Valorization of biomass for the design of bioactive materials under irradiation

La valorisation des dérivés phénoliques et terpéniques issus de la biomasse s’insère parfaitement dans le défi actuel de nos sociétés qui pousse la chimie traditionnelle à évoluer vers une chimie durable. De par leur nature insaturée, les terpènes se montrent particulièrement intéressants pour synthétiser de nouveaux matériaux par réaction de chimie thiol-ène. Parallèlement, les dérivés phénoliques peuvent être facilement modifiés en synthons insaturés, susceptibles de réagir dans ces mêmes réactions. Ainsi, une large gamme de matériaux à base de linalol et d’eugénol a été élaborée sous irradiation UV. Une approche par photochimie a été privilégiée puisqu’elle s’inscrit parfaitement dans le cadre d’une chimie plus respectueuse de l’environnement. L’effet bénéfique des fonctions oxygénées du linalol et du phénol de l’eugénol sur l’activité antibactérienne a été démontré contre deux souches bactériennes principalement responsables du développement des maladies nosocomiales : S. aureus et E. coli. L’incorporation de nanoparticules de ZnO, de carvacrol ou d’acide tannique lors de la réaction de réticulation permet d’améliorer les propriétés antimicrobiennes de manière significative. L’association avec des polyesters semi-cristallins biosourcés et biodégradables présente une alternative intéressante pour optimiser les performances thermomécaniques des matériaux obtenus.Un deuxième type de matériaux a été synthétisé par photo-réticulation de dérivés phénoliques époxydés comme le résorcinol ou l’eugénol. La polymérisation cationique par ouverture de cycle photoamorcée permet la synthèse de matériaux dont les propriétés mécaniques sont plus élevées que les matériaux obtenus par réaction thiol-ène, et d’autre part de s’affranchir de l’agent réticulant à base de thiol. La synthèse de différents dérivés de l’eugénol mono-époxydés offre l’avantage de pouvoir moduler la composition des matériaux obtenus qui peuvent contenir des fonctions phénol et/ou des insaturations. Les groupements phénols sont indispensables à l’activité antibactérienne et sont à l’origine des propriétés anti-oxydantes. La possibilité d’introduire des insaturations permet une post- fonctionnalisation de la surface des matériaux.Ainsi une large gamme de matériaux réticulés, biosourcés et bioactifs dont les propriétés varient de l’élastomère au thermodurcissable a été synthétisée sous irradiationThe valorization of phenolic and terpene derivatives of biomass is perfectly in line with the current challenge of our societies that drives traditional chemistry to evolve towards a sustainable chemistry. Because of their unsaturated nature, terpenes are particularly interesting for synthesizing new materials by thiol-ene chemistry. At the same time, the phenolic derivatives can easily be modified to unsaturated synthons capable of reacting in these same reactions. Thus, a wide range of materials based on linalool and eugenol has been developed under UV irradiation. An approach by photochemistry has been selected since it fits perfectly within the framework of a chemistry more respectful of the environment. The beneficial effect of the oxygenated functions of linalol and phenolic functions of eugenol on antibacterial activity was demonstrated against two bacterial strains mainly responsible for the development of nosocomial diseases: S. aureus and E. coli. The incorporation of ZnO nanoparticles, carvacrol or tannic acid during the crosslinking reaction makes it possible to improve the antimicrobial properties significantly. The association with semi-crystalline biobased and biodegradable polyesters presents an interesting alternative to optimize the thermomechanical performance of the obtained materials.A second type of materials has been synthesized by photocrosslinking epoxidized phenolic derivatives such as resorcinol or eugenol. The photoinitiated cationic polymerization by opening of the ring enables the synthesis of materials whose mechanical properties are higher than the materials obtained by thiol-ene reaction and on the other hand to get rid of the thiol-based crosslinking agent. The synthesis of various monoepoxidized eugenol derivatives offers the advantage of being able to modulate the composition of the obtained materials which may contain phenol functions and / or unsaturations. The phenol groups are essential to the antibacterial activity and lead to the antioxidant properties. The possibility of introducing unsaturations allows a post-functionalization of the surface of the materials.Thus, a wide range of crosslinked, biosourced and bioactive materials whose properties vary from elastomer to thermosetting have been synthesized under irradiatio

Valorisation de la biomasse pour l'élaboration de matériaux bioactifs sous irradiation

The valorization of phenolic and terpene derivatives of biomass is perfectly in line with the current challenge of our societies that drives traditional chemistry to evolve towards a sustainable chemistry. Because of their unsaturated nature, terpenes are particularly interesting for synthesizing new materials by thiol-ene chemistry. At the same time, the phenolic derivatives can easily be modified to unsaturated synthons capable of reacting in these same reactions. Thus, a wide range of materials based on linalool and eugenol has been developed under UV irradiation. An approach by photochemistry has been selected since it fits perfectly within the framework of a chemistry more respectful of the environment. The beneficial effect of the oxygenated functions of linalol and phenolic functions of eugenol on antibacterial activity was demonstrated against two bacterial strains mainly responsible for the development of nosocomial diseases: S. aureus and E. coli. The incorporation of ZnO nanoparticles, carvacrol or tannic acid during the crosslinking reaction makes it possible to improve the antimicrobial properties significantly. The association with semi-crystalline biobased and biodegradable polyesters presents an interesting alternative to optimize the thermomechanical performance of the obtained materials.A second type of materials has been synthesized by photocrosslinking epoxidized phenolic derivatives such as resorcinol or eugenol. The photoinitiated cationic polymerization by opening of the ring enables the synthesis of materials whose mechanical properties are higher than the materials obtained by thiol-ene reaction and on the other hand to get rid of the thiol-based crosslinking agent. The synthesis of various monoepoxidized eugenol derivatives offers the advantage of being able to modulate the composition of the obtained materials which may contain phenol functions and / or unsaturations. The phenol groups are essential to the antibacterial activity and lead to the antioxidant properties. The possibility of introducing unsaturations allows a post-functionalization of the surface of the materials.Thus, a wide range of crosslinked, biosourced and bioactive materials whose properties vary from elastomer to thermosetting have been synthesized under irradiationLa valorisation des dérivés phénoliques et terpéniques issus de la biomasse s’insère parfaitement dans le défi actuel de nos sociétés qui pousse la chimie traditionnelle à évoluer vers une chimie durable. De par leur nature insaturée, les terpènes se montrent particulièrement intéressants pour synthétiser de nouveaux matériaux par réaction de chimie thiol-ène. Parallèlement, les dérivés phénoliques peuvent être facilement modifiés en synthons insaturés, susceptibles de réagir dans ces mêmes réactions. Ainsi, une large gamme de matériaux à base de linalol et d’eugénol a été élaborée sous irradiation UV. Une approche par photochimie a été privilégiée puisqu’elle s’inscrit parfaitement dans le cadre d’une chimie plus respectueuse de l’environnement. L’effet bénéfique des fonctions oxygénées du linalol et du phénol de l’eugénol sur l’activité antibactérienne a été démontré contre deux souches bactériennes principalement responsables du développement des maladies nosocomiales : S. aureus et E. coli. L’incorporation de nanoparticules de ZnO, de carvacrol ou d’acide tannique lors de la réaction de réticulation permet d’améliorer les propriétés antimicrobiennes de manière significative. L’association avec des polyesters semi-cristallins biosourcés et biodégradables présente une alternative intéressante pour optimiser les performances thermomécaniques des matériaux obtenus.Un deuxième type de matériaux a été synthétisé par photo-réticulation de dérivés phénoliques époxydés comme le résorcinol ou l’eugénol. La polymérisation cationique par ouverture de cycle photoamorcée permet la synthèse de matériaux dont les propriétés mécaniques sont plus élevées que les matériaux obtenus par réaction thiol-ène, et d’autre part de s’affranchir de l’agent réticulant à base de thiol. La synthèse de différents dérivés de l’eugénol mono-époxydés offre l’avantage de pouvoir moduler la composition des matériaux obtenus qui peuvent contenir des fonctions phénol et/ou des insaturations. Les groupements phénols sont indispensables à l’activité antibactérienne et sont à l’origine des propriétés anti-oxydantes. La possibilité d’introduire des insaturations permet une post- fonctionnalisation de la surface des matériaux.Ainsi une large gamme de matériaux réticulés, biosourcés et bioactifs dont les propriétés varient de l’élastomère au thermodurcissable a été synthétisée sous irradiatio

Co-Networks Poly(hydroxyalkanoates)-Terpenes to Enhance Antibacterial Properties

Biocompatible and biodegradable bacterial polyesters, poly(hydroxyalkanoates) (PHAs), were combined with linalool, a well-known monoterpene, extracted from spice plants to design novel antibacterial materials. Their chemical association by a photo-induced thiol-ene reaction provided materials having both high mechanical resistance and flexibility. The influence of the nature of the crosslinking agent and the weight ratio of linalool on the thermo-mechanical performances were carefully evaluated. The elongation at break increases from 7% for the native PHA to 40% for PHA–linalool co-networks using a tetrafunctional cross-linking agent. The materials highlighted tremendous anti-adherence properties against Escherichia coli and Staphylococcus aureus by increasing linalool ratios. A significant decrease in antibacterial adhesion of 63% and 82% was observed for E. coli and S. aureus, respectively

Novel poly(3-hydroxy butyrate) macro RAFT agent. Synthesis and characterization of thermoresponsive block copolymers

WOS: 000532737000001TARAMASCOPUSTARAMAWOSA novel reversible addition fragmentation transfer (RAFT) agent based on the poly-3-hydroxy butyrate (PHB) with threehydroxyl groups (PHB-R2) and thermoresponsive amphiphilic block copolymers derived from N-isopropyl acryl amide(NIPAM) are described. Hydroxylated PHB is obtained by the reaction between PHB and diethanol amine (DEA) to preparehydroxylated PHB (PHB-DEA). It is then reacted with a RAFT agent, 2-(dodecylthiocarbonothioylthio)-2-methylpropionic acid(DDMAT). Hydroxyl ends of the hydroxylated PHB are capped with carboxylic acid end of the trithiocarbonate. The blockcopolymers obtained by the polymerization of NIPAM initiated by PHB-R2 were characterized by1H NMR and physicochem-ical techniques. PHB content in the obtained block copolymers is varying between 14 and 45 wt%. The thermo-responsive PHB-PNIPAM block copolymers show the lower critical solution temperature (LCST) 28 and 30 °C while LCSTof the pure PNIPAMis 32 °C.Kapadokya Üniversitesi: KuN.2018-BAGP-001 Bulent Ecevit Üniversitesi: BEU-2017-72118496-0

Enhancement of Biological Properties of Photoinduced Biobased Networks by Post-Functionalization with Antibacterial Molecule

International audienc

Co-Networks Poly(hydroxyalkanoates)-Terpenes to Enhance Antibacterial Properties

International audienceBiocompatible and biodegradable bacterial polyesters, poly(hydroxyalkanoates) (PHAs), were combined with linalool, a well-known monoterpene, extracted from spice plants to design novel antibacterial materials. Their chemical association by a photo-induced thiol-ene reaction provided materials having both high mechanical resistance and flexibility. The influence of the nature of the crosslinking agent and the weight ratio of linalool on the thermo-mechanical performances were carefully evaluated. The elongation at break increases from 7% for the native PHA to 40% for PHA–linalool co-networks using a tetrafunctional cross-linking agent. The materials highlighted tremendous anti-adherence properties against Escherichia coli and Staphylococcus aureus by increasing linalool ratios. A significant decrease in antibacterial adhesion of 63% and 82% was observed for E. coli and S. aureus, respectively

Antibacterial and antioxidant photoinitiated epoxy co-networks of resorcinol and eugenol derivatives

International audienc

Poly(3-hydroxyalkanoate) sulfonate: From nanoparticles toward water soluble polyesters

International audienc

N6L-functionalized nanoparticles for targeted and inhibited pancreatic cancer cells

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Multiscale Structural Characterization of Biobased Diallyl–Eugenol Polymer Networks

International audienceBiosourced eugenol-based polymer networks have a potential functionality for antibacterial coating applications. The presence of carvacrol, a phenol compound, exacerbates these properties. However, the relationship between the network structure and the macroscopic thermomechanical behavior is not known for these biopolymers. Thus, this work details a robust study of this relationship through a multiscale experimental approach combining Dielectric spectroscopy, DMA, Tensile testing and Time domain DQ 1 H NMR. It was shown that carvacrol has an influence on the molecular mobility of the materials. Namely it induces the appearance of a shouldering on the γ relaxation and a diminishing of T α. More surprisingly, up to 20% wt , carvacrol increases the elastic E and Young's E moduli. This observation can be interpreted as an increase of the crosslink density ν C of the networks. Time domain DQ 1 H NMR shows that the 1 residual dipolar coupling constant D res also increases. Thus, carvacrol seems to act as both a thermal plasticizer and a mechanical reinforcement, which may seem to be antagonistic trends. For carvacrol contents over 20% wt these properties diminish due to a saturation of this molecule in the networks and the onset of a phase separation. By combining the aforementioned techniques, it was proven that carvacrol linearly increased the measured crosslink density and thermomechanical properties by physically bonding to the networks through π − π interactions. These interactions would act as physical crosslinks. This work demonstrates that by correlating the results of various multiscale experimental techniques, a better comprehension of the structure-property relationship can be established for biobased functional polymer networks