio of zeolites using FTIR spectroscopy technique Article de journal Microporous and Mesoporous Materials, 311 , p. 110683, 2021. @article{Ma2021, title = {Facile and fast determination of Si/Al ratio of zeolites using FTIR spectroscopy technique}, author = {Yik-Ken Ma and Severinne Rigolet and Laure Michelin and Jean-Louis Paillaud and Svetlana Mintova and Fitri Khoerunnisa and Jean T Daou and Eng-Poh Ng}, doi = {10.1016/j.micromeso.2020.110683}, year = {2021}, date = {2021-02-01}, journal = {Microporous and Mesoporous Materials}, volume = {311}, pages = {110683}, keywords = {}, pubstate = {published}, tppubtype = {article} } |
2021 |
Chen, Hong; Noirbent, Guillaume; Zhang, Yijun; Sun, Ke; Liu, Shaohui; Brunel, Damien; Gigmes, Didier; Graff, Bernadette; Morlet-Savary, Fabrice; Xiao, Pu; Dumur, Frederic; Lalevee, Jacques Photopolymerization and 3D/4D applications using newly developed dyes: Search around the natural chalcone scaffold in photoinitiating systems (Article de journal) Dyes and Pigments, 188 , p. 109213, 2021. @article{Chen2021c, title = {Photopolymerization and 3D/4D applications using newly developed dyes: Search around the natural chalcone scaffold in photoinitiating systems}, author = {Hong Chen and Guillaume Noirbent and Yijun Zhang and Ke Sun and Shaohui Liu and Damien Brunel and Didier Gigmes and Bernadette Graff and Fabrice Morlet-Savary and Pu Xiao and Frederic Dumur and Jacques Lalevee}, doi = {10.1016/j.dyepig.2021.109213}, year = {2021}, date = {2021-04-01}, journal = {Dyes and Pigments}, volume = {188}, pages = {109213}, abstract = {Chalcones are well-known natural dyes, 18 different derivatives selected from the rational molecular design (i.e. through molecular orbital calculations) were synthesized. If used in conjunction with an amine (i.e. ethyl 1, 4-(dimethylamino) benzoate, EDB) and an iodonium salt (bis(4-tert-butylphenyl) iodonium hexafluorophosphate, Iod) as photoinitiating systems (PISs), these dyes can initiate both the free radical polymerization of polyethylene glycol diacrylate (PEG-diacrylate) and the cationic polymerization of 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate (EPOX) via oxidation-reduction reaction mechanisms. Furthermore, among the 18 different suggested structures, except for dyes 9 and 10, which have been synthesized and used in other fields, the remaining 16 dyes have never been synthesized before. The photopolymerization efficiency of acrylates carried out under LED@405 nm are excellent both for thin films (the thickness is about 0.2 mm) and thick films (the thickness is about 2 mm). Furthermore, all of them can also boost the cationic polymerization of EPOX upon LED irradiation at 405 nm, in the presence of an iodonium salt and an amine. More interestingly, stereoscopic 3D patterns were successfully fabricated by the direct laser write (DLW) technique which demonstrated reversible swelling properties and reversible shape-memory effects induced via swelling and dehydration for the access to 4D printing.}, keywords = {}, pubstate = {published}, tppubtype = {article} } Chalcones are well-known natural dyes, 18 different derivatives selected from the rational molecular design (i.e. through molecular orbital calculations) were synthesized. If used in conjunction with an amine (i.e. ethyl 1, 4-(dimethylamino) benzoate, EDB) and an iodonium salt (bis(4-tert-butylphenyl) iodonium hexafluorophosphate, Iod) as photoinitiating systems (PISs), these dyes can initiate both the free radical polymerization of polyethylene glycol diacrylate (PEG-diacrylate) and the cationic polymerization of 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate (EPOX) via oxidation-reduction reaction mechanisms. Furthermore, among the 18 different suggested structures, except for dyes 9 and 10, which have been synthesized and used in other fields, the remaining 16 dyes have never been synthesized before. The photopolymerization efficiency of acrylates carried out under LED@405 nm are excellent both for thin films (the thickness is about 0.2 mm) and thick films (the thickness is about 2 mm). Furthermore, all of them can also boost the cationic polymerization of EPOX upon LED irradiation at 405 nm, in the presence of an iodonium salt and an amine. More interestingly, stereoscopic 3D patterns were successfully fabricated by the direct laser write (DLW) technique which demonstrated reversible swelling properties and reversible shape-memory effects induced via swelling and dehydration for the access to 4D printing. |
Jellali, Salah; Charabi, Yassine; Usman, Muhammad; Al-Badi, Abdullah; Jeguirim, Mejdi Investigations on Biogas Recovery from Anaerobic Digestion of Raw Sludge and Its Mixture with Agri-Food Wastes: Application to the Largest Industrial Estate in Oman (Article de journal) Sustainability, 13 (7), p. 3698, 2021. @article{Jellali2021a, title = {Investigations on Biogas Recovery from Anaerobic Digestion of Raw Sludge and Its Mixture with Agri-Food Wastes: Application to the Largest Industrial Estate in Oman}, author = {Salah Jellali and Yassine Charabi and Muhammad Usman and Abdullah Al-Badi and Mejdi Jeguirim}, doi = {10.3390/su13073698}, year = {2021}, date = {2021-04-01}, journal = {Sustainability}, volume = {13}, number = {7}, pages = {3698}, abstract = {This work is intended to evaluate the technical, environmental, and economic feasibility of converting the sludge produced at an industrial estate's wastewater treatment plant (WWTP) in Oman into energy through anaerobic digestion (AD). In this study, three different scenarios were analyzed. They concerned the digestion of the total amount of the produced sludge alone (240 m(3) day(-1)) (scenario 1), and its co-digestion with wet agri-food wastes (AFW) at rates of two tonnes day(-1) (scenario 2) and ten tonnes day(-1) (scenario 3). Based on the analyses of sludge samples, an intensive literature review regarding sludge and AFW Physico-chemical and energetic characteristics and the use of the cost-benefit analysis (CBA) approach, it was found that, for the overall duration of the project (20 years), the AD of the sludge alone (scenario 1) permitted the production of 43.9 GWh of electricity, the reduction of greenhouse gas (GHG) emissions (more than 37,000 tonnes equivalent CO2 (TCO2)) and exhibited positive net present value (NPV: $393,483) and an internal return rate (IRR) of 19.4%. Co-digesting sludge with AFW significantly increased all of these key performance indicators. For instance, scenario 3 results in the recovery of electrical energy of 82.2 GWh and avoids the emission of 70,602 tCO(2). Moreover, a higher NPV and IRR of $851,876 and 21.8%, respectively, and a payback period (PBP) of only seven years were calculated. The sensitivity analysis revealed that a decrease in total expenses by 15% results in a significant increase of the NPV and the IRR to $1,418,704 and 33.9%, respectively, for scenario 3. Considering a pessimistic assumption (an increase of the total expenses by 15%), all studied scenarios remain attractive. For instance, for scenario 3, the NPV, IRR, and PBP were evaluated to $285,047, 13.5%, and 9 years, respectively. Therefore, the co-digestion of sludge with agri-food wastes for energy recovery purposes could be considered a promising, eco-friendly, and economically viable approach in the Omani industrial estates.}, keywords = {}, pubstate = {published}, tppubtype = {article} } This work is intended to evaluate the technical, environmental, and economic feasibility of converting the sludge produced at an industrial estate's wastewater treatment plant (WWTP) in Oman into energy through anaerobic digestion (AD). In this study, three different scenarios were analyzed. They concerned the digestion of the total amount of the produced sludge alone (240 m(3) day(-1)) (scenario 1), and its co-digestion with wet agri-food wastes (AFW) at rates of two tonnes day(-1) (scenario 2) and ten tonnes day(-1) (scenario 3). Based on the analyses of sludge samples, an intensive literature review regarding sludge and AFW Physico-chemical and energetic characteristics and the use of the cost-benefit analysis (CBA) approach, it was found that, for the overall duration of the project (20 years), the AD of the sludge alone (scenario 1) permitted the production of 43.9 GWh of electricity, the reduction of greenhouse gas (GHG) emissions (more than 37,000 tonnes equivalent CO2 (TCO2)) and exhibited positive net present value (NPV: $393,483) and an internal return rate (IRR) of 19.4%. Co-digesting sludge with AFW significantly increased all of these key performance indicators. For instance, scenario 3 results in the recovery of electrical energy of 82.2 GWh and avoids the emission of 70,602 tCO(2). Moreover, a higher NPV and IRR of $851,876 and 21.8%, respectively, and a payback period (PBP) of only seven years were calculated. The sensitivity analysis revealed that a decrease in total expenses by 15% results in a significant increase of the NPV and the IRR to $1,418,704 and 33.9%, respectively, for scenario 3. Considering a pessimistic assumption (an increase of the total expenses by 15%), all studied scenarios remain attractive. For instance, for scenario 3, the NPV, IRR, and PBP were evaluated to $285,047, 13.5%, and 9 years, respectively. Therefore, the co-digestion of sludge with agri-food wastes for energy recovery purposes could be considered a promising, eco-friendly, and economically viable approach in the Omani industrial estates. |
Ng, Eng-Poh; Ahmad, Nur Hidayahni; Khoerunnisa, Fitri; Mintova, Svetlana; Ling, Tau Chuan; Daou, Jean T Offretite Zeolite Single Crystals Synthesized by Amphiphile-Templating Approach (Article de journal) Molecules, 26 (8), p. 2238, 2021. @article{Ng2021h, title = {Offretite Zeolite Single Crystals Synthesized by Amphiphile-Templating Approach}, author = {Eng-Poh Ng and Nur Hidayahni Ahmad and Fitri Khoerunnisa and Svetlana Mintova and Tau Chuan Ling and Jean T Daou}, doi = {10.3390/molecules26082238}, year = {2021}, date = {2021-04-01}, journal = {Molecules}, volume = {26}, number = {8}, pages = {2238}, abstract = {Offretite zeolite synthesis in the presence of cetyltrimethylammonium bromide (CTABr) is reported. The offretite crystals were synthesized with a high crystallinity and hexagonal prismatic shape after only 72 h of hydrothermal treatment at 180 degrees C. The CTABr has dual-functions during the crystallization of offretite, viz. as structure-directing agent and as mesoporogen. The resulting offretite crystals, with a Si/Al ratio of 4.1, possess more acid sites than the conventional offretite due to their high crystallinity and hierarchical structure. The synthesized offretite is also more reactive than its conventional counterpart in the acylation of 2-methylfuran for biofuel production under non-microwave instant heating condition, giving 83.5% conversion with 100% selectivity to the desired product 2-acetyl-5-methylfuran. Hence, this amphiphile synthesis approach offers another cost-effective and alternative route for crystallizing zeolite materials that require expensive organic templates.}, keywords = {}, pubstate = {published}, tppubtype = {article} } Offretite zeolite synthesis in the presence of cetyltrimethylammonium bromide (CTABr) is reported. The offretite crystals were synthesized with a high crystallinity and hexagonal prismatic shape after only 72 h of hydrothermal treatment at 180 degrees C. The CTABr has dual-functions during the crystallization of offretite, viz. as structure-directing agent and as mesoporogen. The resulting offretite crystals, with a Si/Al ratio of 4.1, possess more acid sites than the conventional offretite due to their high crystallinity and hierarchical structure. The synthesized offretite is also more reactive than its conventional counterpart in the acylation of 2-methylfuran for biofuel production under non-microwave instant heating condition, giving 83.5% conversion with 100% selectivity to the desired product 2-acetyl-5-methylfuran. Hence, this amphiphile synthesis approach offers another cost-effective and alternative route for crystallizing zeolite materials that require expensive organic templates. |
Lai, H; Zhu, D; Peng, X; Zhang, J; Lalevee, J; Xiao, P N-Aryl glycines as versatile initiators for various polymerizations (Article de journal) Polymer Chemistry, 12 (13), p. 1991–2000, 2021. @article{Lai2021, title = {N-Aryl glycines as versatile initiators for various polymerizations}, author = {H Lai and D Zhu and X Peng and J Zhang and J Lalevee and P Xiao}, doi = {10.1039/d1py00030f}, year = {2021}, date = {2021-04-01}, journal = {Polymer Chemistry}, volume = {12}, number = {13}, pages = {1991--2000}, abstract = {The design and development of versatile initiators for various types of polymerization reactions, i.e. thermal-/photo-crosslinked/controlled polymerizations, is highly interesting to fabricate high-performance polymer materials. Herein, we synthesized two N-aryl glycine-based initiators, N-(1-naphthyl)glycine (NNG) and N-(1-pyrenyl)glycine (NPYG), and investigated their ability to trigger thermal- or light-induced polymerizations. Relevant photochemical mechanisms to generate reactive species were studied by steady state photolysis, fluorescence, and electron paramagnetic resonance spin-trapping techniques. The synthesized N-aryl glycine-based initiators can act as monocomponent photoinitiators or be incorporated into multicomponent photoinitiating systems for free radical or cationic crosslinked photopolymerization under diverse blue LEDs. Moreover, NPYG was also capable of initiating reversible addition-fragmentation chain transfer polymerization under either thermal- or light-induced reaction.}, keywords = {}, pubstate = {published}, tppubtype = {article} } The design and development of versatile initiators for various types of polymerization reactions, i.e. thermal-/photo-crosslinked/controlled polymerizations, is highly interesting to fabricate high-performance polymer materials. Herein, we synthesized two N-aryl glycine-based initiators, N-(1-naphthyl)glycine (NNG) and N-(1-pyrenyl)glycine (NPYG), and investigated their ability to trigger thermal- or light-induced polymerizations. Relevant photochemical mechanisms to generate reactive species were studied by steady state photolysis, fluorescence, and electron paramagnetic resonance spin-trapping techniques. The synthesized N-aryl glycine-based initiators can act as monocomponent photoinitiators or be incorporated into multicomponent photoinitiating systems for free radical or cationic crosslinked photopolymerization under diverse blue LEDs. Moreover, NPYG was also capable of initiating reversible addition-fragmentation chain transfer polymerization under either thermal- or light-induced reaction. |
Bouzidi, Imen; Fkiri, Anis; Sellami, Badreddine; Harrath, Abdel Halim; Boufahja, Fehmi; Mezni, Amine; Vidal, Loic; Vaulot, Cyril; Josien, Ludovic; Beyrem, Hamouda; Mougin, Karine Does the photocatalytic activity of nanoparticles protect the marine mussel Mytilus galloprovincialis from polycyclic aromatic hydrocarbon toxicity? (Article de journal) Environmental science and pollution research international, 2021. @article{Bouzidi2021, title = {Does the photocatalytic activity of nanoparticles protect the marine mussel Mytilus galloprovincialis from polycyclic aromatic hydrocarbon toxicity?}, author = {Imen Bouzidi and Anis Fkiri and Badreddine Sellami and Abdel Halim Harrath and Fehmi Boufahja and Amine Mezni and Loic Vidal and Cyril Vaulot and Ludovic Josien and Hamouda Beyrem and Karine Mougin}, doi = {10.1007/s11356-021-13908-4}, year = {2021}, date = {2021-04-01}, journal = {Environmental science and pollution research international}, abstract = {In the present study, five NPs (containing ZnO, Au-ZnO, Cu-ZnO, TiO2, and Au-TiO2) were characterized using dynamic light scattering and transmission electron microscopy, in order to observe their behavior under environmental change. The applicability of NPs for degradation of three polycyclic aromatic hydrocarbons (PAHs), including benzo(a)pyrene, fluoranthene, and benzanthracene, using UV irradiation showed the high photocatalytic efficiency of doped NPs for the removal of the study pollutants. To predict the environmental impact and interaction between NPs and PAHs on marine organisms, Mytilus galloprovincialis mussels were exposed to concentrations of each chemical (50 and 100 mug/L) for 14 days. The mussel's response was determined using the oxidative stress biomarker approach. Measured biomarkers in the mussel's digestive gland showed possible oxidative mechanisms in a concentration-dependent manner occurring after exposure to PAHs and NPs separately. Overall, this finding provides an interesting combination to remove PAHs in water, and the incorporation of chemical element into the crystallographic structure of NPs and the combination of two different NPs to form a binary hybrid NPs are promising materials.}, keywords = {}, pubstate = {published}, tppubtype = {article} } In the present study, five NPs (containing ZnO, Au-ZnO, Cu-ZnO, TiO2, and Au-TiO2) were characterized using dynamic light scattering and transmission electron microscopy, in order to observe their behavior under environmental change. The applicability of NPs for degradation of three polycyclic aromatic hydrocarbons (PAHs), including benzo(a)pyrene, fluoranthene, and benzanthracene, using UV irradiation showed the high photocatalytic efficiency of doped NPs for the removal of the study pollutants. To predict the environmental impact and interaction between NPs and PAHs on marine organisms, Mytilus galloprovincialis mussels were exposed to concentrations of each chemical (50 and 100 mug/L) for 14 days. The mussel's response was determined using the oxidative stress biomarker approach. Measured biomarkers in the mussel's digestive gland showed possible oxidative mechanisms in a concentration-dependent manner occurring after exposure to PAHs and NPs separately. Overall, this finding provides an interesting combination to remove PAHs in water, and the incorporation of chemical element into the crystallographic structure of NPs and the combination of two different NPs to form a binary hybrid NPs are promising materials. |
Le, Cuong Minh Quoc; Vidal, Loic; Schmutz, Marc; Chemtob, Abraham Droplet nucleation in miniemulsion thiol-ene step photopolymerization (Article de journal) Polymer Chemistry, 12 (14), p. 2084–2094, 2021. @article{Le2021, title = {Droplet nucleation in miniemulsion thiol-ene step photopolymerization}, author = {Cuong Minh Quoc Le and Loic Vidal and Marc Schmutz and Abraham Chemtob}, doi = {10.1039/d1py00139f}, year = {2021}, date = {2021-04-01}, journal = {Polymer Chemistry}, volume = {12}, number = {14}, pages = {2084--2094}, abstract = {Complex and unique polymer colloids have been prepared by miniemulsion polymerization through particle nucleation confined to monomer droplets. Unlike radical chain polymerization, the reaction conditions for a predominant droplet nucleation have not been investigated in step polymerizations such as thiol-ene polymerization. To clarify this issue, an aqueous thiol-ene miniemulsion based on diallyl adipate and 2,2-(ethylenedioxy)diethanedithiol is prepared. Droplet stability is affected by Ostwald ripening due to the limited solubility of hexadecane (costabilizer) in the monomer phase. The control of chemical stability is also difficult, since a self-initiated polymerization is caused by adventitious radicals generated in the emulsification stage (ultrasonication). However, the addition of an appropriate concentration of a radical scavenger (quinone) can halt polymerization for several hours. Under these conditions, batch photopolymerization kinetics, molecular weight progress and particle size distribution have been determined with reproducible results. Emphasis is placed on understanding how initiator solubility, droplet size and monomer solubility affect droplet nucleation. For this purpose, a reliable measurement of droplet (particle) size distributions is achieved by combining size data from dynamic light scattering and transmission electron microscopy. When using a water-soluble photoinitiator, a substantial homogeneous nucleation is reported even for highly water-insoluble monomers. Only when the droplet diameter is low enough (about 100 nm), then droplet nucleation prevails. Conversely, a water-insoluble initiator drives a robust and complete droplet nucleation irrespective of the reaction conditions.}, keywords = {}, pubstate = {published}, tppubtype = {article} } Complex and unique polymer colloids have been prepared by miniemulsion polymerization through particle nucleation confined to monomer droplets. Unlike radical chain polymerization, the reaction conditions for a predominant droplet nucleation have not been investigated in step polymerizations such as thiol-ene polymerization. To clarify this issue, an aqueous thiol-ene miniemulsion based on diallyl adipate and 2,2-(ethylenedioxy)diethanedithiol is prepared. Droplet stability is affected by Ostwald ripening due to the limited solubility of hexadecane (costabilizer) in the monomer phase. The control of chemical stability is also difficult, since a self-initiated polymerization is caused by adventitious radicals generated in the emulsification stage (ultrasonication). However, the addition of an appropriate concentration of a radical scavenger (quinone) can halt polymerization for several hours. Under these conditions, batch photopolymerization kinetics, molecular weight progress and particle size distribution have been determined with reproducible results. Emphasis is placed on understanding how initiator solubility, droplet size and monomer solubility affect droplet nucleation. For this purpose, a reliable measurement of droplet (particle) size distributions is achieved by combining size data from dynamic light scattering and transmission electron microscopy. When using a water-soluble photoinitiator, a substantial homogeneous nucleation is reported even for highly water-insoluble monomers. Only when the droplet diameter is low enough (about 100 nm), then droplet nucleation prevails. Conversely, a water-insoluble initiator drives a robust and complete droplet nucleation irrespective of the reaction conditions. |
Lee, Zhong-Han; Hammoud, Fatima; Hijazi, Akram; Graff, Bernadette; Lalevee, Jacques; Chen, Yung-Chung Synthesis and free radical photopolymerization of triphenylamine-based oxime ester photoinitiators (Article de journal) Polymer Chemistry, 12 (9), p. 1286–1297, 2021. @article{Lee2021, title = {Synthesis and free radical photopolymerization of triphenylamine-based oxime ester photoinitiators}, author = {Zhong-Han Lee and Fatima Hammoud and Akram Hijazi and Bernadette Graff and Jacques Lalevee and Yung-Chung Chen}, doi = {10.1039/d0py01768j}, year = {2021}, date = {2021-03-01}, journal = {Polymer Chemistry}, volume = {12}, number = {9}, pages = {1286--1297}, abstract = {Four visible light triphenylamine-based oxime ester photoinitiators (TP-1-4) were synthesized and confirmed successfully through H-1 NMR, C-13 NMR, and electron impact mass spectrometry (EI-MS) measurements as well as elementary analyses (EA). The design strategy for triphenylamine substituted photoinitiators involved the use of hydrogen atoms only for TP-1, one methoxy group for TP-2, two methoxy groups for TP-3 and two methyl groups for TP-4. The incorporation of triphenylamine derivatives in oxime esters gives near UV and visible light absorption characters with maximum absorption peaks at around 360 nm. Upon using a UV lamp as an irradiation source, all the oxime esters showed good double bond conversion efficiency in a range of 72-92% in the free radical polymerization of trimethylolpropane triacrylate (TMPTA) through photo-DSC experiments. Among all, TP-1 displayed the highest final conversion efficiency. Accordingly, the photochemical reaction behavior was studied using photolysis, cyclic voltammograms (CV), electron spin resonance (ESR) and theoretical calculations. Additionally, selected photoinitiating systems exhibited outstanding 3D patterns with high resolution and good edge definition through direct laser write (DLW) experiments @405 nm. This work thus demonstrates a judicious chemical design to fine-tune the photopolymerization character in triphenylamine oxime ester analogues.}, keywords = {}, pubstate = {published}, tppubtype = {article} } Four visible light triphenylamine-based oxime ester photoinitiators (TP-1-4) were synthesized and confirmed successfully through H-1 NMR, C-13 NMR, and electron impact mass spectrometry (EI-MS) measurements as well as elementary analyses (EA). The design strategy for triphenylamine substituted photoinitiators involved the use of hydrogen atoms only for TP-1, one methoxy group for TP-2, two methoxy groups for TP-3 and two methyl groups for TP-4. The incorporation of triphenylamine derivatives in oxime esters gives near UV and visible light absorption characters with maximum absorption peaks at around 360 nm. Upon using a UV lamp as an irradiation source, all the oxime esters showed good double bond conversion efficiency in a range of 72-92% in the free radical polymerization of trimethylolpropane triacrylate (TMPTA) through photo-DSC experiments. Among all, TP-1 displayed the highest final conversion efficiency. Accordingly, the photochemical reaction behavior was studied using photolysis, cyclic voltammograms (CV), electron spin resonance (ESR) and theoretical calculations. Additionally, selected photoinitiating systems exhibited outstanding 3D patterns with high resolution and good edge definition through direct laser write (DLW) experiments @405 nm. This work thus demonstrates a judicious chemical design to fine-tune the photopolymerization character in triphenylamine oxime ester analogues. |
Liu, Shaohui; Zhang, Yijun; Sun, Ke; Graff, Bernadette; Xiao, Pu; Dumur, Frederic; Lalevee, Jacques Design of photoinitiating systems based on the chalcone-anthracene scaffold for LED cationic photopolymerization and application in 3D printing (Article de journal) European Polymer Journal, 147 , p. 110300, 2021. @article{Liu2021b, title = {Design of photoinitiating systems based on the chalcone-anthracene scaffold for LED cationic photopolymerization and application in 3D printing}, author = {Shaohui Liu and Yijun Zhang and Ke Sun and Bernadette Graff and Pu Xiao and Frederic Dumur and Jacques Lalevee}, doi = {10.1016/j.eurpolymj.2021.110300}, year = {2021}, date = {2021-03-01}, journal = {European Polymer Journal}, volume = {147}, pages = {110300}, abstract = {In this study, light-emitting diodes (LEDs) used as secure, low-cost and possessing long emission wavelengths irradiation sources were applied in photopolymerization. Seven novel anthracene derivatives (noted A1-A7) were proposed and evaluated in photosensitive systems. Three of them were never synthesized before (A1, A2 and A7) and the other derivatives were evaluated in other fields. Due to the in-silico design of molecular structure by molecular modeling, the proposed chalcone-anthracenes showed a broad absorption band in the visible region with favorable molar extinction coefficients. Photoinitiation abilities of the different photo-initiating systems were examined by the Real-Time Fourier Transformed Infrared Spectroscopy. The free radical polymerization of acrylates under LED@405 nm irradiation in laminate was evaluated and high final function conversions (FCs) were obtained in the presence of three-component photoinitiating systems based on chalcone-anthracenes/iodonium salt/amine. Meanwhile, the chalcone-anthracene derivatives exhibited high photoinitiation abilities in cationic photopolymerization of epoxides in combination with an iodonium salt under LED@405 nm irradiation. The final function conversions of epoxy using some anthracene/iodonium salt systems were even higher than the well-established dibutoxyanthracene (DBA)/iodonium salt benchmark system. In addition, due to the good light absorption properties, the cationic photopolymerization also was carried out in the presence of the chalcone-anthracene/iodonium salt systems under LED@470 nm or laser diode@447 nm irradiation (not possible to do with the reference DBA systems). Markedly, these derivatives were also able to sensitize sulfonium salts. The photochemical reactivity of anthracene derivatives was investigated through the steady state photolysis and fluorescence quenching experiments. Furthermore, the proposed interaction mechanisms of chalcone-anthracene derivatives and additives (iodonium salt and amine) were discussed using the free energy changes of electron transfer reactions. Interestingly, the cationic photopolymerization of A5/iodonium salt system was applied in 3D printing and the 3D patterns showed a good spatial resolution.}, keywords = {}, pubstate = {published}, tppubtype = {article} } In this study, light-emitting diodes (LEDs) used as secure, low-cost and possessing long emission wavelengths irradiation sources were applied in photopolymerization. Seven novel anthracene derivatives (noted A1-A7) were proposed and evaluated in photosensitive systems. Three of them were never synthesized before (A1, A2 and A7) and the other derivatives were evaluated in other fields. Due to the in-silico design of molecular structure by molecular modeling, the proposed chalcone-anthracenes showed a broad absorption band in the visible region with favorable molar extinction coefficients. Photoinitiation abilities of the different photo-initiating systems were examined by the Real-Time Fourier Transformed Infrared Spectroscopy. The free radical polymerization of acrylates under LED@405 nm irradiation in laminate was evaluated and high final function conversions (FCs) were obtained in the presence of three-component photoinitiating systems based on chalcone-anthracenes/iodonium salt/amine. Meanwhile, the chalcone-anthracene derivatives exhibited high photoinitiation abilities in cationic photopolymerization of epoxides in combination with an iodonium salt under LED@405 nm irradiation. The final function conversions of epoxy using some anthracene/iodonium salt systems were even higher than the well-established dibutoxyanthracene (DBA)/iodonium salt benchmark system. In addition, due to the good light absorption properties, the cationic photopolymerization also was carried out in the presence of the chalcone-anthracene/iodonium salt systems under LED@470 nm or laser diode@447 nm irradiation (not possible to do with the reference DBA systems). Markedly, these derivatives were also able to sensitize sulfonium salts. The photochemical reactivity of anthracene derivatives was investigated through the steady state photolysis and fluorescence quenching experiments. Furthermore, the proposed interaction mechanisms of chalcone-anthracene derivatives and additives (iodonium salt and amine) were discussed using the free energy changes of electron transfer reactions. Interestingly, the cationic photopolymerization of A5/iodonium salt system was applied in 3D printing and the 3D patterns showed a good spatial resolution. |
Blin, Jean-Luc; Michelin, Laure; Lebeau, Benedicte; Naydenov, Anton; Velinova, Ralitsa; Kolev, Hristo; Gaudin, Pierrick; Vidal, Loic; Dotzeva, Anna; Tenchev, Krasimir; Todorova, Silviya Co-Ce Oxides Supported on SBA-15 for VOCs Oxidation (Article de journal) Catalysts, 11 (3), p. 366, 2021. @article{Blin2021, title = {Co-Ce Oxides Supported on SBA-15 for VOCs Oxidation}, author = {Jean-Luc Blin and Laure Michelin and Benedicte Lebeau and Anton Naydenov and Ralitsa Velinova and Hristo Kolev and Pierrick Gaudin and Loic Vidal and Anna Dotzeva and Krasimir Tenchev and Silviya Todorova}, doi = {10.3390/catal11030366}, year = {2021}, date = {2021-03-01}, journal = {Catalysts}, volume = {11}, number = {3}, pages = {366}, abstract = {Reported here are new data on the structural and catalytic properties of a series of mono-component cobalt and bi-component Co-Ce catalysts supported on SBA-15 (Santa Barbara Amorphous-15)). The catalysts performance has been evaluated by tests on combustion of methane, propane, and n-hexane. It was established that the preparation of the Co-Ce catalysts by the 'two-solvent' technique does not significantly change the mesoporous structure, however, its pores are clogging with the Co and Ce guest species. Cobalt and cerium are uniformly distributed and preferentially fill up the channels of SBA-15, but oxide agglomerates located on the surface are observed as well. The highest activity of the mono-component cobalt sample is explained by its higher reducibility as a result of lower interaction of the cobalt oxide with the SBA-15. The fine dispersion of cobalt and cerium oxide and their strong interaction in the channels of the SBA-15 molecular sieve, leads to the formation of difficult-to-reduce oxide phases and, consequently, to lower catalytic activity compared to monocomponent cobalt oxide catalyst. The synthesised mesoporous structure can prevent the agglomeration of the oxide particles, thus leading to the successful development of a new and stable catalyst for decreasing greenhouse gas emissions.}, keywords = {}, pubstate = {published}, tppubtype = {article} } Reported here are new data on the structural and catalytic properties of a series of mono-component cobalt and bi-component Co-Ce catalysts supported on SBA-15 (Santa Barbara Amorphous-15)). The catalysts performance has been evaluated by tests on combustion of methane, propane, and n-hexane. It was established that the preparation of the Co-Ce catalysts by the 'two-solvent' technique does not significantly change the mesoporous structure, however, its pores are clogging with the Co and Ce guest species. Cobalt and cerium are uniformly distributed and preferentially fill up the channels of SBA-15, but oxide agglomerates located on the surface are observed as well. The highest activity of the mono-component cobalt sample is explained by its higher reducibility as a result of lower interaction of the cobalt oxide with the SBA-15. The fine dispersion of cobalt and cerium oxide and their strong interaction in the channels of the SBA-15 molecular sieve, leads to the formation of difficult-to-reduce oxide phases and, consequently, to lower catalytic activity compared to monocomponent cobalt oxide catalyst. The synthesised mesoporous structure can prevent the agglomeration of the oxide particles, thus leading to the successful development of a new and stable catalyst for decreasing greenhouse gas emissions. |
Ors, Taylan; Gouraud, Fanny; Michel, Vincent; Huger, Marc; Gey, Nathalie; Micha, Jean-Sebastien; Castelnau, Olivier; Guinebretiere, Rene Huge local elastic strains in bulk nanostructured pure zirconia materials (Article de journal) Materials Science and Engineering A-structural Materials Properties Microstructure and Processing, 806 , p. 140817, 2021. @article{Ors2021, title = {Huge local elastic strains in bulk nanostructured pure zirconia materials}, author = {Taylan Ors and Fanny Gouraud and Vincent Michel and Marc Huger and Nathalie Gey and Jean-Sebastien Micha and Olivier Castelnau and Rene Guinebretiere}, doi = {10.1016/j.msea.2021.140817}, year = {2021}, date = {2021-03-01}, journal = {Materials Science and Engineering A-structural Materials Properties Microstructure and Processing}, volume = {806}, pages = {140817}, abstract = {From the liquid state to room temperature, two successive solid-state phase transitions occur in pure zirconia. It is well-known that the last one (tetragonal to monoclinic) is martensitic and induces large volume variations and shear strains. Elastic and inelastic behaviors of zirconia-based materials are strongly influenced by this transition and the associated strain fields that it induces. Knowledge of strain and stress at the crystal scale is thus a crucial point. Using fully dense pure zirconia polycrystals obtained by a fuse casting process, we have determined at a sub-micrometric scale, by X-ray Laue microdiffraction, the strains map at room temperature in as-cast specimens and after a post elaboration high temperature thermal treatment. We observed that the fluctuation of deviatoric elastic strain is huge, the standard deviation of normal component being in the range of 1-2%. The heat treatment tends to even further increase this range of fluctuation, despite the development of a multiscale crack network formed during the cooling. Correspondingly, the associated stress level is also huge. It lies in the 5 GPa range with stress gradient amounting 1 GPa mu m(-1).}, keywords = {}, pubstate = {published}, tppubtype = {article} } From the liquid state to room temperature, two successive solid-state phase transitions occur in pure zirconia. It is well-known that the last one (tetragonal to monoclinic) is martensitic and induces large volume variations and shear strains. Elastic and inelastic behaviors of zirconia-based materials are strongly influenced by this transition and the associated strain fields that it induces. Knowledge of strain and stress at the crystal scale is thus a crucial point. Using fully dense pure zirconia polycrystals obtained by a fuse casting process, we have determined at a sub-micrometric scale, by X-ray Laue microdiffraction, the strains map at room temperature in as-cast specimens and after a post elaboration high temperature thermal treatment. We observed that the fluctuation of deviatoric elastic strain is huge, the standard deviation of normal component being in the range of 1-2%. The heat treatment tends to even further increase this range of fluctuation, despite the development of a multiscale crack network formed during the cooling. Correspondingly, the associated stress level is also huge. It lies in the 5 GPa range with stress gradient amounting 1 GPa mu m(-1). |
Subervie, Daniel; Quemener, Frederic Le; Canterel, Remi; Dugas, Pierre-Yves; Boyron, Olivier; Lalevee, Jacques; Bourgeat-Lami, Elodie; Lansalot, Muriel; Lacote, Emmanuel Visible-Light Emulsion Photopolymerization of Acrylates and Methacrylates: Mechanistic Insights and Introduction of a Simplified Sulfur-Based Photoinitiating System (Article de journal) Macromolecules, 54 (5), p. 2124–2133, 2021. @article{Subervie2021, title = {Visible-Light Emulsion Photopolymerization of Acrylates and Methacrylates: Mechanistic Insights and Introduction of a Simplified Sulfur-Based Photoinitiating System}, author = {Daniel Subervie and Frederic Le Quemener and Remi Canterel and Pierre-Yves Dugas and Olivier Boyron and Jacques Lalevee and Elodie Bourgeat-Lami and Muriel Lansalot and Emmanuel Lacote}, doi = {10.1021/acs.macromol.0c01692}, year = {2021}, date = {2021-03-01}, journal = {Macromolecules}, volume = {54}, number = {5}, pages = {2124--2133}, abstract = {The emulsion photopolymerization under visible light of acrylate and methacrylate monomers is reported. We previously introduced an NHC-borane-based system that was efficient for the emulsion photopolymerization of styrene [acridine orange (AO)/disulfide/NHC-borane]. This system relies on the disulfide photoreduction from the excited AO, followed by H-atom abstraction from the NHC-borane by the thiyl radical generated from the disulfide, eventually forming initiating NHC-boryl radicals. For the photopolymerization of (meth)acrylates, the boron-based photoinitiating system was simplified; as under LED illumination, the water-soluble disulfide alone is able to generate thiyl radicals that could initiate the polymerizations. With this disulfide/blue light system, MMA efficiently polymerized in emulsion, with solid contents up to 40%. The simplified system led to smaller particles than the full photoinitiating boron-based system, but the latter gave slightly better particle size distributions. Compared to styrene, the particle sizes attained for MMA were generally smaller. The disulfide photoinitiator gives access to a wide range of poly(meth)acrylic latexes, but it does not initiate the photopolymerization of styrene. We suggest that the propagation rate prevails on monomer solubility in the case of (meth)acrylates, which explains the efficiency of the photopolymerization with a much weaker initiating system. The method can also lead to the production of random copolymer latexes, such as P(MMA-co-St) and the film-forming P(MMA-co-BA). The fact that the disulfide is able to lead to the former further supports the predominant role of the propagation rate on the polymerization. Finally, the polymerization allows for temporal control. It proceeds under light and stops in the dark.}, keywords = {}, pubstate = {published}, tppubtype = {article} } The emulsion photopolymerization under visible light of acrylate and methacrylate monomers is reported. We previously introduced an NHC-borane-based system that was efficient for the emulsion photopolymerization of styrene [acridine orange (AO)/disulfide/NHC-borane]. This system relies on the disulfide photoreduction from the excited AO, followed by H-atom abstraction from the NHC-borane by the thiyl radical generated from the disulfide, eventually forming initiating NHC-boryl radicals. For the photopolymerization of (meth)acrylates, the boron-based photoinitiating system was simplified; as under LED illumination, the water-soluble disulfide alone is able to generate thiyl radicals that could initiate the polymerizations. With this disulfide/blue light system, MMA efficiently polymerized in emulsion, with solid contents up to 40%. The simplified system led to smaller particles than the full photoinitiating boron-based system, but the latter gave slightly better particle size distributions. Compared to styrene, the particle sizes attained for MMA were generally smaller. The disulfide photoinitiator gives access to a wide range of poly(meth)acrylic latexes, but it does not initiate the photopolymerization of styrene. We suggest that the propagation rate prevails on monomer solubility in the case of (meth)acrylates, which explains the efficiency of the photopolymerization with a much weaker initiating system. The method can also lead to the production of random copolymer latexes, such as P(MMA-co-St) and the film-forming P(MMA-co-BA). The fact that the disulfide is able to lead to the former further supports the predominant role of the propagation rate on the polymerization. Finally, the polymerization allows for temporal control. It proceeds under light and stops in the dark. |
Yatsui, Takashi; Brandenburg, Felix; Leuschel, Benjamin; Soppera, Olivier Synthesis of silver nanostructure on gold nanoparticle using near field assisted second harmonic generation. (Article de journal) Scientific reports, 11 (1), p. 5642–5642, 2021. @article{Yatsui2021, title = {Synthesis of silver nanostructure on gold nanoparticle using near field assisted second harmonic generation.}, author = {Takashi Yatsui and Felix Brandenburg and Benjamin Leuschel and Olivier Soppera}, doi = {10.1038/s41598-021-84944-w}, year = {2021}, date = {2021-03-01}, journal = {Scientific reports}, volume = {11}, number = {1}, pages = {5642--5642}, abstract = {By using gold (Au) nanoparticles (NPs) as an optical near-field source under far-field illumination in combination with a silver (Ag) ion solution containing a photoinitiator, we coated Ag on Au NPs using a near-field (NF)-assisted process. We evaluated the change in the size of the NPs using transmission electron microscopy. Evaluation of the synthesized Ag volume over illumination power confirmed the squared power dependence of the NP volume with illumination using 808nm light, i.e., a wavelength longer than the absorption edge wavelength of the photoinitiator molecules. The rate of volume increase was much lower than the plasmonic field enhancement effect. Therefore, the squared power dependency of the volume increase using a wavelength longer than the absorption edge wavelength originated from NF-assisted second-harmonic generation and the resulting excitation.}, keywords = {}, pubstate = {published}, tppubtype = {article} } By using gold (Au) nanoparticles (NPs) as an optical near-field source under far-field illumination in combination with a silver (Ag) ion solution containing a photoinitiator, we coated Ag on Au NPs using a near-field (NF)-assisted process. We evaluated the change in the size of the NPs using transmission electron microscopy. Evaluation of the synthesized Ag volume over illumination power confirmed the squared power dependence of the NP volume with illumination using 808nm light, i.e., a wavelength longer than the absorption edge wavelength of the photoinitiator molecules. The rate of volume increase was much lower than the plasmonic field enhancement effect. Therefore, the squared power dependency of the volume increase using a wavelength longer than the absorption edge wavelength originated from NF-assisted second-harmonic generation and the resulting excitation. |
Steciuk, Gwladys; Schaf, Oliver; Tortet, Laurence; Pizzala, Helene; Palatinus, Lukas; Hornfeck, Wolfgang; Paillaud, Jean-Louis A New Lithium-Rich Zeolitic 10-MR Zincolithosilicate MZS-1 Hydrothermally Synthesized under High Pressure and Characterized by 3D Electron Diffraction (Article de journal) European Journal of Inorganic Chemistry, 2021 (7), p. 628–638, 2021. @article{Steciuk2021, title = {A New Lithium-Rich Zeolitic 10-MR Zincolithosilicate MZS-1 Hydrothermally Synthesized under High Pressure and Characterized by 3D Electron Diffraction}, author = {Gwladys Steciuk and Oliver Schaf and Laurence Tortet and Helene Pizzala and Lukas Palatinus and Wolfgang Hornfeck and Jean-Louis Paillaud}, doi = {10.1002/ejic.202000939}, year = {2021}, date = {2021-02-01}, journal = {European Journal of Inorganic Chemistry}, volume = {2021}, number = {7}, pages = {628--638}, abstract = {We report the structure of a new high lithium content zincolithosilicate (MZS-1) obtained after hydrothermal treatment under high pressure from a glass precursor. After synthesis microcrystalline mixture of phases was obtained among which the main phase was unknown. Due to the sub micrometric size of the crystallites its structure was determined from precession-assisted 3D electron diffraction measured at 100 K and refined using the dynamical theory of diffraction. More accurate lattice parameters are obtained from Rietveld refinement of synchrotron powder data collected at the ambient temperature. The characteristic framework is described at the ambient temperature using an average unit cell a(0)=8.57999(5) angstrom, b(0)=14.12332(8) angstrom, c(0)=4.96827(3) angstrom in the space group Ccc2. The structure of the new zeolitic 10-membered ring zincosilicate with chemical formula per unit cell (SiO2)(2)Zn0.408LiO(OH)(2)(Li,H)(2.184) (Z=4) is composed of undulated silicate layers made of fused 6-membered rings connected via vertices of (Zn,Li)O-4 tetrahedra. A weak superstructure doubling the a(0) parameter is observed and is explained by a Zn/Li ordering within the (Zn,Li)O-4 layers.}, keywords = {}, pubstate = {published}, tppubtype = {article} } We report the structure of a new high lithium content zincolithosilicate (MZS-1) obtained after hydrothermal treatment under high pressure from a glass precursor. After synthesis microcrystalline mixture of phases was obtained among which the main phase was unknown. Due to the sub micrometric size of the crystallites its structure was determined from precession-assisted 3D electron diffraction measured at 100 K and refined using the dynamical theory of diffraction. More accurate lattice parameters are obtained from Rietveld refinement of synchrotron powder data collected at the ambient temperature. The characteristic framework is described at the ambient temperature using an average unit cell a(0)=8.57999(5) angstrom, b(0)=14.12332(8) angstrom, c(0)=4.96827(3) angstrom in the space group Ccc2. The structure of the new zeolitic 10-membered ring zincosilicate with chemical formula per unit cell (SiO2)(2)Zn0.408LiO(OH)(2)(Li,H)(2.184) (Z=4) is composed of undulated silicate layers made of fused 6-membered rings connected via vertices of (Zn,Li)O-4 tetrahedra. A weak superstructure doubling the a(0) parameter is observed and is explained by a Zn/Li ordering within the (Zn,Li)O-4 layers. |
Mouafo, Louis Donald Notemgnou; Godel, Florian; Simon, Laurent; Dappe, Yannick J; Baaziz, Walid; Noumbe, Ulrich Nguetchuissi; Lorchat, Etienne; Martin, Marie-Blandine; Berciaud, Stephane; Doudin, Bernard; Ersen, Ovidiu; Dlubak, Bruno; Seneor, Pierre; Dayen, Jean-Francois 0D/2D Heterostructures Vertical Single Electron Transistor (Article de journal) Advanced Functional Materials, 31 (9), p. 2008255, 2021. @article{Mouafo2021, title = {0D/2D Heterostructures Vertical Single Electron Transistor}, author = {Louis Donald Notemgnou Mouafo and Florian Godel and Laurent Simon and Yannick J Dappe and Walid Baaziz and Ulrich Nguetchuissi Noumbe and Etienne Lorchat and Marie-Blandine Martin and Stephane Berciaud and Bernard Doudin and Ovidiu Ersen and Bruno Dlubak and Pierre Seneor and Jean-Francois Dayen}, doi = {10.1002/adfm.202008255}, year = {2021}, date = {2021-02-01}, journal = {Advanced Functional Materials}, volume = {31}, number = {9}, pages = {2008255}, abstract = {Mixed-dimensional heterostructures formed by the stacking of 2D materials with nanostructures of distinct dimensionality constitute a new class of nanomaterials that offers multifunctionality that goes beyond those of single dimensional systems. An unexplored architecture of single electron transistor (SET) is developed that employs heterostructures made of nanoclusters (0D) grown on a 2D molybdenum disulfide (MoS2) channel. Combining the large Coulomb energy of the nanoclusters with the electronic capabilities of the 2D layer, the concept of 0D-2D vertical SET is unveiled. The MoS2 underneath serves both as a charge tunable channel interconnecting the electrode, and as bottom electrode for each v-SET cell. In addition, its atomic thickness makes it thinner than the Debye screening length, providing electric field transparency functionality that allows for an efficient electric back gate control of the nanoclusters charge state. The Coulomb diamond pattern characteristics of SET are reported, with specific doping dependent nonlinear features arising from the 0D/2D geometry that are elucidated by theoretical modeling. These results hold promise for multifunctional single electron device taking advantage of the versatility of the 2D materials library, with as example envisioned spintronics applications while coupling quantum dots to magnetic 2D material, or to ferroelectric layers for neuromorphic devices.}, keywords = {}, pubstate = {published}, tppubtype = {article} } Mixed-dimensional heterostructures formed by the stacking of 2D materials with nanostructures of distinct dimensionality constitute a new class of nanomaterials that offers multifunctionality that goes beyond those of single dimensional systems. An unexplored architecture of single electron transistor (SET) is developed that employs heterostructures made of nanoclusters (0D) grown on a 2D molybdenum disulfide (MoS2) channel. Combining the large Coulomb energy of the nanoclusters with the electronic capabilities of the 2D layer, the concept of 0D-2D vertical SET is unveiled. The MoS2 underneath serves both as a charge tunable channel interconnecting the electrode, and as bottom electrode for each v-SET cell. In addition, its atomic thickness makes it thinner than the Debye screening length, providing electric field transparency functionality that allows for an efficient electric back gate control of the nanoclusters charge state. The Coulomb diamond pattern characteristics of SET are reported, with specific doping dependent nonlinear features arising from the 0D/2D geometry that are elucidated by theoretical modeling. These results hold promise for multifunctional single electron device taking advantage of the versatility of the 2D materials library, with as example envisioned spintronics applications while coupling quantum dots to magnetic 2D material, or to ferroelectric layers for neuromorphic devices. |
Jeguirim, Mejdi; Jellali, Salah Wastewater Treatment, Valorization, and Reuse (Article de journal) Water, 13 (4), p. 548, 2021. @article{Jeguirim2021, title = {Wastewater Treatment, Valorization, and Reuse}, author = {Mejdi Jeguirim and Salah Jellali}, doi = {10.3390/w13040548}, year = {2021}, date = {2021-02-01}, journal = {Water}, volume = {13}, number = {4}, pages = {548}, keywords = {}, pubstate = {published}, tppubtype = {article} } |
Rougerie, Pablo; dos Santos, Rafaela Silva; Farina, Marcos; Anselme, Karine Molecular Mechanisms of Topography Sensing by Osteoblasts: An Update (Article de journal) Applied Sciences-basel, 11 (4), p. 1791, 2021. @article{Rougerie2021, title = {Molecular Mechanisms of Topography Sensing by Osteoblasts: An Update}, author = {Pablo Rougerie and Rafaela Silva dos Santos and Marcos Farina and Karine Anselme}, doi = {10.3390/app11041791}, year = {2021}, date = {2021-02-01}, journal = {Applied Sciences-basel}, volume = {11}, number = {4}, pages = {1791}, abstract = {Featured Application The evaluation of the behavior of cultured cells on substrates with controlled topographies can contribute significantly to the optimization of biomaterials for bioengineering, due to the fact that cells are able to recognize topographies at different length scales and can be influenced by them. This review aims to bring together studies in the field that identify important molecular factors involved in this mechanism. In the case of osteoblasts, specific surface topographies of biomaterials used as bone grafts could lead to a fast recovery of bone defects associated with expected tissue homeostasis. In this review we have brought up the present knowledge on the interaction of osteoblasts with different substrates and we expect that its content can help in the future design of the next generation of materials for bone engineering. Bone is a specialized tissue formed by different cell types and a multiscale, complex mineralized matrix. The architecture and the surface chemistry of this microenvironment can be factors of considerable influence on cell biology, and can affect cell proliferation, commitment to differentiation, gene expression, matrix production and/or composition. It has been shown that osteoblasts encounter natural motifs in vivo, with various topographies (shapes, sizes, organization), and that cell cultures on flat surfaces do not reflect the total potential of the tissue. Therefore, studies investigating the role of topographies on cell behavior are important in order to better understand the interaction between cells and surfaces, to improve osseointegration processes in vivo between tissues and biomaterials, and to find a better topographic surface to enhance bone repair. In this review, we evaluate the main available data about surface topographies, techniques for topographies' production, mechanical signal transduction from surfaces to cells and the impact of cell-surface interactions on osteoblasts or preosteoblasts' behavior.}, keywords = {}, pubstate = {published}, tppubtype = {article} } Featured Application The evaluation of the behavior of cultured cells on substrates with controlled topographies can contribute significantly to the optimization of biomaterials for bioengineering, due to the fact that cells are able to recognize topographies at different length scales and can be influenced by them. This review aims to bring together studies in the field that identify important molecular factors involved in this mechanism. In the case of osteoblasts, specific surface topographies of biomaterials used as bone grafts could lead to a fast recovery of bone defects associated with expected tissue homeostasis. In this review we have brought up the present knowledge on the interaction of osteoblasts with different substrates and we expect that its content can help in the future design of the next generation of materials for bone engineering. Bone is a specialized tissue formed by different cell types and a multiscale, complex mineralized matrix. The architecture and the surface chemistry of this microenvironment can be factors of considerable influence on cell biology, and can affect cell proliferation, commitment to differentiation, gene expression, matrix production and/or composition. It has been shown that osteoblasts encounter natural motifs in vivo, with various topographies (shapes, sizes, organization), and that cell cultures on flat surfaces do not reflect the total potential of the tissue. Therefore, studies investigating the role of topographies on cell behavior are important in order to better understand the interaction between cells and surfaces, to improve osseointegration processes in vivo between tissues and biomaterials, and to find a better topographic surface to enhance bone repair. In this review, we evaluate the main available data about surface topographies, techniques for topographies' production, mechanical signal transduction from surfaces to cells and the impact of cell-surface interactions on osteoblasts or preosteoblasts' behavior. |
Anfar, Zakaria; Fakir, Abdellah Ait El; Zbair, Mohamed; Hafidi, Zakaria; Amedlous, Abdallah; Majdoub, Mohammed; Farsad, Salaheddine; Amjlef, Asma; Jada, Amane; Alem, Noureddine El Chemical Engineering Journal, 405 , p. 126660, 2021. @article{Anfar2021, title = {New functionalization approach synthesis of Sulfur doped, Nitrogen doped and Co-doped porous carbon: Superior metal-free Carbocatalyst for the catalytic oxidation of aqueous organics pollutants}, author = {Zakaria Anfar and Abdellah Ait El Fakir and Mohamed Zbair and Zakaria Hafidi and Abdallah Amedlous and Mohammed Majdoub and Salaheddine Farsad and Asma Amjlef and Amane Jada and Noureddine El Alem}, doi = {10.1016/j.cej.2020.126660}, year = {2021}, date = {2021-02-01}, journal = {Chemical Engineering Journal}, volume = {405}, pages = {126660}, abstract = {New green synthesis methods of novel commercially applicable carbocatalysts suitable for the catalytic oxidation of organic pollutants, remain a challenge. Herein, Nitrogen doped (N-PC), Sulfur doped (S-PC) and Co-doped (N, S-PC) porous carbon, were synthesized via a new facile environmentally functionalization approach followed by pyrolysis. Thus, Almond Shell (AS) as Bio-sourced material was used for porous carbon (PC) preparation as support. Thereafter, the introduction of Melamine, Diphenyl Disulfide and Thiourea on the PC matrix with high-COCl- and -CCl- groups facilitated the surface functionalization, and allowed us the introduction of high N and S heteroatoms contents in the PC networks surface. It was found that the optimized carbocatalysts could effectively activate PS, and exhibited excellent catalytic performances for the organic pollutants degradation, with an exceptionally low activation energy and fast kinetic reaction. Based on a systematic comparison, it was found that the N-PC exhibited the superior catalytic activity for activating the PS and degrading various organic pollutants. Such superior catalytic activity of the N-PC Carbocatalyst resulted from its high surface area, its low defect degree with the higher content of Graphitic-N. In addition, all experimental and theoretical investigations demonstrated the critical role of graphitic-N for the PS activation. It is expected that the doping process by N will significantly break the chemical inertness of the PC network and will make the N-PC surface more positively charged accelerating hence its interaction with the negatively charged S2O82-. Furthermore, the O-1(2) was found to be the predominant reactive oxygen species (ROS) as assessed by radical scavenging tests and EPR experi-ments. The carbocatalysts were not easily influenced by the water aqueous phase, which give us more obvious advantages over the PS activation.}, keywords = {}, pubstate = {published}, tppubtype = {article} } New green synthesis methods of novel commercially applicable carbocatalysts suitable for the catalytic oxidation of organic pollutants, remain a challenge. Herein, Nitrogen doped (N-PC), Sulfur doped (S-PC) and Co-doped (N, S-PC) porous carbon, were synthesized via a new facile environmentally functionalization approach followed by pyrolysis. Thus, Almond Shell (AS) as Bio-sourced material was used for porous carbon (PC) preparation as support. Thereafter, the introduction of Melamine, Diphenyl Disulfide and Thiourea on the PC matrix with high-COCl- and -CCl- groups facilitated the surface functionalization, and allowed us the introduction of high N and S heteroatoms contents in the PC networks surface. It was found that the optimized carbocatalysts could effectively activate PS, and exhibited excellent catalytic performances for the organic pollutants degradation, with an exceptionally low activation energy and fast kinetic reaction. Based on a systematic comparison, it was found that the N-PC exhibited the superior catalytic activity for activating the PS and degrading various organic pollutants. Such superior catalytic activity of the N-PC Carbocatalyst resulted from its high surface area, its low defect degree with the higher content of Graphitic-N. In addition, all experimental and theoretical investigations demonstrated the critical role of graphitic-N for the PS activation. It is expected that the doping process by N will significantly break the chemical inertness of the PC network and will make the N-PC surface more positively charged accelerating hence its interaction with the negatively charged S2O82-. Furthermore, the O-1(2) was found to be the predominant reactive oxygen species (ROS) as assessed by radical scavenging tests and EPR experi-ments. The carbocatalysts were not easily influenced by the water aqueous phase, which give us more obvious advantages over the PS activation. |
Liu, Shaohui; Brunel, Damien; Noirbent, Guillaume; Mau, Alexandre; Chen, Hong; Morlet-Savary, Fabrice; Graff, Bernadette; Gigmes, Didier; Xiao, Pu; Dumur, Frederic; Lalevee, Jacques New multifunctional benzophenone-based photoinitiators with high migration stability and their applications in 3D printing (Article de journal) Materials Chemistry Frontiers, 5 (4), p. 1982–1994, 2021. @article{Liu2021, title = {New multifunctional benzophenone-based photoinitiators with high migration stability and their applications in 3D printing}, author = {Shaohui Liu and Damien Brunel and Guillaume Noirbent and Alexandre Mau and Hong Chen and Fabrice Morlet-Savary and Bernadette Graff and Didier Gigmes and Pu Xiao and Frederic Dumur and Jacques Lalevee}, doi = {10.1039/d0qm00885k}, year = {2021}, date = {2021-02-01}, journal = {Materials Chemistry Frontiers}, volume = {5}, number = {4}, pages = {1982--1994}, abstract = {In this paper, seven new photoinitiators based on the benzophenone scaffold are specifically designed for photopolymerization under mild conditions upon light-emitting diode (LED) irradiation, i.e. four benzophenone-triphenylamine photoinitiators (denoted as BT1-BT4) and three benzophenone-carbazole photoinitiators (denoted as BC1-BC3). Noticeably, these structures have never been reported in the literature except for BT4, so these molecules have been specifically designed for photopolymerization applications. Remarkably, various combinations of chemical groups were investigated in this work to determine the effects of the substitution patterns on their photoinitiation abilities. The formation of benzophenone-triphenylamine and benzophenone-carbazole hybrid structures not only contributes to red-shift of the absorption maxima but also strongly enhances their molar extinction coefficients. The different compounds showed high photoinitiation abilities upon irradiation with an LED@405 nm, and the free radical photopolymerization of acrylates and the cationic polymerization of epoxides could be promoted with high final function conversions (e.g. 77% for the BT3/iodonium salt/amine system in free radical photopolymerization). Remarkably, these new PIs are also able to sensitize sulfonium salts upon irradiation @405 nm. Markedly, because of the benzophenone moiety, a monocomponent Type II PI behavior could be observed, e.g. these compounds could initiate the polymerization alone. Remarkably, benzophenone-triphenylamine compounds BT2, BT3 and BT4 exhibited better hydrogen abstraction abilities as Type II photoinitiators than the benchmark and commercial photoinitiator 2-isopropylthioxanthone in the absence of amines as well as in the presence of amines. Furthermore, the interaction between the photoinitiators and the different additives was investigated by steady state photolysis and fluorescence quenching experiments. The free radical generation in the BT3/amine system was confirmed by the electron spin resonance-spin trapping technique, and the chemical mechanisms related to the polymerization efficiency are discussed. In addition, the migration stability of BT3 was investigated, which was excellent due to its high molecular weight and its trifunctional character. Finally, the three-component photoinitiating system based on BT3 was successfully applied in 3D printing and the 3D patterns showed a good spatial resolution.}, keywords = {}, pubstate = {published}, tppubtype = {article} } In this paper, seven new photoinitiators based on the benzophenone scaffold are specifically designed for photopolymerization under mild conditions upon light-emitting diode (LED) irradiation, i.e. four benzophenone-triphenylamine photoinitiators (denoted as BT1-BT4) and three benzophenone-carbazole photoinitiators (denoted as BC1-BC3). Noticeably, these structures have never been reported in the literature except for BT4, so these molecules have been specifically designed for photopolymerization applications. Remarkably, various combinations of chemical groups were investigated in this work to determine the effects of the substitution patterns on their photoinitiation abilities. The formation of benzophenone-triphenylamine and benzophenone-carbazole hybrid structures not only contributes to red-shift of the absorption maxima but also strongly enhances their molar extinction coefficients. The different compounds showed high photoinitiation abilities upon irradiation with an LED@405 nm, and the free radical photopolymerization of acrylates and the cationic polymerization of epoxides could be promoted with high final function conversions (e.g. 77% for the BT3/iodonium salt/amine system in free radical photopolymerization). Remarkably, these new PIs are also able to sensitize sulfonium salts upon irradiation @405 nm. Markedly, because of the benzophenone moiety, a monocomponent Type II PI behavior could be observed, e.g. these compounds could initiate the polymerization alone. Remarkably, benzophenone-triphenylamine compounds BT2, BT3 and BT4 exhibited better hydrogen abstraction abilities as Type II photoinitiators than the benchmark and commercial photoinitiator 2-isopropylthioxanthone in the absence of amines as well as in the presence of amines. Furthermore, the interaction between the photoinitiators and the different additives was investigated by steady state photolysis and fluorescence quenching experiments. The free radical generation in the BT3/amine system was confirmed by the electron spin resonance-spin trapping technique, and the chemical mechanisms related to the polymerization efficiency are discussed. In addition, the migration stability of BT3 was investigated, which was excellent due to its high molecular weight and its trifunctional character. Finally, the three-component photoinitiating system based on BT3 was successfully applied in 3D printing and the 3D patterns showed a good spatial resolution. |
Rahal, Mahmoud; Mokbel, Haifaa; Graff, Bernadette; Pertici, Vincent; Gigmes, Didier; Toufaily, Joumana; Hamieh, Tayssir; Dumur, Frederic; Lalevee, Jacques Naphthalimide-Based Dyes as Photoinitiators under Visible Light Irradiation and their Applications: Photocomposite Synthesis, 3D printing and Polymerization in Water (Article de journal) Chemphotochem, 2021. @article{Rahal2021, title = {Naphthalimide-Based Dyes as Photoinitiators under Visible Light Irradiation and their Applications: Photocomposite Synthesis, 3D printing and Polymerization in Water}, author = {Mahmoud Rahal and Haifaa Mokbel and Bernadette Graff and Vincent Pertici and Didier Gigmes and Joumana Toufaily and Tayssir Hamieh and Frederic Dumur and Jacques Lalevee}, doi = {10.1002/cptc.202000306}, year = {2021}, date = {2021-02-01}, journal = {Chemphotochem}, publisher = {Wiley}, abstract = {In this work, six new fluorescent dyes derived from the naphthalimide scaffold (Napht1-Napht6) were synthesized and used as high-performance photoinitiating systems (PISs) in two and three-component systems (combined with iodonium salt (Iod) and/or an electron donor amine (such as N-phenylglycine[NPG])) for the radical photopolymerization of acrylate and methacrylate monomers under visible light using a light-emitting diode at 405 nm. Markedly, these dyes were never synthesized before. In fact, these PISs showed high initiation efficiency with both demonstrating high final reactive function conversions and high polymerization rates. A further interest of our study is to determine the effect of the different substituents (chromophoric group) on the naphthalimide function, concerning the efficiency of initiation of the free radical polymerization. In order to improve the mechanical properties of the obtained polymers, these derivatives were also tested for the photopolymerization of a blend of acrylate/epoxy monomers (TA/EPOX); these latter properties were characterized by traction tests. To demonstrate the initiation efficiency of these dyes, several methods and characterization techniques were used, including steady state photolysis, real-time Fourier transform infrared spectroscopy, emission spectroscopy as well as cyclic voltammetry. In our study, these naphthalimides were used for the synthesis of photocomposites (one and multiple layers of glass fibres) using a UV@395 nm (4 W/cm(2)) conveyor, as well as in the preparation of 3D printed polymers. Markedly, one of the naphthalimide derivatives (Napht-4) can be used as a new high-performance water soluble photoinitiator for photopolymerization in water and hydrogel synthesis.}, keywords = {}, pubstate = {published}, tppubtype = {article} } In this work, six new fluorescent dyes derived from the naphthalimide scaffold (Napht1-Napht6) were synthesized and used as high-performance photoinitiating systems (PISs) in two and three-component systems (combined with iodonium salt (Iod) and/or an electron donor amine (such as N-phenylglycine[NPG])) for the radical photopolymerization of acrylate and methacrylate monomers under visible light using a light-emitting diode at 405 nm. Markedly, these dyes were never synthesized before. In fact, these PISs showed high initiation efficiency with both demonstrating high final reactive function conversions and high polymerization rates. A further interest of our study is to determine the effect of the different substituents (chromophoric group) on the naphthalimide function, concerning the efficiency of initiation of the free radical polymerization. In order to improve the mechanical properties of the obtained polymers, these derivatives were also tested for the photopolymerization of a blend of acrylate/epoxy monomers (TA/EPOX); these latter properties were characterized by traction tests. To demonstrate the initiation efficiency of these dyes, several methods and characterization techniques were used, including steady state photolysis, real-time Fourier transform infrared spectroscopy, emission spectroscopy as well as cyclic voltammetry. In our study, these naphthalimides were used for the synthesis of photocomposites (one and multiple layers of glass fibres) using a UV@395 nm (4 W/cm(2)) conveyor, as well as in the preparation of 3D printed polymers. Markedly, one of the naphthalimide derivatives (Napht-4) can be used as a new high-performance water soluble photoinitiator for photopolymerization in water and hydrogel synthesis. |
Ma, Yik-Ken; Rigolet, Severinne; Michelin, Laure; Paillaud, Jean-Louis; Mintova, Svetlana; Khoerunnisa, Fitri; Daou, Jean T; Ng, Eng-Poh Facile and fast determination of Si/Al ratio of zeolites using FTIR spectroscopy technique (Article de journal) Microporous and Mesoporous Materials, 311 , p. 110683, 2021. @article{Ma2021, title = {Facile and fast determination of Si/Al ratio of zeolites using FTIR spectroscopy technique}, author = {Yik-Ken Ma and Severinne Rigolet and Laure Michelin and Jean-Louis Paillaud and Svetlana Mintova and Fitri Khoerunnisa and Jean T Daou and Eng-Poh Ng}, doi = {10.1016/j.micromeso.2020.110683}, year = {2021}, date = {2021-02-01}, journal = {Microporous and Mesoporous Materials}, volume = {311}, pages = {110683}, keywords = {}, pubstate = {published}, tppubtype = {article} } |
Xu, Yangyang; Noirbent, Guillaume; Brunel, Damien; Ding, Zhaofu; Gigmes, Didier; Graff, Bernadette; Xiao, Pu; Dumur, Frederic; Lalevee, Jacques Allyloxy ketones as efficient photoinitiators with high migration stability in free radical polymerization and 3D printing (Article de journal) Dyes and Pigments, 185 , p. 108900, 2021. @article{Xu2021, title = {Allyloxy ketones as efficient photoinitiators with high migration stability in free radical polymerization and 3D printing}, author = {Yangyang Xu and Guillaume Noirbent and Damien Brunel and Zhaofu Ding and Didier Gigmes and Bernadette Graff and Pu Xiao and Frederic Dumur and Jacques Lalevee}, doi = {10.1016/j.dyepig.2020.108900}, year = {2021}, date = {2021-02-01}, journal = {Dyes and Pigments}, volume = {185}, pages = {108900}, keywords = {}, pubstate = {published}, tppubtype = {article} } |
Zhang, Yijun; Xu, Yangyang; Simon-Masseron, Angelique; Lalevee, Jacques Radical photoinitiation with LEDs and applications in the 3D printing of composites. (Article de journal) Chemical Society reviews, 2021. @article{Zhang2021, title = {Radical photoinitiation with LEDs and applications in the 3D printing of composites.}, author = {Yijun Zhang and Yangyang Xu and Angelique Simon-Masseron and Jacques Lalevee}, doi = {10.1039/d0cs01411g}, year = {2021}, date = {2021-02-01}, journal = {Chemical Society reviews}, keywords = {}, pubstate = {published}, tppubtype = {article} } |
Revol, Baptiste Paul; Vauthier, Madeline; Thomassey, Matthieu; Bouquey, Michel; Ruch, Frederic; Nardin, Michel Design of experience to evaluate the Interfacial compatibility on high tenacity viscose fibers reinforced Polyamide-6 composites (Article de journal) Composites Science and Technology, 203 , p. 108615, 2021. @article{Revol2021, title = {Design of experience to evaluate the Interfacial compatibility on high tenacity viscose fibers reinforced Polyamide-6 composites}, author = {Baptiste Paul Revol and Madeline Vauthier and Matthieu Thomassey and Michel Bouquey and Frederic Ruch and Michel Nardin}, doi = {10.1016/j.compscitech.2020.108615}, year = {2021}, date = {2021-02-01}, journal = {Composites Science and Technology}, volume = {203}, pages = {108615}, keywords = {}, pubstate = {published}, tppubtype = {article} } |
Gaca, Magdalena; Ilcikova, Marketa; Mrlik, Miroslav; Cvek, Martin; Vaulot, Cyril; Urbanek, Pavel; Pietrasik, Robert; Krupa, Igor; Pietrasik, Joanna Impact of ionic liquids on the processing and photo-actuation behavior of SBR composites containing graphene nanoplatelets (Article de journal) Sensors and Actuators B-chemical, 329 , p. 129195, 2021. @article{Gaca2021, title = {Impact of ionic liquids on the processing and photo-actuation behavior of SBR composites containing graphene nanoplatelets}, author = {Magdalena Gaca and Marketa Ilcikova and Miroslav Mrlik and Martin Cvek and Cyril Vaulot and Pavel Urbanek and Robert Pietrasik and Igor Krupa and Joanna Pietrasik}, doi = {10.1016/j.snb.2020.129195}, year = {2021}, date = {2021-02-01}, journal = {Sensors and Actuators B-chemical}, volume = {329}, pages = {129195}, keywords = {}, pubstate = {published}, tppubtype = {article} } |
Riikonen, Joakim; Rantanen, Jimi; Thapa, Rinez; Le, Nguyen T; Rigolet, Severinne; Fioux, Philippe; Turhanen, Petri; Bodiford, Nelli K; Kalluri, Jhansi R; Ikonen, Timo; Nissinen, Tuomo; Lebeau, Benedicte; Vepsalainen, Jouko; Coffer, Jeffery L; Lehto, Vesa-Pekka Rapid synthesis of nanostructured porous silicon carbide from biogenic silica (Article de journal) Journal of the American Ceramic Society, 104 (2), p. 766–775, 2021. @article{Riikonen2021b, title = {Rapid synthesis of nanostructured porous silicon carbide from biogenic silica}, author = {Joakim Riikonen and Jimi Rantanen and Rinez Thapa and Nguyen T Le and Severinne Rigolet and Philippe Fioux and Petri Turhanen and Nelli K Bodiford and Jhansi R Kalluri and Timo Ikonen and Tuomo Nissinen and Benedicte Lebeau and Jouko Vepsalainen and Jeffery L Coffer and Vesa-Pekka Lehto}, doi = {10.1111/jace.17519}, year = {2021}, date = {2021-02-01}, journal = {Journal of the American Ceramic Society}, volume = {104}, number = {2}, pages = {766--775}, abstract = {Nanostructured silicon carbide (SiC) is an exceptional material with numerous applications, for example, in catalysis, biomedicine, high-performance composites, and sensing. In this study, a fast and scalable method of producing nanostructured SiC from plant materials by magnesiothermic reduction via self-propagating high-temperature synthesis (SHS) route was developed. The produced biogenic material possessed a high surface area above 200 m(2)/g with a SiC crystallite size below 10 nm, which has not been done previously by SHS. This method enables affordable synthesis of the material plant-based precursors in a reaction that only takes a few seconds, thereby paving a way for nanostructured SiC production in high volumes using renewable resources. The material was also functionalized with carboxylic acid and bisphosphonate moieties, and its use as metal adsorbent in applications such as wastewater remediation was demonstrated.}, keywords = {}, pubstate = {published}, tppubtype = {article} } Nanostructured silicon carbide (SiC) is an exceptional material with numerous applications, for example, in catalysis, biomedicine, high-performance composites, and sensing. In this study, a fast and scalable method of producing nanostructured SiC from plant materials by magnesiothermic reduction via self-propagating high-temperature synthesis (SHS) route was developed. The produced biogenic material possessed a high surface area above 200 m(2)/g with a SiC crystallite size below 10 nm, which has not been done previously by SHS. This method enables affordable synthesis of the material plant-based precursors in a reaction that only takes a few seconds, thereby paving a way for nanostructured SiC production in high volumes using renewable resources. The material was also functionalized with carboxylic acid and bisphosphonate moieties, and its use as metal adsorbent in applications such as wastewater remediation was demonstrated. |
Riikonen, Joakim; Rantanen, Jimi; Thapa, Rinez; Le, Nguyen T; Rigolet, Severinne; Fioux, Philippe; Turhanen, Petri; Bodiford, Nelli K; Kalluri, Jhansi R; Ikonen, Timo; Nissinen, Tuomo; Lebeau, Benedicte; Vepsalainen, Jouko; Coffer, Jeffery L; Lehto, Vesa-Pekka Rapid synthesis of nanostructured porous silicon carbide from biogenic silica (Article de journal) Journal of the American Ceramic Society, 104 (2), p. 766–775, 2021. @article{Riikonen2021, title = {Rapid synthesis of nanostructured porous silicon carbide from biogenic silica}, author = { Joakim Riikonen and Jimi Rantanen and Rinez Thapa and Nguyen T. Le and Severinne Rigolet and Philippe Fioux and Petri Turhanen and Nelli K. Bodiford and Jhansi R. Kalluri and Timo Ikonen and Tuomo Nissinen and Benedicte Lebeau and Jouko Vepsalainen and Jeffery L. Coffer and Vesa-Pekka Lehto}, doi = {10.1111/jace.17519}, year = {2021}, date = {2021-02-01}, journal = {Journal of the American Ceramic Society}, volume = {104}, number = {2}, pages = {766--775}, abstract = {Nanostructured silicon carbide (SiC) is an exceptional material with numerous applications, for example, in catalysis, biomedicine, high-performance composites, and sensing. In this study, a fast and scalable method of producing nanostructured SiC from plant materials by magnesiothermic reduction via self-propagating high-temperature synthesis (SHS) route was developed. The produced biogenic material possessed a high surface area above 200 m(2)/g with a SiC crystallite size below 10 nm, which has not been done previously by SHS. This method enables affordable synthesis of the material plant-based precursors in a reaction that only takes a few seconds, thereby paving a way for nanostructured SiC production in high volumes using renewable resources. The material was also functionalized with carboxylic acid and bisphosphonate moieties, and its use as metal adsorbent in applications such as wastewater remediation was demonstrated.}, keywords = {}, pubstate = {published}, tppubtype = {article} } Nanostructured silicon carbide (SiC) is an exceptional material with numerous applications, for example, in catalysis, biomedicine, high-performance composites, and sensing. In this study, a fast and scalable method of producing nanostructured SiC from plant materials by magnesiothermic reduction via self-propagating high-temperature synthesis (SHS) route was developed. The produced biogenic material possessed a high surface area above 200 m(2)/g with a SiC crystallite size below 10 nm, which has not been done previously by SHS. This method enables affordable synthesis of the material plant-based precursors in a reaction that only takes a few seconds, thereby paving a way for nanostructured SiC production in high volumes using renewable resources. The material was also functionalized with carboxylic acid and bisphosphonate moieties, and its use as metal adsorbent in applications such as wastewater remediation was demonstrated. |
Gao, Shuxi; Sun, Longfeng; Xu, Kai; Gui, Xuefeng; Liu, Lingli Silsesquioxane-cored miktoarm copolymer amphiphiles for fabrication of oxidation-responsive silica-encapsulated polysulfide microspheres (Article de journal) European Polymer Journal, 143 , p. 110196, 2021. @article{Gao2021, title = {Silsesquioxane-cored miktoarm copolymer amphiphiles for fabrication of oxidation-responsive silica-encapsulated polysulfide microspheres}, author = {Shuxi Gao and Longfeng Sun and Kai Xu and Xuefeng Gui and Lingli Liu}, doi = {10.1016/j.eurpolymj.2020.110196}, year = {2021}, date = {2021-01-01}, journal = {European Polymer Journal}, volume = {143}, pages = {110196}, abstract = {The configuration and amphipathicity of polymer templates are crucial in fabrication of hybrid microspheres via the self-assembling process. Here, a new star-like silsesquioxane-cored miktoarm copolymer (M-T-8-P) with desired amphiphilicity was synthesized and sufficiently characterized by various methods. The hybrid amphipathic architectures endowed M-T-8-P an attractive capability of stable encapsulation for oxidation-reponsive polysulfides (PSL) synthesized from sulfur and monoterpenes, and facilitated the formation of stable M-T-8-P/PSL complex micelles, which further templated the construction of oxidation-active silica microspheres with micrometer dimensions through a simple one-pot sol-gel route. With the increasing of PSL/M-T-8-P feed ratio, the size of microspheres and the content of PSL in the resulting microsphere were increased due to PSL droplets providing a soft-template for silica particles to build larger-sized silica microspheres with PSL cores, but the regularity of microspheres was decreased. The increased content of PSL and oxidation treatment could significantly enhanced adsorption capacity of hybrid microsphere for palladium (II). On the basis of these promising results, the hybrid copolymer and microspheres might find the applications in water treatment and environmental protection.}, keywords = {}, pubstate = {published}, tppubtype = {article} } The configuration and amphipathicity of polymer templates are crucial in fabrication of hybrid microspheres via the self-assembling process. Here, a new star-like silsesquioxane-cored miktoarm copolymer (M-T-8-P) with desired amphiphilicity was synthesized and sufficiently characterized by various methods. The hybrid amphipathic architectures endowed M-T-8-P an attractive capability of stable encapsulation for oxidation-reponsive polysulfides (PSL) synthesized from sulfur and monoterpenes, and facilitated the formation of stable M-T-8-P/PSL complex micelles, which further templated the construction of oxidation-active silica microspheres with micrometer dimensions through a simple one-pot sol-gel route. With the increasing of PSL/M-T-8-P feed ratio, the size of microspheres and the content of PSL in the resulting microsphere were increased due to PSL droplets providing a soft-template for silica particles to build larger-sized silica microspheres with PSL cores, but the regularity of microspheres was decreased. The increased content of PSL and oxidation treatment could significantly enhanced adsorption capacity of hybrid microsphere for palladium (II). On the basis of these promising results, the hybrid copolymer and microspheres might find the applications in water treatment and environmental protection. |
Haounati, Redouane; Ouachtak, Hassan; Haouti, Rachid El; Akhouairi, Siham; Largo, Fadwa; Akbal, Feryal; Benlhachemi, Abdeljalil; Jada, Amane; Addi, Abdelaziz Ait Elaboration and properties of a new SDS/CTAB@Montmorillonite organoclay composite as a superb adsorbent for the removal of malachite green from aqueous solutions (Article de journal) Separation and Purification Technology, 255 , p. 117335, 2021. @article{Haounati2021, title = {Elaboration and properties of a new SDS/CTAB@Montmorillonite organoclay composite as a superb adsorbent for the removal of malachite green from aqueous solutions}, author = {Redouane Haounati and Hassan Ouachtak and Rachid El Haouti and Siham Akhouairi and Fadwa Largo and Feryal Akbal and Abdeljalil Benlhachemi and Amane Jada and Abdelaziz Ait Addi}, doi = {10.1016/j.seppur.2020.117335}, year = {2021}, date = {2021-01-01}, journal = {Separation and Purification Technology}, volume = {255}, pages = {117335}, abstract = {In this study, the SDS/CTAB@Mt composite as a novel adsorbent has been prepared via a facile synergistic effect of cationic surfactant (CTAB) and anionic surfactant (SDS) for the modification of montmorillonite, and it was utilized to remove malachite green (MG) from aqueous solutions. The structure and the morphology of the SDS/CTAB@Mt composite were characterized by X-ray diffraction (XRD), Fourier Transform Infra-Red (FT-IR) spectroscopy, Scanning Electron Microscopy (SEM), Transmission Electron Microscopy (TEM), Energy Dispersive Analysis of X-rays (EDAX), and N-2 adsorption/desorption isotherms (BET method). The SDS/CTAB@Mt composite was found to be highly negatively surface charged, and showed good adsorption properties for MG molecules, reaching a maximum dye adsorbed amount of 1021.45 mg/g. Further, at the equilibrium, the experimental adsorption isotherms were in good agreement with the theoretical predicted data by the Langmuir model (R-2 = 0.99), indicating that the MG molecules were homogenously adsorbed and formed a monolayer on the SDS/CTAB@Mt surface. Moreover, the adsorption kinetics data were well fitted with pseudo-second-order model (R-2 = 0.99). From the adsorption temperature effect study, the thermodynamic parameters, such as G, Delta H and Delta S were assessed, and their values revealed that the adsorption reaction was spontaneous, exothermic and resulted in a decrease of the MG adsorbed molecules randomness on the adsorbent surface. Finally, a new adsorption mechanism was proposed and confirmed that the MG molecules adsorption from water onto the SDS/CTAB@Mt adsorbent resulted from synergistic effect of the hydrophobic and the hydrophilic interactions.}, keywords = {}, pubstate = {published}, tppubtype = {article} } In this study, the SDS/CTAB@Mt composite as a novel adsorbent has been prepared via a facile synergistic effect of cationic surfactant (CTAB) and anionic surfactant (SDS) for the modification of montmorillonite, and it was utilized to remove malachite green (MG) from aqueous solutions. The structure and the morphology of the SDS/CTAB@Mt composite were characterized by X-ray diffraction (XRD), Fourier Transform Infra-Red (FT-IR) spectroscopy, Scanning Electron Microscopy (SEM), Transmission Electron Microscopy (TEM), Energy Dispersive Analysis of X-rays (EDAX), and N-2 adsorption/desorption isotherms (BET method). The SDS/CTAB@Mt composite was found to be highly negatively surface charged, and showed good adsorption properties for MG molecules, reaching a maximum dye adsorbed amount of 1021.45 mg/g. Further, at the equilibrium, the experimental adsorption isotherms were in good agreement with the theoretical predicted data by the Langmuir model (R-2 = 0.99), indicating that the MG molecules were homogenously adsorbed and formed a monolayer on the SDS/CTAB@Mt surface. Moreover, the adsorption kinetics data were well fitted with pseudo-second-order model (R-2 = 0.99). From the adsorption temperature effect study, the thermodynamic parameters, such as G, Delta H and Delta S were assessed, and their values revealed that the adsorption reaction was spontaneous, exothermic and resulted in a decrease of the MG adsorbed molecules randomness on the adsorbent surface. Finally, a new adsorption mechanism was proposed and confirmed that the MG molecules adsorption from water onto the SDS/CTAB@Mt adsorbent resulted from synergistic effect of the hydrophobic and the hydrophilic interactions. |
Jonas, Florian; Lebeau, Benedicte; Siffert, Stephane; Michelin, Laure; Poupin, Christophe; Cousin, Renaud; Josien, Ludovic; Vidal, Loic; Mallet, Martine; Gaudin, Pierrick; Blin, Jean-Luc Nanoporous CeO2-ZrO2 Oxides for Oxidation of Volatile Organic Compounds (Article de journal) Acs Applied Nano Materials, 4 (2), p. 1786–1797, 2021. @article{Jonas2021, title = {Nanoporous CeO2-ZrO2 Oxides for Oxidation of Volatile Organic Compounds}, author = {Florian Jonas and Benedicte Lebeau and Stephane Siffert and Laure Michelin and Christophe Poupin and Renaud Cousin and Ludovic Josien and Loic Vidal and Martine Mallet and Pierrick Gaudin and Jean-Luc Blin}, doi = {10.1021/acsanm.0c03212}, year = {2021}, date = {2021-01-01}, journal = {Acs Applied Nano Materials}, volume = {4}, number = {2}, pages = {1786--1797}, abstract = {Here, mixed nanostructured ceria/zirconia oxides have been prepared either by wet impregnation on nanostructured ZrO2 or by co-condensation through an evaporation-induced self-assembly (EISA)-derived pathway. This latter method and impregnation on amorphous ZrO2, followed or not by heating at 480 degrees C, lead to a uniform cerium distribution in the zirconia framework, and solid solutions are formed. Stabilization of the tetragonal structure of nano-ZrO(2 )with the increase of the cerium content is observed by X-ray diffraction (XRD) and Raman spectroscopy. The surface Ce/Zr molar ratio determined by X-ray photoelectron spectrometry (XPS) is very close to the bulk one, calculated from the X-ray fluorescence analysis. In contrast to the appearance of nanosized ceria particles with the increase of the cerium content, a monoclinic/tetragonal mixture and enrichment of the surface in cerium are noted if the impregnation is carried out on nanostructured ZrO2 previously calcined at 480 degrees C. The obtained catalysts have been tested for the oxidation of toluene, used as a model volatile organic compound. The catalytic efficiency of the mixed oxides has also been compared to that of pure commercial ceria. Results show that the preparation method has a significant effect on the catalytic properties of the materials. Although pure ceria presents the best activity and selectivity, the nanostructured ZrO(2 )previously calcined at 480 degrees C and impregnated by 10 mol % CeO2 is almost as efficient as pure ceria.}, keywords = {}, pubstate = {published}, tppubtype = {article} } Here, mixed nanostructured ceria/zirconia oxides have been prepared either by wet impregnation on nanostructured ZrO2 or by co-condensation through an evaporation-induced self-assembly (EISA)-derived pathway. This latter method and impregnation on amorphous ZrO2, followed or not by heating at 480 degrees C, lead to a uniform cerium distribution in the zirconia framework, and solid solutions are formed. Stabilization of the tetragonal structure of nano-ZrO(2 )with the increase of the cerium content is observed by X-ray diffraction (XRD) and Raman spectroscopy. The surface Ce/Zr molar ratio determined by X-ray photoelectron spectrometry (XPS) is very close to the bulk one, calculated from the X-ray fluorescence analysis. In contrast to the appearance of nanosized ceria particles with the increase of the cerium content, a monoclinic/tetragonal mixture and enrichment of the surface in cerium are noted if the impregnation is carried out on nanostructured ZrO2 previously calcined at 480 degrees C. The obtained catalysts have been tested for the oxidation of toluene, used as a model volatile organic compound. The catalytic efficiency of the mixed oxides has also been compared to that of pure commercial ceria. Results show that the preparation method has a significant effect on the catalytic properties of the materials. Although pure ceria presents the best activity and selectivity, the nanostructured ZrO(2 )previously calcined at 480 degrees C and impregnated by 10 mol % CeO2 is almost as efficient as pure ceria. |
Arar, Ahmad; Mousawi, Assi Al; Morlet-Savary, Fabrice; Lalevee, Jacques Peroxide-free redox initiating systems for polymerization in mild conditions (Article de journal) Polymer Chemistry, 12 (12), p. 1816–1822, 2021. @article{Arar2021a, title = {Peroxide-free redox initiating systems for polymerization in mild conditions}, author = {Ahmad Arar and Assi Al Mousawi and Fabrice Morlet-Savary and Jacques Lalevee}, doi = {10.1039/d1py00172h}, year = {2021}, date = {2021-01-01}, journal = {Polymer Chemistry}, volume = {12}, number = {12}, pages = {1816--1822}, abstract = {Redox free radical polymerization (RFRP) is considered as a cost-effective technique for the production of polymers in a very short time scale and without any energy consumption. Its principle is based on blending two components (2K for two cartridges) composed of an oxidizing and a reducing agent, respectively. In this paper, original Redox Initiating Systems (RISs) comprising metal salts as oxidizing agents and reducing agents are developed for mild conditions (at room temperature, under air and without monomer purification or stabilizer removal). An economic, low toxicity and high stability process is attained. A good control of the gel time is also possible. Based on electron spin resonance experiments, an original chemical mechanism is also provided for these redox initiators.}, keywords = {}, pubstate = {published}, tppubtype = {article} } Redox free radical polymerization (RFRP) is considered as a cost-effective technique for the production of polymers in a very short time scale and without any energy consumption. Its principle is based on blending two components (2K for two cartridges) composed of an oxidizing and a reducing agent, respectively. In this paper, original Redox Initiating Systems (RISs) comprising metal salts as oxidizing agents and reducing agents are developed for mild conditions (at room temperature, under air and without monomer purification or stabilizer removal). An economic, low toxicity and high stability process is attained. A good control of the gel time is also possible. Based on electron spin resonance experiments, an original chemical mechanism is also provided for these redox initiators. |
Ntetsikas, Konstantinos; Moschovas, Dimitrios; Zapsas, George; Moutsios, Ioannis; Tsitoni, Konstantina; Manesi, Gkreti-Maria; Nabiullin, Azat F; Hadjichristidis, Nikos; Ivanov, Dimitri A; Avgeropoulos, Apostolos Synthesis, characterization and self-assembly of linear and miktoarm star copolymers of exclusively immiscible polydienes (Article de journal) Polymer Chemistry, 2021. @article{Ntetsikas2021, title = {Synthesis, characterization and self-assembly of linear and miktoarm star copolymers of exclusively immiscible polydienes}, author = {Konstantinos Ntetsikas and Dimitrios Moschovas and George Zapsas and Ioannis Moutsios and Konstantina Tsitoni and Gkreti-Maria Manesi and Azat F Nabiullin and Nikos Hadjichristidis and Dimitri A Ivanov and Apostolos Avgeropoulos}, doi = {10.1039/d1py00258a}, year = {2021}, date = {2021-01-01}, journal = {Polymer Chemistry}, abstract = {Linear and non-linear copolymers of the PB-b-PI sequence [PB: polybutadiene of high 1,4-microstructure (similar to 92%) and PI: polyisoprene of high 3,4-microstructure (similar to 55-60%)] and their corresponding miktoarm star copolymers of the PB(PI3,4)(2) and PB(PI3,4)(3) type were synthesized by combining anionic polymerization and selective chlorosilane chemistry. Molecular characteristics, thermal properties and structure/properties relationship are reported for the specific copolymers and especially the self-assembly is of major importance and interest due to the nature of the blocks. The identical electron densities between the two polydienes led to impossible morphological characterization through small angle X-ray scattering (SAXS) and only transmission electron microscopy results verify the adopted morphology for each copolymer, justifying the assumption that the segment-segment interaction parameter between the two polydienes of high 1,4-microstructure (similar to 92%) for the PB and similar to 55-60% 3,4-microstructure for the PI is well above zero. The consistency of the bulk morphology results of this study compared with those of the extensively studied system of the PS(PI)(n=1,2,3) type (PS: polystyrene), were unexpectedly coherent. High chain flexibility provided by the two polydiene segments, leads to promising properties unattainable from corresponding thermoplastic triblock copolymers of these polydienes with PS (PS-b-PI-b-PS, PS-b-PB-b-PS), especially for rheological studies.}, keywords = {}, pubstate = {published}, tppubtype = {article} } Linear and non-linear copolymers of the PB-b-PI sequence [PB: polybutadiene of high 1,4-microstructure (similar to 92%) and PI: polyisoprene of high 3,4-microstructure (similar to 55-60%)] and their corresponding miktoarm star copolymers of the PB(PI3,4)(2) and PB(PI3,4)(3) type were synthesized by combining anionic polymerization and selective chlorosilane chemistry. Molecular characteristics, thermal properties and structure/properties relationship are reported for the specific copolymers and especially the self-assembly is of major importance and interest due to the nature of the blocks. The identical electron densities between the two polydienes led to impossible morphological characterization through small angle X-ray scattering (SAXS) and only transmission electron microscopy results verify the adopted morphology for each copolymer, justifying the assumption that the segment-segment interaction parameter between the two polydienes of high 1,4-microstructure (similar to 92%) for the PB and similar to 55-60% 3,4-microstructure for the PI is well above zero. The consistency of the bulk morphology results of this study compared with those of the extensively studied system of the PS(PI)(n=1,2,3) type (PS: polystyrene), were unexpectedly coherent. High chain flexibility provided by the two polydiene segments, leads to promising properties unattainable from corresponding thermoplastic triblock copolymers of these polydienes with PS (PS-b-PI-b-PS, PS-b-PB-b-PS), especially for rheological studies. |
Brahmi, Chaima; Benltifa, Mahmoud; Ghali, Mariem; Dumur, Frederic; Simonnet-Jegat, Corine; Monnier, Valerie; Morlet-Savary, Fabrice; Bousselmi, Latifa; Lalevee, Jacques Polyoxometalates/polymer composites for the photodegradation of bisphenol-A (Article de journal) Journal of Applied Polymer Science, p. e50864, 2021. @article{Brahmi2021, title = {Polyoxometalates/polymer composites for the photodegradation of bisphenol-A}, author = {Chaima Brahmi and Mahmoud Benltifa and Mariem Ghali and Frederic Dumur and Corine Simonnet-Jegat and Valerie Monnier and Fabrice Morlet-Savary and Latifa Bousselmi and Jacques Lalevee}, doi = {10.1002/app.50864}, year = {2021}, date = {2021-01-01}, journal = {Journal of Applied Polymer Science}, pages = {e50864}, abstract = {Nowadays water scarcity represents a threat for human and living beings. Therefore, to satisfy the demands of people for clean and safe water, new technologies for wastewater treatment have been developed. Thus, photocatalysis has emerged as a green chemical approach for such treatment. In this context, new polyoxometalate (POM)/polymer composites with relevant photocatalytic properties have been developed via an easy and cheap photopolymerization process upon mild visible light irradiation at 405 nm. This fruitful association between POM and polymer allowed the obtention of shaped materials facile to collect and reuse at the end of the photocatalytic treatment avoiding then the usual time-consuming regeneration methods. The prepared photocomposites displayed excellent photocatalytic performance for the removal of bisphenol-A from water under different sources of irradiation. Hence, 100%, 88%, and 50% of this model compound were decomposed by the phosphomolybdic composite under just 90 min of UV lamp, solar and LED@375 nm irradiations, respectively. The effectiveness of these developed photocatalysts towards the degradation of other organic compounds, as well as the degradation mechanism based on the generation of highly reactive chemicals such as (OH)-O-center dot radicals promoting the degradation were already reported. Bisphenol-A degradation pathway and the identification of the photoproducts were discussed using mass spectroscopy technique. Therefore, this paper highlighted the photocatalytic efficiency of the new manufactured materials for the photodegradation of the bisphenol-A, thus expanding their application fields, under different sources of irradiation and under pure solar irradiation which make their applications more interesting and less energy consuming.}, keywords = {}, pubstate = {published}, tppubtype = {article} } Nowadays water scarcity represents a threat for human and living beings. Therefore, to satisfy the demands of people for clean and safe water, new technologies for wastewater treatment have been developed. Thus, photocatalysis has emerged as a green chemical approach for such treatment. In this context, new polyoxometalate (POM)/polymer composites with relevant photocatalytic properties have been developed via an easy and cheap photopolymerization process upon mild visible light irradiation at 405 nm. This fruitful association between POM and polymer allowed the obtention of shaped materials facile to collect and reuse at the end of the photocatalytic treatment avoiding then the usual time-consuming regeneration methods. The prepared photocomposites displayed excellent photocatalytic performance for the removal of bisphenol-A from water under different sources of irradiation. Hence, 100%, 88%, and 50% of this model compound were decomposed by the phosphomolybdic composite under just 90 min of UV lamp, solar and LED@375 nm irradiations, respectively. The effectiveness of these developed photocatalysts towards the degradation of other organic compounds, as well as the degradation mechanism based on the generation of highly reactive chemicals such as (OH)-O-center dot radicals promoting the degradation were already reported. Bisphenol-A degradation pathway and the identification of the photoproducts were discussed using mass spectroscopy technique. Therefore, this paper highlighted the photocatalytic efficiency of the new manufactured materials for the photodegradation of the bisphenol-A, thus expanding their application fields, under different sources of irradiation and under pure solar irradiation which make their applications more interesting and less energy consuming. |
Chen, Hong; Noirbent, Guillaume; Liu, Shaohui; Zhang, Yijun; Sun, Ke; Morlet-Savary, Fabrice; Gigmes, Didier; Xiao, Pu; Dumur, Frederic; Lalevee, Jacques Journal of Polymer Science, 2021. @article{Chen2021b, title = {In situ generation of Ag nanoparticles during photopolymerization by using newly developed dyes-based three-component photoinitiating systems and the related 3D printing applications and their shape change behavior}, author = {Hong Chen and Guillaume Noirbent and Shaohui Liu and Yijun Zhang and Ke Sun and Fabrice Morlet-Savary and Didier Gigmes and Pu Xiao and Frederic Dumur and Jacques Lalevee}, doi = {10.1002/pol.20210154}, year = {2021}, date = {2021-01-01}, journal = {Journal of Polymer Science}, abstract = {Silver nanoparticles (AgNPs) play a crucial role in biology and medical research as their extensive and efficient antibacterial activity and high electrical and thermal conductivity. However, the generation of them with a certain morphology under mild conditions (under air, solvent-free, room temperature, etc.,) is still a huge challenge. Herein, a simple one-step method is proposed to generate AgNPs in situ at room temperature under air by combining the photopolymerization process with the formation process of AgNPs within a few minutes. In detailed, 12 different dyes based on 2,5-diethylene-cyclopentan-1-one were first synthesized and used as high-performance type II photoinitiator. When using in conjunction of bis-(4-tert-butylphenyl) iodonium hexafluorophosphate (Iod) and ethyl 4-dimethylaminobenzoate (EDB), they can effectively boost the free radical photopolymerization (FRP) of polyethylene glycol diacrylate (PEG-DA) and the cationic photopolymerization (CP) of 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate (EPOX) upon irradiation with LED@405 nm. Furthermore, all the formulations containing/without AgNPs can be successfully used to perform the direct laser write experiment. However, even if all of the obtained 3D patterns exhibited reversible swelling performance and shape-memory effects caused by swelling and dehydration for the access to 4D printing, the presence of AgNPs will affect these properties.}, keywords = {}, pubstate = {published}, tppubtype = {article} } Silver nanoparticles (AgNPs) play a crucial role in biology and medical research as their extensive and efficient antibacterial activity and high electrical and thermal conductivity. However, the generation of them with a certain morphology under mild conditions (under air, solvent-free, room temperature, etc.,) is still a huge challenge. Herein, a simple one-step method is proposed to generate AgNPs in situ at room temperature under air by combining the photopolymerization process with the formation process of AgNPs within a few minutes. In detailed, 12 different dyes based on 2,5-diethylene-cyclopentan-1-one were first synthesized and used as high-performance type II photoinitiator. When using in conjunction of bis-(4-tert-butylphenyl) iodonium hexafluorophosphate (Iod) and ethyl 4-dimethylaminobenzoate (EDB), they can effectively boost the free radical photopolymerization (FRP) of polyethylene glycol diacrylate (PEG-DA) and the cationic photopolymerization (CP) of 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate (EPOX) upon irradiation with LED@405 nm. Furthermore, all the formulations containing/without AgNPs can be successfully used to perform the direct laser write experiment. However, even if all of the obtained 3D patterns exhibited reversible swelling performance and shape-memory effects caused by swelling and dehydration for the access to 4D printing, the presence of AgNPs will affect these properties. |
Zhang, Yijun; Liu, Shaohui; Chen, Hong; Josien, Ludovic; Schrodj, Gautier; Simon-Masseron, Angelique; Lalevee, Jacques Development of a Zeolite/Polymer-Based Hydrogel Composite through Photopolymerization for 3D Printing Application (Article de journal) Macromolecular Materials and Engineering, p. 2100129, 2021. @article{Zhang2021c, title = {Development of a Zeolite/Polymer-Based Hydrogel Composite through Photopolymerization for 3D Printing Application}, author = {Yijun Zhang and Shaohui Liu and Hong Chen and Ludovic Josien and Gautier Schrodj and Angelique Simon-Masseron and Jacques Lalevee}, doi = {10.1002/mame.202100129}, year = {2021}, date = {2021-01-01}, journal = {Macromolecular Materials and Engineering}, pages = {2100129}, abstract = {In recent years, hydrogels have been widely applied in daily life and industry. More and more fillers have been combined with hydrogel to broaden their fields of application and improve their mechanical properties. However, there are few works about zeolite-based hydrogel composites via photopolymerization. Hence, in this work, it is reported that the fabrication of hydrogel composites containing zeolite (FAU-13X approximate to 40 wt%) under mild photopolymerization conditions (visible LED light irradiation, at room temperature, under air, and without any monomer purification). Markedly, compared to pure hydrogel, the elastic modulus (G ') of hydrogel composite contains 10% FAU-13X increased by more than 100%. When the zeolite content reached 40%, the water swelling ratio in mass reached 120%, and that in volume remained at 150%. In addition, 3D patterns with flat surface are obtained through direct laser write as a lithography technique. This means these hydrogel composites can be applied in the field of water absorption materials and 3D printing.}, keywords = {}, pubstate = {published}, tppubtype = {article} } In recent years, hydrogels have been widely applied in daily life and industry. More and more fillers have been combined with hydrogel to broaden their fields of application and improve their mechanical properties. However, there are few works about zeolite-based hydrogel composites via photopolymerization. Hence, in this work, it is reported that the fabrication of hydrogel composites containing zeolite (FAU-13X approximate to 40 wt%) under mild photopolymerization conditions (visible LED light irradiation, at room temperature, under air, and without any monomer purification). Markedly, compared to pure hydrogel, the elastic modulus (G ') of hydrogel composite contains 10% FAU-13X increased by more than 100%. When the zeolite content reached 40%, the water swelling ratio in mass reached 120%, and that in volume remained at 150%. In addition, 3D patterns with flat surface are obtained through direct laser write as a lithography technique. This means these hydrogel composites can be applied in the field of water absorption materials and 3D printing. |
Hammoud, Fatima; Rahal, Mahmoud; Egly, Julien; Morlet-Savary, Fabrice; Hijazi, Akram; Bellemin-Laponnaz, Stephane; Mauro, Matteo; Lalevee, Jacques Cubane Cu4I4(phosphine)(4) complexes as new co-initiators for free radical photopolymerization: towards aromatic amine-free systems (Article de journal) Polymer Chemistry, 2021. @article{Hammoud2021, title = {Cubane Cu4I4(phosphine)(4) complexes as new co-initiators for free radical photopolymerization: towards aromatic amine-free systems}, author = {Fatima Hammoud and Mahmoud Rahal and Julien Egly and Fabrice Morlet-Savary and Akram Hijazi and Stephane Bellemin-Laponnaz and Matteo Mauro and Jacques Lalevee}, doi = {10.1039/d1py00277e}, year = {2021}, date = {2021-01-01}, journal = {Polymer Chemistry}, abstract = {The investigation of copper-iodide cubane derivatives as new co-initiators for the free radical polymerization (FRP) of acrylate monomers under mild irradiation conditions is described here for the first time. These tetranuclear Cu(I)-based complexes have the general formula, Cu4I4(phosphine)(4), where phosphine is triphenylphosphine (Cu1) or diphenylphosphine (Cu2). In the presence of commercial Type II photoinitiators such as isopropylthioxanthone (ITX) or camphorquinone (CQ), this class of co-initiators achieves high final conversions of the reactive functional groups. A comparison between the aromatic amine, namely ethyldimethylaminobenzoate (EDB), used as a benchmark hydrogen donor, and these copper-based co-initiators is made, which demonstrates that the latter can be considered as valid, environmentally friendly alternatives to toxic aromatic amines. Markedly, photoluminescent materials can be generated thanks to the presence of cubanes linked to the polymer network.}, keywords = {}, pubstate = {published}, tppubtype = {article} } The investigation of copper-iodide cubane derivatives as new co-initiators for the free radical polymerization (FRP) of acrylate monomers under mild irradiation conditions is described here for the first time. These tetranuclear Cu(I)-based complexes have the general formula, Cu4I4(phosphine)(4), where phosphine is triphenylphosphine (Cu1) or diphenylphosphine (Cu2). In the presence of commercial Type II photoinitiators such as isopropylthioxanthone (ITX) or camphorquinone (CQ), this class of co-initiators achieves high final conversions of the reactive functional groups. A comparison between the aromatic amine, namely ethyldimethylaminobenzoate (EDB), used as a benchmark hydrogen donor, and these copper-based co-initiators is made, which demonstrates that the latter can be considered as valid, environmentally friendly alternatives to toxic aromatic amines. Markedly, photoluminescent materials can be generated thanks to the presence of cubanes linked to the polymer network. |
Messaoudi, Noureddine El; Khomri, Mohammed El; Chegini, Zahra Goodarzvand; Chlif, Nisrine; Dbik, Abdellah; Bentahar, Safae; Iqbal, Munawar; Jada, Amane; Lacherai, Abdellah Desorption study and reusability of raw and H2SO4 modified jujube shells (Zizyphus lotus) for the methylene blue adsorption (Article de journal) International Journal of Environmental Analytical Chemistry, 2021. @article{ElMessaoudi2021, title = {Desorption study and reusability of raw and H2SO4 modified jujube shells (Zizyphus lotus) for the methylene blue adsorption}, author = {Noureddine El Messaoudi and Mohammed El Khomri and Zahra Goodarzvand Chegini and Nisrine Chlif and Abdellah Dbik and Safae Bentahar and Munawar Iqbal and Amane Jada and Abdellah Lacherai}, doi = {10.1080/03067319.2021.1912338}, year = {2021}, date = {2021-01-01}, journal = {International Journal of Environmental Analytical Chemistry}, abstract = {In the study, the raw jujube shells of Zizyphus lotus (RJS) and the chemically modified adsorbent with sulphuric acid H2SO4 (SAMJS) were tested as promising adsorbents for removing methylene blue (MB) dye from aqueous solution. After the adsorption, the influence of operating parameters like different eluents,eluent volume andconcentration, contact time, and temperature on MB desorption from the MB-loaded raw jujube shells (MB-RJS) andthe modified adsorbent (MB-SAMJS) was studied. Desorption equilibrium efficiencies of MB form MB-RJS and MB-SAMJS were 92.88 % and 96.94 % at 50 min and 24 degrees C, respectively. Kinetic data were obtained very well with a second-order model. The calculated thermodynamic suggests that the MB desorption from MB-RJS and MB-SAMJS is spontaneous and endothermic. The regeneration and desorption studies demonstrated the reusability of RJS and SAMJS for four adsorption-desorption cycles with approximately 73.12 % and 84.08 % of MB removalusing 0.5 M HNO3, respectively.}, keywords = {}, pubstate = {published}, tppubtype = {article} } In the study, the raw jujube shells of Zizyphus lotus (RJS) and the chemically modified adsorbent with sulphuric acid H2SO4 (SAMJS) were tested as promising adsorbents for removing methylene blue (MB) dye from aqueous solution. After the adsorption, the influence of operating parameters like different eluents,eluent volume andconcentration, contact time, and temperature on MB desorption from the MB-loaded raw jujube shells (MB-RJS) andthe modified adsorbent (MB-SAMJS) was studied. Desorption equilibrium efficiencies of MB form MB-RJS and MB-SAMJS were 92.88 % and 96.94 % at 50 min and 24 degrees C, respectively. Kinetic data were obtained very well with a second-order model. The calculated thermodynamic suggests that the MB desorption from MB-RJS and MB-SAMJS is spontaneous and endothermic. The regeneration and desorption studies demonstrated the reusability of RJS and SAMJS for four adsorption-desorption cycles with approximately 73.12 % and 84.08 % of MB removalusing 0.5 M HNO3, respectively. |
Gerard, Violaine; Galopin, Christophe; Ay, Emel; Launay, Valentin; Morlet-Savary, Fabrice; Graff, Bernadette; Lalevee, Jacques Photostability of l-tryptophan in aqueous solution: Effect of atmosphere and antioxidants addition. (Article de journal) Food chemistry, 359 , p. 129949–129949, 2021. @article{Gerard2021, title = {Photostability of l-tryptophan in aqueous solution: Effect of atmosphere and antioxidants addition.}, author = {Violaine Gerard and Christophe Galopin and Emel Ay and Valentin Launay and Fabrice Morlet-Savary and Bernadette Graff and Jacques Lalevee}, doi = {10.1016/j.foodchem.2021.129949}, year = {2021}, date = {2021-01-01}, journal = {Food chemistry}, volume = {359}, pages = {129949--129949}, abstract = {l-Tryptophan (l-Trp) is an amino acid important in nutrition, and mainly provided by food supplements. However, it is known to be unstable under light irradiation, which is an issue for the nutrition and feed industry. In the present study, the photostability of l-Trp was studied in acidic aqueous solutions under air and under an inert atmosphere, N2. The photodegradation was followed using UV-visible and fluorescence spectroscopy after photolysis. Moreover, molecular orbitals and bond dissociation energies calculations, and electron spin resonance spectroscopy were performed. From all these results, a photodegradation occurring through a free radical pathway was suggested. Interestingly, several antioxidants were tested to improve the photostability of l-Trp, especially during irradiation under air, since the l-Trp was evidenced to be much less stable under air than under N2. The results showed that sodium benzoate or EDTA were not efficient, but antioxidants such as chlorogenic acid, ascorbic acid or potassium sorbate improved significantly the photostability of l-Trp in acidic solutions.}, keywords = {}, pubstate = {published}, tppubtype = {article} } l-Tryptophan (l-Trp) is an amino acid important in nutrition, and mainly provided by food supplements. However, it is known to be unstable under light irradiation, which is an issue for the nutrition and feed industry. In the present study, the photostability of l-Trp was studied in acidic aqueous solutions under air and under an inert atmosphere, N2. The photodegradation was followed using UV-visible and fluorescence spectroscopy after photolysis. Moreover, molecular orbitals and bond dissociation energies calculations, and electron spin resonance spectroscopy were performed. From all these results, a photodegradation occurring through a free radical pathway was suggested. Interestingly, several antioxidants were tested to improve the photostability of l-Trp, especially during irradiation under air, since the l-Trp was evidenced to be much less stable under air than under N2. The results showed that sodium benzoate or EDTA were not efficient, but antioxidants such as chlorogenic acid, ascorbic acid or potassium sorbate improved significantly the photostability of l-Trp in acidic solutions. |
Zhang, Yijun; Chen, Hong; Liu, Shaohui; Josien, Ludovic; Schrodj, Gautier; Simon-Masseron, Angelique; Lalevee, Jacques Photopolymerization of Pollen Based Biosourced Composites and Applications in 3D and 4D Printing (Article de journal) Macromolecular Materials and Engineering, p. 2000774, 2021. @article{Zhang2021a, title = {Photopolymerization of Pollen Based Biosourced Composites and Applications in 3D and 4D Printing}, author = {Yijun Zhang and Hong Chen and Shaohui Liu and Ludovic Josien and Gautier Schrodj and Angelique Simon-Masseron and Jacques Lalevee}, doi = {10.1002/mame.202000774}, year = {2021}, date = {2021-01-01}, journal = {Macromolecular Materials and Engineering}, pages = {2000774}, abstract = {Pollen have the potential to be effective plant-based biorenewable reinforcing fillers for polymers due to their chemical stability and unique micro- or nano-structured surfaces. Pollen-polymer composites can form the basis for a new class of light-weight and sustainable materials if compatible polymer-filler systems can be engineered through photopolymerization, but this idea is previously unexplored. The first demonstration of photopolymerization and 3D printing with the incorporation of pine pollen as filler in poly(ethylene glycol) diacrylate are presented. The filler properties affecting the related depth of cure and the mechanical, thermal, and functional properties are examined in detail. In addition, the lithography technique is applied to the photocomposites for the production of 3D patterns. 4D printing behavior is also possible through the water swelling and dehydration induced actuation of the 3D printed composites with spatial resolution features. This work is expected to provide a new way to a field for photopolymerization reactions in natural material-resin composites and thereby to expand potential applications in 3D and 4D printing.}, keywords = {}, pubstate = {published}, tppubtype = {article} } Pollen have the potential to be effective plant-based biorenewable reinforcing fillers for polymers due to their chemical stability and unique micro- or nano-structured surfaces. Pollen-polymer composites can form the basis for a new class of light-weight and sustainable materials if compatible polymer-filler systems can be engineered through photopolymerization, but this idea is previously unexplored. The first demonstration of photopolymerization and 3D printing with the incorporation of pine pollen as filler in poly(ethylene glycol) diacrylate are presented. The filler properties affecting the related depth of cure and the mechanical, thermal, and functional properties are examined in detail. In addition, the lithography technique is applied to the photocomposites for the production of 3D patterns. 4D printing behavior is also possible through the water swelling and dehydration induced actuation of the 3D printed composites with spatial resolution features. This work is expected to provide a new way to a field for photopolymerization reactions in natural material-resin composites and thereby to expand potential applications in 3D and 4D printing. |
Liu, Shaohui; Graff, Bernadette; Xiao, Pu; Dumur, Frederic; Lalevee, Jacques Nitro-Carbazole Based Oxime Esters as Dual Photo/Thermal Initiators for 3D Printing and Composite Preparation (Article de journal) Macromolecular Rapid Communications, p. 2100207, 2021. @article{Liu2021a, title = {Nitro-Carbazole Based Oxime Esters as Dual Photo/Thermal Initiators for 3D Printing and Composite Preparation}, author = {Shaohui Liu and Bernadette Graff and Pu Xiao and Frederic Dumur and Jacques Lalevee}, doi = {10.1002/marc.202100207}, year = {2021}, date = {2021-01-01}, journal = {Macromolecular Rapid Communications}, pages = {2100207}, abstract = {A series of Type I photoinitiators (PIs) based on a nitrocarbazole scaffold are developed and examined for the first time as photoinitiators for visible light photopolymerization. Three oxime esters (OXE-M, OXE-V, OXE-P) varying by the terminal groups (acetyl, acryloyl and benzoyl) attached via the oxime ester group are originally prepared. As a result of this, the three PIs exhibit excellent photoinitiation abilities in the presence of acrylate monomers upon LED@ 405 nm irradiation. Markedly, OXE-M exhibits a better performance than the benchmark Type I phosphine-oxide (diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide TPO). Chemical mechanisms supporting the polymerization process with these PIs are investigated by steady state photolysis, molecular orbital calculations and real-time Fourier transformed infrared spectroscopy. After the cleavage of NO bond and decarboxylation, free radicals are generated to initiate the free radical polymerization efficiently. Free radical photopolymerization of OXE-M is applied in direct laser write and 3D printing. Interestingly, OXE-M exhibits thermal initiation behaviors in monomers and can be used as dual photo and thermal initiators. The highly opaque feature of carbon fibers makes it difficult for light penetration, so dual photo/thermal curing are used here to prepare carbon fiber composites.}, keywords = {}, pubstate = {published}, tppubtype = {article} } A series of Type I photoinitiators (PIs) based on a nitrocarbazole scaffold are developed and examined for the first time as photoinitiators for visible light photopolymerization. Three oxime esters (OXE-M, OXE-V, OXE-P) varying by the terminal groups (acetyl, acryloyl and benzoyl) attached via the oxime ester group are originally prepared. As a result of this, the three PIs exhibit excellent photoinitiation abilities in the presence of acrylate monomers upon LED@ 405 nm irradiation. Markedly, OXE-M exhibits a better performance than the benchmark Type I phosphine-oxide (diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide TPO). Chemical mechanisms supporting the polymerization process with these PIs are investigated by steady state photolysis, molecular orbital calculations and real-time Fourier transformed infrared spectroscopy. After the cleavage of NO bond and decarboxylation, free radicals are generated to initiate the free radical polymerization efficiently. Free radical photopolymerization of OXE-M is applied in direct laser write and 3D printing. Interestingly, OXE-M exhibits thermal initiation behaviors in monomers and can be used as dual photo and thermal initiators. The highly opaque feature of carbon fibers makes it difficult for light penetration, so dual photo/thermal curing are used here to prepare carbon fiber composites. |
Aubry, Berengere; Canterel, Remi; Lansalot, Muriel; Bourgeat-Lami, Elodie; Airoudj, Aissam; Graff, Bernadette; Dietlin, Celine; Morlet-Savary, Fabrice; Blahut, Jan; Benda, Ladislav; Pintacuda, Guido; Lacote, Emmanuel; Lalevee, Jacques Development of a borane-(meth)acrylate photo-click reaction. (Article de journal) Angewandte Chemie (International ed. in English), 2021. @article{Aubry2021, title = {Development of a borane-(meth)acrylate photo-click reaction.}, author = {Berengere Aubry and Remi Canterel and Muriel Lansalot and Elodie Bourgeat-Lami and Aissam Airoudj and Bernadette Graff and Celine Dietlin and Fabrice Morlet-Savary and Jan Blahut and Ladislav Benda and Guido Pintacuda and Emmanuel Lacote and Jacques Lalevee}, doi = {10.1002/anie.202103008}, year = {2021}, date = {2021-01-01}, journal = {Angewandte Chemie (International ed. in English)}, abstract = {The development of 3D printing fuels the need for new photoinitiating systems working under mild conditions and/or leading to polymers with new and/or enhanced properties. In this context, we introduce herein N-Heterocyclic Carbene-borane complexes as reagents for a new type of photo-click reaction, the borane-(meth)acrylate click reaction. Remarkably, the higher bond number of boranes relative to thiols induced an increase of the network density associated with faster polymerization kinetics. Solid-state NMR evidenced the strong participation of the boron centers on the network properties, while DMA and AFM showed that the materials exhibit improved mechanical properties, as well as reduced solvent swelling.}, keywords = {}, pubstate = {published}, tppubtype = {article} } The development of 3D printing fuels the need for new photoinitiating systems working under mild conditions and/or leading to polymers with new and/or enhanced properties. In this context, we introduce herein N-Heterocyclic Carbene-borane complexes as reagents for a new type of photo-click reaction, the borane-(meth)acrylate click reaction. Remarkably, the higher bond number of boranes relative to thiols induced an increase of the network density associated with faster polymerization kinetics. Solid-state NMR evidenced the strong participation of the boron centers on the network properties, while DMA and AFM showed that the materials exhibit improved mechanical properties, as well as reduced solvent swelling. |
Marteau, Julie; Anselme, Karine; Pieuchot, Laurent; Chauvy, Pierre-Francois; Bigerelle, Maxence Topography characterization of sinusoidal surfaces obtained with electrochemical machining (Article de journal) Surface Topography-metrology and Properties, 9 (2), p. 025002, 2021. @article{Marteau2021, title = {Topography characterization of sinusoidal surfaces obtained with electrochemical machining}, author = {Julie Marteau and Karine Anselme and Laurent Pieuchot and Pierre-Francois Chauvy and Maxence Bigerelle}, doi = {10.1088/2051-672X/abeae9}, year = {2021}, date = {2021-01-01}, journal = {Surface Topography-metrology and Properties}, volume = {9}, number = {2}, pages = {025002}, abstract = {The study and understanding of functionality and its link with surface topography requires surfaces that enable us to decouple the examined effect. The sinusoidal function offers an easy solution for the decoupling of amplitude and frequency. However, the corresponding surfaces would require very good characteristics: shape regularity, low waviness and low microroughness. This study thoroughly characterized sinusoidal surface (egg-box shapes) having periods ranging from 30 mu m to 300 mu m and peak-to-valley amplitudes comprised between 3 and 30 mu m. The microroughness of the examined surfaces was quantified with the arithmetic mean deviation S-a and was found to be around 1 nm for most examined surfaces. The waviness of the surfaces, which was also quantified with Sa, was lower than 0.15 mu m for all the surfaces. The relative error computed for the period of the sinusoidal surfaces was lower than 1.3%. Finally, the shape regularity was assessed by comparing the measurements to a mathematical function and the computed average residues were smaller than 0.8 mu m. These characteristics highlighted the very good noise-to-signal ratio of the produced surfaces, which can be used in very different fields (biology, mechanics, optics horizontal ellipsis ) to examine topography effect on functionality (cell adhesion, brightness horizontal ellipsis ).}, keywords = {}, pubstate = {published}, tppubtype = {article} } The study and understanding of functionality and its link with surface topography requires surfaces that enable us to decouple the examined effect. The sinusoidal function offers an easy solution for the decoupling of amplitude and frequency. However, the corresponding surfaces would require very good characteristics: shape regularity, low waviness and low microroughness. This study thoroughly characterized sinusoidal surface (egg-box shapes) having periods ranging from 30 mu m to 300 mu m and peak-to-valley amplitudes comprised between 3 and 30 mu m. The microroughness of the examined surfaces was quantified with the arithmetic mean deviation S-a and was found to be around 1 nm for most examined surfaces. The waviness of the surfaces, which was also quantified with Sa, was lower than 0.15 mu m for all the surfaces. The relative error computed for the period of the sinusoidal surfaces was lower than 1.3%. Finally, the shape regularity was assessed by comparing the measurements to a mathematical function and the computed average residues were smaller than 0.8 mu m. These characteristics highlighted the very good noise-to-signal ratio of the produced surfaces, which can be used in very different fields (biology, mechanics, optics horizontal ellipsis ) to examine topography effect on functionality (cell adhesion, brightness horizontal ellipsis ). |
Chen, Hong; Noirbent, Guillaume; Liu, Shaohui; Brunel, Damien; Graff, Bernadette; Gigmes, Didier; Zhang, Yijun; Sun, Ke; Morlet-Savary, Fabrice; Xiao, Pu; Dumur, Frederic; Lalevee, Jacques Bis-chalcone derivatives derived from natural products as near-UV/visible light sensitive photoinitiators for 3D/4D printing (Article de journal) Materials Chemistry Frontiers, 5 (2), p. 901–916, 2021. @article{Chen2021a, title = {Bis-chalcone derivatives derived from natural products as near-UV/visible light sensitive photoinitiators for 3D/4D printing}, author = {Hong Chen and Guillaume Noirbent and Shaohui Liu and Damien Brunel and Bernadette Graff and Didier Gigmes and Yijun Zhang and Ke Sun and Fabrice Morlet-Savary and Pu Xiao and Frederic Dumur and Jacques Lalevee}, doi = {10.1039/d0qm00755b}, year = {2021}, date = {2021-01-01}, journal = {Materials Chemistry Frontiers}, volume = {5}, number = {2}, pages = {901--916}, abstract = {Four series of bis-chalcone compounds based on benzylpiperidinone, tetrahydrothiopyranone, pyridine or biphenyl central parts are designed and synthesized, enabling the development of ten bis-chalcones varying both by the central cores and by the substitution patterns (ortho, meta, para-positions) and the choice of the different groups attached to the peripheral substituents (alkoxy or allyloxy-substituted aromatic rings, thiophene, or ferrocene). In this series of ten bis-chalcones, eight of them were never synthesized before (i.e. only bis-chalcones 8 and 10 were already reported albeit never used as photoinitiators). These different dyes are proposed as new near-UV/visible light sensitive photoinitiators, in combination with an amine and an iodonium salt, to initiate the free radical photopolymerization (FRP) of PEG-diacrylate and the cationic photopolymerization (CP) of EPOX under LED@405 nm and LED@375 nm irradiation conditions. For the photopolymerization of acrylates carried out between thin films in laminate, all the bis-chalcones proposed in this work show higher photoinitiation abilities upon irradiation with a LED at 375 nm than at 405 nm, which is mainly due to their excellent light absorption properties in the near-UV region. Markedly, in contrast with the other two series of bis-chalcone compounds, pyridine-based bis-chalcones prove to be the most efficient photoinitiators, especially the bis-chalcones 5 and 9. Furthermore, all of them can also promote the cationic polymerization of epoxides upon LED irradiation at 375 nm, in the presence of an iodonium salt and an amine. More interestingly, some 3D patterns fabricated through the free radical polymerization of PEG-diacrylate demonstrate reversible swelling properties and shape-memory for access to 4D printing.}, keywords = {}, pubstate = {published}, tppubtype = {article} } Four series of bis-chalcone compounds based on benzylpiperidinone, tetrahydrothiopyranone, pyridine or biphenyl central parts are designed and synthesized, enabling the development of ten bis-chalcones varying both by the central cores and by the substitution patterns (ortho, meta, para-positions) and the choice of the different groups attached to the peripheral substituents (alkoxy or allyloxy-substituted aromatic rings, thiophene, or ferrocene). In this series of ten bis-chalcones, eight of them were never synthesized before (i.e. only bis-chalcones 8 and 10 were already reported albeit never used as photoinitiators). These different dyes are proposed as new near-UV/visible light sensitive photoinitiators, in combination with an amine and an iodonium salt, to initiate the free radical photopolymerization (FRP) of PEG-diacrylate and the cationic photopolymerization (CP) of EPOX under LED@405 nm and LED@375 nm irradiation conditions. For the photopolymerization of acrylates carried out between thin films in laminate, all the bis-chalcones proposed in this work show higher photoinitiation abilities upon irradiation with a LED at 375 nm than at 405 nm, which is mainly due to their excellent light absorption properties in the near-UV region. Markedly, in contrast with the other two series of bis-chalcone compounds, pyridine-based bis-chalcones prove to be the most efficient photoinitiators, especially the bis-chalcones 5 and 9. Furthermore, all of them can also promote the cationic polymerization of epoxides upon LED irradiation at 375 nm, in the presence of an iodonium salt and an amine. More interestingly, some 3D patterns fabricated through the free radical polymerization of PEG-diacrylate demonstrate reversible swelling properties and shape-memory for access to 4D printing. |
Beda, Adrian; Rabuel, Francois; Morcrette, Mathieu; Knopf, Stephan; Taberna, Pierre-Louis; Simon, Patrice; Ghimbeu, Camelia Matei Hard carbon key properties allow for the achievement of high Coulombic efficiency and high volumetric capacity in Na-ion batteries (Article de journal) Journal of Materials Chemistry A, 9 (3), p. 1743–1758, 2021. @article{Beda2021a, title = {Hard carbon key properties allow for the achievement of high Coulombic efficiency and high volumetric capacity in Na-ion batteries}, author = {Adrian Beda and Francois Rabuel and Mathieu Morcrette and Stephan Knopf and Pierre-Louis Taberna and Patrice Simon and Camelia Matei Ghimbeu}, doi = {10.1039/d0ta07687b}, year = {2021}, date = {2021-01-01}, journal = {Journal of Materials Chemistry A}, volume = {9}, number = {3}, pages = {1743--1758}, abstract = {The volumetric capacity and the initial Coulombic efficiency are features of major importance when it comes to the development of full-cell batteries, and are thus key characteristics to boost Na-ion batteries (NIBs) commercialization. To allow the improvement of these parameters, several hard carbon properties that are rarely addressed, such as tapped density and electrode porosity after calendaring, were investigated herein in relation with their physico-chemical characteristics and electrochemical performance. A series of sustainable and scalable synthesized hard carbon spheres with controlled properties were used in this purpose. It was found that the electrode porosity after calendaring decreases rather linearly with the graphite interlayer space (d(002)), the lowest value (41%) being reached for high temperature treated carbons (>1500 degrees C). No clear correlation could be established between the electrode porosity and the tapped density. This could be understood by the dependence of the tapped density on several interplaying parameters, including the porosity (open, closed and inter-grain) and the morphology (particle shape and size). The compact carbon electrodes could deliver a high volumetric capacity of similar to 300 mA h cm(-3). Such performance was achieved by combining low electrode porosity, low interlayer space, and low specific surface area as emphasized by comparison with several other labmade and commercial hard carbons. Moreover, these carbon spheres revealed an initial Coulombic efficiency of 92%, which is among the highest value reported for hard carbon. This could be correlated in large extent with the low values of the specific surface area of ultra-micropores (<0.7 nm), and further to the low amount of active sites and oxygen-containing functional groups. Several valuable propertyperformance correlations could be established, allowing for predicting the behavior of hard carbons in the Na-ion half-cells and full-cells.}, keywords = {}, pubstate = {published}, tppubtype = {article} } The volumetric capacity and the initial Coulombic efficiency are features of major importance when it comes to the development of full-cell batteries, and are thus key characteristics to boost Na-ion batteries (NIBs) commercialization. To allow the improvement of these parameters, several hard carbon properties that are rarely addressed, such as tapped density and electrode porosity after calendaring, were investigated herein in relation with their physico-chemical characteristics and electrochemical performance. A series of sustainable and scalable synthesized hard carbon spheres with controlled properties were used in this purpose. It was found that the electrode porosity after calendaring decreases rather linearly with the graphite interlayer space (d(002)), the lowest value (41%) being reached for high temperature treated carbons (>1500 degrees C). No clear correlation could be established between the electrode porosity and the tapped density. This could be understood by the dependence of the tapped density on several interplaying parameters, including the porosity (open, closed and inter-grain) and the morphology (particle shape and size). The compact carbon electrodes could deliver a high volumetric capacity of similar to 300 mA h cm(-3). Such performance was achieved by combining low electrode porosity, low interlayer space, and low specific surface area as emphasized by comparison with several other labmade and commercial hard carbons. Moreover, these carbon spheres revealed an initial Coulombic efficiency of 92%, which is among the highest value reported for hard carbon. This could be correlated in large extent with the low values of the specific surface area of ultra-micropores (<0.7 nm), and further to the low amount of active sites and oxygen-containing functional groups. Several valuable propertyperformance correlations could be established, allowing for predicting the behavior of hard carbons in the Na-ion half-cells and full-cells. |
Caron, Aurore; Noirbent, Guillaume; Gigmes, Didier; Dumur, Frederic; Lalevee, Jacques Near-Infrared PhotoInitiating Systems: Photothermal versus Triplet-Triplet Annihilation-Based Upconversion Polymerization (Article de journal) Macromolecular Rapid Communications, p. 2100047, 2021. @article{Caron2021, title = {Near-Infrared PhotoInitiating Systems: Photothermal versus Triplet-Triplet Annihilation-Based Upconversion Polymerization}, author = {Aurore Caron and Guillaume Noirbent and Didier Gigmes and Frederic Dumur and Jacques Lalevee}, doi = {10.1002/marc.202100047}, year = {2021}, date = {2021-01-01}, journal = {Macromolecular Rapid Communications}, pages = {2100047}, abstract = {NIR light-induced polymerization has attracted more and more attention in the photopolymerization field due to the possibility to use safer and more penetrating wavelengths, reducing the hazardousness. Here, a novel perspective for the free radical polymerization of acrylate-based monomers based on triplet-triplet annihilation upconversion (TTA-UC) is proposed, avoiding the introduction of heavy metals, usually required in the TTA processes. Thermal imaging experiments and Fourier transform infrared spectroscopy are respectively used to record the temperature during NIR irradiation and measure the reactive function conversion. The competition between the TTA-UC and the NIR photothermal activation is investigated to compare the relative efficiency of both NIR processes. In view of the results obtained by the different methods, the photothermal effect seems to get the upper hand over the photoactivation of the system.}, keywords = {}, pubstate = {published}, tppubtype = {article} } NIR light-induced polymerization has attracted more and more attention in the photopolymerization field due to the possibility to use safer and more penetrating wavelengths, reducing the hazardousness. Here, a novel perspective for the free radical polymerization of acrylate-based monomers based on triplet-triplet annihilation upconversion (TTA-UC) is proposed, avoiding the introduction of heavy metals, usually required in the TTA processes. Thermal imaging experiments and Fourier transform infrared spectroscopy are respectively used to record the temperature during NIR irradiation and measure the reactive function conversion. The competition between the TTA-UC and the NIR photothermal activation is investigated to compare the relative efficiency of both NIR processes. In view of the results obtained by the different methods, the photothermal effect seems to get the upper hand over the photoactivation of the system. |
Rahal, Mahmoud; Graff, Bernadette; Toufaily, Joumana; Hamieh, Tayssir; Noirbent, Guillaume; Gigmes, Didier; Dumur, Frederic; Lalevee, Jacques Molecules (Basel, Switzerland), 26 (6), 2021. @article{Rahal2021a, title = {3-Carboxylic Acid and Formyl-Derived Coumarins as Photoinitiators in Photo-Oxidation or Photo-Reduction Processes for Photopolymerization upon Visible Light: Photocomposite Synthesis and 3D Printing Applications.}, author = {Mahmoud Rahal and Bernadette Graff and Joumana Toufaily and Tayssir Hamieh and Guillaume Noirbent and Didier Gigmes and Frederic Dumur and Jacques Lalevee}, doi = {10.3390/molecules26061753}, year = {2021}, date = {2021-01-01}, journal = {Molecules (Basel, Switzerland)}, volume = {26}, number = {6}, abstract = {In this paper, nine organic compounds based on the coumarin scaffold and different substituents were synthesized and used as high-performance photoinitiators for free radical photopolymerization (FRP) of meth(acrylate) functions under visible light irradiation using LED at 405 nm. In fact, these compounds showed a very high initiation capacity and very good polymerization profiles (both high rate of polymerization (Rp) and final conversion (FC)) using two and three-component photoinitiating systems based on coum/iodonium salt (0.1%/1% w/w) and coum/iodonium salt/amine (0.1%/1%/1% w/w/w), respectively. To demonstrate the efficiency of the initiation of photopolymerization, several techniques were used to study the photophysical and photochemical properties of coumarins, such as: UV-visible absorption spectroscopy, steady-state photolysis, real-time FTIR, and cyclic voltammetry. On the other hand, these compounds were also tested in direct laser write experiments (3D printing). The synthesis of photocomposites based on glass fiber or carbon fiber using an LED conveyor at 385 nm (0.7 W/cm2) was also examined.}, keywords = {}, pubstate = {published}, tppubtype = {article} } In this paper, nine organic compounds based on the coumarin scaffold and different substituents were synthesized and used as high-performance photoinitiators for free radical photopolymerization (FRP) of meth(acrylate) functions under visible light irradiation using LED at 405 nm. In fact, these compounds showed a very high initiation capacity and very good polymerization profiles (both high rate of polymerization (Rp) and final conversion (FC)) using two and three-component photoinitiating systems based on coum/iodonium salt (0.1%/1% w/w) and coum/iodonium salt/amine (0.1%/1%/1% w/w/w), respectively. To demonstrate the efficiency of the initiation of photopolymerization, several techniques were used to study the photophysical and photochemical properties of coumarins, such as: UV-visible absorption spectroscopy, steady-state photolysis, real-time FTIR, and cyclic voltammetry. On the other hand, these compounds were also tested in direct laser write experiments (3D printing). The synthesis of photocomposites based on glass fiber or carbon fiber using an LED conveyor at 385 nm (0.7 W/cm2) was also examined. |
Fakir, Abdellah Ait El; Anfar, Zakaria; Amedlous, Abdallah; Zbair, Mohamed; Hafidi, Zakaria; Achouri, Mohammed El; Jada, Amane; Alem, Noureddine El Engineering of new hydrogel beads based conducting polymers: Metal-free catalysis for highly organic pollutants degradation (Article de journal) Applied Catalysis B-environmental, 286 , p. 119948, 2021. @article{ElFakir2021, title = {Engineering of new hydrogel beads based conducting polymers: Metal-free catalysis for highly organic pollutants degradation}, author = {Abdellah Ait El Fakir and Zakaria Anfar and Abdallah Amedlous and Mohamed Zbair and Zakaria Hafidi and Mohammed El Achouri and Amane Jada and Noureddine El Alem}, doi = {10.1016/j.apcatb.2021.119948}, year = {2021}, date = {2021-01-01}, journal = {Applied Catalysis B-environmental}, volume = {286}, pages = {119948}, abstract = {Engineering of new heterogeneous metal-free catalysts is of great importance for persulfate activation. Herein, Innovative conductive polymers Polyaniline (PANI) and Polypyrrole (PPy) were used as promising catalysts for PS activation to effectively degrade organic pollutants. In fact, PANI and PPy can provide the necessary electron transfer based on nitrogen atoms located in the conjugated chains compared to their counterparts in the defective sites. In addition, PANI and PPy were immobilized inside membrane formed by cross linking alginate biopolymer by divalent calcium ions, in order to develop a new stable hydrogel beads catalyst. The prepared hydrogels-activated PS process could maintain excellent catalytic properties, mitigate catalysts deactivation, increased chemical stability and offer hope for their application in the industrial scale. The radical scavenging experiments monitored by the electron paramagnetic resonance and functional theory calculations, indicated the role of the PANI and PPy conjugated chains and the nature of the reaction pathways.}, keywords = {}, pubstate = {published}, tppubtype = {article} } Engineering of new heterogeneous metal-free catalysts is of great importance for persulfate activation. Herein, Innovative conductive polymers Polyaniline (PANI) and Polypyrrole (PPy) were used as promising catalysts for PS activation to effectively degrade organic pollutants. In fact, PANI and PPy can provide the necessary electron transfer based on nitrogen atoms located in the conjugated chains compared to their counterparts in the defective sites. In addition, PANI and PPy were immobilized inside membrane formed by cross linking alginate biopolymer by divalent calcium ions, in order to develop a new stable hydrogel beads catalyst. The prepared hydrogels-activated PS process could maintain excellent catalytic properties, mitigate catalysts deactivation, increased chemical stability and offer hope for their application in the industrial scale. The radical scavenging experiments monitored by the electron paramagnetic resonance and functional theory calculations, indicated the role of the PANI and PPy conjugated chains and the nature of the reaction pathways. |
Dahou, T; Defoort, F; Khiari, B; Labaki, M; Dupont, C; Jeguirim, M Role of inorganics on the biomass char gasification reactivity: A review involving reaction mechanisms and kinetics models (Article de journal) Renewable & Sustainable Energy Reviews, 135 , p. 110136, 2021. @article{Dahou2021, title = {Role of inorganics on the biomass char gasification reactivity: A review involving reaction mechanisms and kinetics models}, author = {T Dahou and F Defoort and B Khiari and M Labaki and C Dupont and M Jeguirim}, doi = {10.1016/j.rser.2020.110136}, year = {2021}, date = {2021-01-01}, journal = {Renewable & Sustainable Energy Reviews}, volume = {135}, pages = {110136}, abstract = {This review article presents the effects of the inorganic elements and compounds on gasification and their mechanisms of action. The influence of inorganics on the gasification reaction have been described in the literature. However, the specific phenomena involved and the mechanisms of action are not stated with consensus. Therefore, the present review gathers the various mechanisms proposed by authors. Some have been demonstrated to be unlikely such as the mechanisms involving intercalation compounds or mechanical actions. In order to give more practical applications of this work, the review also gathers the gasification kinetic models that take these inorganic effects into account.}, keywords = {}, pubstate = {published}, tppubtype = {article} } This review article presents the effects of the inorganic elements and compounds on gasification and their mechanisms of action. The influence of inorganics on the gasification reaction have been described in the literature. However, the specific phenomena involved and the mechanisms of action are not stated with consensus. Therefore, the present review gathers the various mechanisms proposed by authors. Some have been demonstrated to be unlikely such as the mechanisms involving intercalation compounds or mechanical actions. In order to give more practical applications of this work, the review also gathers the gasification kinetic models that take these inorganic effects into account. |
Chen, Hong; Zhang, Yijun; Bonfiglio, Anna; Morlet-Savary, Fabrice; Mauro, Matteo; Lalevee, Jacques Rhenium(I) N-Heterocyclic Carbene Complexes in Photoinitiating Systems for Polymerization upon Visible Light: Development of Photosensitive Resins for 3D and 4D Applications (Article de journal) Acs Applied Polymer Materials, 3 (1), p. 464–473, 2021. @article{Chen2021, title = {Rhenium(I) N-Heterocyclic Carbene Complexes in Photoinitiating Systems for Polymerization upon Visible Light: Development of Photosensitive Resins for 3D and 4D Applications}, author = {Hong Chen and Yijun Zhang and Anna Bonfiglio and Fabrice Morlet-Savary and Matteo Mauro and Jacques Lalevee}, doi = {10.1021/acsapm.0c01207}, year = {2021}, date = {2021-01-01}, journal = {Acs Applied Polymer Materials}, volume = {3}, number = {1}, pages = {464--473}, abstract = {Two fac-rhenium tris-carbonyl complexes bearing a pi-accepting pyridoannelated N-heterocyclic carbene (NHC) ligand with general formula Re(CO)(3) (pyipy)X, where pyipy is 2-pyridil-imidazo[1,5-a]pyridine-3-ylidene and X = CI (Re1) and Br (Re2), are investigated as photoredox catalytic systems in light-promoted polymerization reactions. Both rhenium(I) complexes are able to efficiently generate radicals to initiate free radical polymerization. Remarkably, excellent radical polymerization profiles and final conversions are obtained under soft irradiations (LED lamp, lambda(exc) = 405 nm) by using the proposed complexes with iodonium salt and amine as photoinitiating systems (PISs) for polyethyleneglycol (PEG)-acrylate monomers. The involved mechanism is investigated by means of different spectroscopic techniques and further supported by electrochemical data. In addition, using the prepared three-component PISs, outstanding 3D patterns with spatial resolution could be obtained through direct laser write experiments. Remarkably, the resulting material displays reversible deformation that can be controlled with heating-hydration cycles due to stimuli-responsiveness of PEG chains of the polymeric network, thus opening the way for innovative smart and stimuli-responsive 4D-printed materials and soft actuators.}, keywords = {}, pubstate = {published}, tppubtype = {article} } Two fac-rhenium tris-carbonyl complexes bearing a pi-accepting pyridoannelated N-heterocyclic carbene (NHC) ligand with general formula Re(CO)(3) (pyipy)X, where pyipy is 2-pyridil-imidazo[1,5-a]pyridine-3-ylidene and X = CI (Re1) and Br (Re2), are investigated as photoredox catalytic systems in light-promoted polymerization reactions. Both rhenium(I) complexes are able to efficiently generate radicals to initiate free radical polymerization. Remarkably, excellent radical polymerization profiles and final conversions are obtained under soft irradiations (LED lamp, lambda(exc) = 405 nm) by using the proposed complexes with iodonium salt and amine as photoinitiating systems (PISs) for polyethyleneglycol (PEG)-acrylate monomers. The involved mechanism is investigated by means of different spectroscopic techniques and further supported by electrochemical data. In addition, using the prepared three-component PISs, outstanding 3D patterns with spatial resolution could be obtained through direct laser write experiments. Remarkably, the resulting material displays reversible deformation that can be controlled with heating-hydration cycles due to stimuli-responsiveness of PEG chains of the polymeric network, thus opening the way for innovative smart and stimuli-responsive 4D-printed materials and soft actuators. |
Zhang, Yijun; Josien, Ludovic; Salomon, Jean-Pierre; Simon-Masseron, Angelique; Lalevee, Jacques Photopolymerization of Zeolite/Polymer-Based Composites: toward 3D and 4D Printing Applications (Article de journal) Acs Applied Polymer Materials, 3 (1), p. 400–409, 2021. @article{Zhang2021b, title = {Photopolymerization of Zeolite/Polymer-Based Composites: toward 3D and 4D Printing Applications}, author = {Yijun Zhang and Ludovic Josien and Jean-Pierre Salomon and Angelique Simon-Masseron and Jacques Lalevee}, doi = {10.1021/acsapm.0c01170}, year = {2021}, date = {2021-01-01}, journal = {Acs Applied Polymer Materials}, volume = {3}, number = {1}, pages = {400--409}, abstract = {In recent years, photopolymerization has found wide applications in industry and daily life, especially 3D printing. However, some defective properties of photopolymers limit their development, such as their mechanical properties, density, compressive strength, and functionality. Herein, in this work, we reported the fabrication of composites containing seven different kinds of zeolites used as fillers under mild photopolymerization conditions (LTA-5A was selected as the benchmark zeolite), that is, visible LED light irradiation at room temperature under air. The filler properties affecting the related depth of cure and the enhanced mechanical (the storage modulus increased by 10-fold compared to that of a pure polymer) and functional properties were examined in detail. In addition, the production of 3D patterns was performed through direct laser writing (DLW) as a lithography technique. As a real breakthrough, the 3D printing of zeolite/polymer composites is presented here for the first time with high filler contents (up to 75 wt %) using this stereolithography approach. 4D behavior can be established in the presence of water, that is, the 3D object can change the shape and return to the starting geometry after desiccation. Remarkably, after debinding of the composites by thermal treatment, a high zeolite porosity can be regenerated. Therefore, the 3D printing of zeolites is possible in two steps: (i) photopolymerization of organic/zeolite composites to generate the desired shape, followed by (ii) removal of the organic part by thermal treatment. This work is expected to lead to valuable developments in the field of photopolymerization reactions in highly filled composites (with the filler content exceeding 50 wt %) and thereby expand their potential application for 3D or 4D printing in the fields of for example, high-performance lightweight materials and adsorption.}, keywords = {}, pubstate = {published}, tppubtype = {article} } In recent years, photopolymerization has found wide applications in industry and daily life, especially 3D printing. However, some defective properties of photopolymers limit their development, such as their mechanical properties, density, compressive strength, and functionality. Herein, in this work, we reported the fabrication of composites containing seven different kinds of zeolites used as fillers under mild photopolymerization conditions (LTA-5A was selected as the benchmark zeolite), that is, visible LED light irradiation at room temperature under air. The filler properties affecting the related depth of cure and the enhanced mechanical (the storage modulus increased by 10-fold compared to that of a pure polymer) and functional properties were examined in detail. In addition, the production of 3D patterns was performed through direct laser writing (DLW) as a lithography technique. As a real breakthrough, the 3D printing of zeolite/polymer composites is presented here for the first time with high filler contents (up to 75 wt %) using this stereolithography approach. 4D behavior can be established in the presence of water, that is, the 3D object can change the shape and return to the starting geometry after desiccation. Remarkably, after debinding of the composites by thermal treatment, a high zeolite porosity can be regenerated. Therefore, the 3D printing of zeolites is possible in two steps: (i) photopolymerization of organic/zeolite composites to generate the desired shape, followed by (ii) removal of the organic part by thermal treatment. This work is expected to lead to valuable developments in the field of photopolymerization reactions in highly filled composites (with the filler content exceeding 50 wt %) and thereby expand their potential application for 3D or 4D printing in the fields of for example, high-performance lightweight materials and adsorption. |
Hadroug, Samar; Jellali, Salah; Jeguirim, Mejdi; Kwapinska, Marzena; Hamdi, Helmi; Leahy, James J; Kwapinski, Witold Static and Dynamic Investigations on Leaching/Retention of Nutrients from Raw Poultry Manure Biochars and Amended Agricultural Soil (Article de journal) Sustainability, 13 (3), p. 1212, 2021. @article{Hadroug2021, title = {Static and Dynamic Investigations on Leaching/Retention of Nutrients from Raw Poultry Manure Biochars and Amended Agricultural Soil}, author = {Samar Hadroug and Salah Jellali and Mejdi Jeguirim and Marzena Kwapinska and Helmi Hamdi and James J Leahy and Witold Kwapinski}, doi = {10.3390/su13031212}, year = {2021}, date = {2021-01-01}, journal = {Sustainability}, volume = {13}, number = {3}, pages = {1212}, publisher = {MDPI AG}, abstract = {In this study, nutrients release/adsorption from/by raw poultry manure-derived biochar produced at a pyrolysis temperature of 600 degrees C (RPM-B) was assessed under static and dynamic conditions. Batch sequential leaching experiments of RPM-B for a total contact time of 10 days showed that both phosphorus and potassium were slowly released but with higher amounts compared to various other animal- and lignocellulosic-derived biochars. The cumulated released P and K amounts were assessed to 93.6 and 17.1 mg g(-1), which represent about 95% and 43% of their original contents in the RPM-B, respectively. The column combined leaching/adsorption experiments showed that amending an alkaline sandy agricultural soil with two doses of RPM-B (at 5% and 8% w:w) resulted in an efficient retention of NO3-N and NH4-N, and on the contrary, important leached amounts of PO4-P, K+, Mg2+, and Ca2+ but with relatively slow kinetic release rates for a long period. Even after 40 days of dynamic leaching, these latter nutrients continued to be released with kinetic rates lower than 10 mg kg(-1) d(-1). Thus, compared to synthetic fertilizers, RPM-B valorization as organic amendment for poor semiarid soils could be considered as an attractive, eco-friendly, and sustainable waste recycling option.}, keywords = {}, pubstate = {published}, tppubtype = {article} } In this study, nutrients release/adsorption from/by raw poultry manure-derived biochar produced at a pyrolysis temperature of 600 degrees C (RPM-B) was assessed under static and dynamic conditions. Batch sequential leaching experiments of RPM-B for a total contact time of 10 days showed that both phosphorus and potassium were slowly released but with higher amounts compared to various other animal- and lignocellulosic-derived biochars. The cumulated released P and K amounts were assessed to 93.6 and 17.1 mg g(-1), which represent about 95% and 43% of their original contents in the RPM-B, respectively. The column combined leaching/adsorption experiments showed that amending an alkaline sandy agricultural soil with two doses of RPM-B (at 5% and 8% w:w) resulted in an efficient retention of NO3-N and NH4-N, and on the contrary, important leached amounts of PO4-P, K+, Mg2+, and Ca2+ but with relatively slow kinetic release rates for a long period. Even after 40 days of dynamic leaching, these latter nutrients continued to be released with kinetic rates lower than 10 mg kg(-1) d(-1). Thus, compared to synthetic fertilizers, RPM-B valorization as organic amendment for poor semiarid soils could be considered as an attractive, eco-friendly, and sustainable waste recycling option. |
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