Photodimerization as an alternative to photocrosslinking of nanoparticles: proof of concept with amphiphilic linear polyoxazoline bearing coumarin unit

International audiencePhotosensitive amphiphilic linear polyoxazolines (CoumC 11-POx n) bearing alkyl chain decorated by a UV-active coumarin end group have been synthesized by cationic ring-opening polymerization (CROP). Using DLS and DOSY NMR experiments, their self-assemblies in water were compared with those of homologous photo-unreactiveamphiphilic polyoxazolines (C m-POx n). In both cases, spherical nanoparticles with D H-values around 10 nm were observed. The CoumC 11-POx n nanoparticles were illuminated upon 300 nm inducing the photo-dimerization of the coumarin units located in theinnercompartment of the nanoparticles. Finally, the pros and the cons of the photo-dimerization of linear copolymersrelated to the photo-crosslinking of graft copolymerswere discussed

Systèmes supramoléculaires à base d'a-cyclodextrines et de poly(oxyéthylène),Structure et propriétés des pseudo-polyrotaxanes, polyrotaxanes et gels glissants

Nous avons étudié le processus de complexation entre les a-cyclodextrines (a-CD) et le poly(oxyéthylène) (PEO) dans l'eau, conduisant ainsi à la formation de complexes d'inclusion appelés pseudo-polyrotaxanes (PPR). A 30°C, nous avons établi que, dans une première étape, les a-CD complexent les chaînes de PEO, formant des molécules de PPR. A plus grande échelle, une agrégation rapide des molécules de PPR a lieu et des nano-cylindres à base d'a-CD complexées se forment. A plus grande échelle encore, les nano-cylindres à base d'a-CD s'associent de manière gaussienne, engendrant la formation de domaines précités. Ensuite, dans une seconde étape, le système subit une auto-réorganisation caractérisée par une augmentation de la compacité des domaines précités, et il se forme un gel physique. Nous avons ensuite investigué les polyrotaxanes (PR), c'est-à-dire les PPR à base d'a-CD et de PEO bouchonnés stériquement aux extrémités, en solution concentrée dans le diméthylsulfoxyde (DMSO) et avons établi qu'ils ont la particularité de former des gels physiques au cours du temps à température ambiante. L'origine moléculaire de l'auto-organisation est la cristallisation des segments de PEO nus et l'agrégation régulière des a-CD complexées provenant de liaisons hydrogène par l'intermédiaire de leurs groupements hydroxyles. Ensuite, nous avons étudié les gels chimiques obtenus par réticulation des PR par l'intermédiaire de leurs a-CD. La réaction de réticulation chimique avec la divinylsulfone (DVS) n'a pas lieu dans des conditions douces si bien que des domaines hautement réticulés cohabitent avec d'autres qui sont moins réticulés.We studied the threading process between a-cyclodextrins (a-CDs) and poly(ethylene oxide) (PEO° in water, thus leading to the formation of inclusion complexes called pseudo-polyrotaxanes (PPRs). At 30°C, we established that, in a first step, a-CDs thread onto PEO chains, forming PPR molecules. At a higher lenght-scale, rapid aggregation of the PPR molecules occurs and threaded a-CD-based nano-cylinders form. A higher lenght-scale, a-CD_based nano-cylinders associate in a Gaussian way engendering the formation of precited domains. Then, in a second step, the system undergoes its reorganization characterized by a compacity increase of the precipitated domains and forms a physical gel. Then, we studied chemical gels obtained by cross-linking PRs via their a-CDs. The chemical cross-linking reaction with divinym sulfone (DVS) does not occur in soft conditions so that highly cross-linked domains cohabit with less cross-linked ones

Systèmes supramoléculaires à base d'a-cyclodextrines et de poly(oxyéthylène),Structure et propriétés des pseudo-polyrotaxanes, polyrotaxanes et gels glissants

Nous avons étudié le processus de complexation entre les a-cyclodextrines (a-CD) et le poly(oxyéthylène) (PEO) dans l'eau, conduisant ainsi à la formation de complexes d'inclusion appelés pseudo-polyrotaxanes (PPR). A 30°C, nous avons établi que, dans uneWe studied the threading process between a-cyclodextrins (a-CDs) and poly(ethylene oxide) (PEO° in water, thus leading to the formation of inclusion complexes called pseudo-polyrotaxanes (PPRs). At 30°C, we established that, in a first step, a-CDs threa

Supramolecular systems based on α-cyclodextrins and poly(ethylene oxide) : structure and properties of pseudo-polyrotaxanes, polyrotaxanes and sliding gels

Nous avons étudié le processus de complexation entre les α-cyclodextrines (α-CD) et le poly(oxyéthylène) (PEO) dans l'eau, conduisant ainsi à la formation de complexes d'inclusion appelés pseudo-polyrotaxanes (PPR). A 30°C, nous avons établi que, dans une première étape, les α-CD complexent les chaïnes de PEO, formant des molécules de PPR. A plus grande échelle, une agrégation rapide des molécules de PPR a lieu et des nano-cylindres à base d'α-CD complexées se forment. A plus grande échelle encore, les nano-cylindres à base d'α-CD s'associent de manière gaussienne, engendrant la formation de domaines précités. Ensuite, dans une seconde étape, le système subit une auto-réorganisation caractérisée par une augmentation de la compacité des domaines précités, et il se forme un gel physique. Nous avons ensuite investigué les polyrotaxanes (PR), c'est-à-dire les PPR à base d'α-CD et de PEO bouchonnés stériquement aux extrémités, en solution concentrée dans le diméthylsulfoxyde (DMSO) et avons établi qu'ils ont la particularité de former des gels physiques au cours du temps à température ambiante. L'origine moléculaire de l'auto-organisation est la cristallisation des segments de PEO nus et l'agrégation régulière des α-CD complexées provenant de liaisons hydrogène par l'intermédiaire de leurs groupements hydroxyles. Ensuite, nous avons étudié les gels chimiques obtenus par réticulation des PR par l'intermédiaire de leurs α-CD. La réaction de réticulation chimique avec la divinylsulfone (DVS) n'a pas lieu dans des conditions douces si bien que des domaines hautement réticulés cohabitent avec d'autres qui sont moins réticulés.We studied the threading process between α-cyclodextrins (α-CDs) and poly(ethylene oxide) (PEO° in water, thus leading to the formation of inclusion complexes called pseudo-polyrotaxanes (PPRs). At 30°C, we established that, in a first step, α-CDs thread onto PEO chains, forming PPR molecules. At a higher lenght-scale, rapid aggregation of the PPR molecules occurs and threaded α-CD-based nano-cylinders form. A higher lenght-scale, α-CD_based nano-cylinders associate in a Gaussian way engendering the formation of precited domains. Then, in a second step, the system undergoes its reorganization characterized by a compacity increase of the precipitated domains and forms a physical gel. Then, we studied chemical gels obtained by cross-linking PRs via their α-CDs. The chemical cross-linking reaction with divinym sulfone (DVS) does not occur in soft conditions so that highly cross-linked domains cohabit with less cross-linked ones

Systèmes supramoléculaires à base d'a-cyclodextrines et de poly(oxyéthylène) (Structure et propriétés des pseudo-polyrotaxanes, polyrotaxanes et gels glissants)

Nous avons étudié le processus de complexation entre les a-cyclodextrines (a-CD) et le poly(oxyéthylène) (PEO) dans l'eau, conduisant ainsi à la formation de complexes d'inclusion appelés pseudo-polyrotaxanes (PPR). A 30C, nous avons établi que, dans une première étape, les a-CD complexent les chaînes de PEO, formant des molécules de PPR. A plus grande échelle, une agrégation rapide des molécules de PPR a lieu et des nano-cylindres à base d'a-CD complexées se forment. A plus grande échelle encore, les nano-cylindres à base d'a-CD s'associent de manière gaussienne, engendrant la formation de domaines précités. Ensuite, dans une seconde étape, le système subit une auto-réorganisation caractérisée par une augmentation de la compacité des domaines précités, et il se forme un gel physique. Nous avons ensuite investigué les polyrotaxanes (PR), c'est-à-dire les PPR à base d'a-CD et de PEO bouchonnés stériquement aux extrémités, en solution concentrée dans le diméthylsulfoxyde (DMSO) et avons établi qu'ils ont la particularité de former des gels physiques au cours du temps à température ambiante. L'origine moléculaire de l'auto-organisation est la cristallisation des segments de PEO nus et l'agrégation régulière des a-CD complexées provenant de liaisons hydrogène par l'intermédiaire de leurs groupements hydroxyles. Ensuite, nous avons étudié les gels chimiques obtenus par réticulation des PR par l'intermédiaire de leurs a-CD. La réaction de réticulation chimique avec la divinylsulfone (DVS) n'a pas lieu dans des conditions douces si bien que des domaines hautement réticulés cohabitent avec d'autres qui sont moins réticulés.We studied the threading process between a-cyclodextrins (a-CDs) and poly(ethylene oxide) (PEO in water, thus leading to the formation of inclusion complexes called pseudo-polyrotaxanes (PPRs). At 30C, we established that, in a first step, a-CDs thread onto PEO chains, forming PPR molecules. At a higher lenght-scale, rapid aggregation of the PPR molecules occurs and threaded a-CD-based nano-cylinders form. A higher lenght-scale, a-CD_based nano-cylinders associate in a Gaussian way engendering the formation of precited domains. Then, in a second step, the system undergoes its reorganization characterized by a compacity increase of the precipitated domains and forms a physical gel. Then, we studied chemical gels obtained by cross-linking PRs via their a-CDs. The chemical cross-linking reaction with divinym sulfone (DVS) does not occur in soft conditions so that highly cross-linked domains cohabit with less cross-linked ones.STRASBOURG-Sc. et Techniques (674822102) / SudocSudocFranceF

Hemicellulosic Polysaccharides Mimics: Synthesis of Tailored Bottlebrush-Like Xyloglucan Oligosaccharide Glycopolymers as Binders of Nanocrystalline Cellulose

International audienceWe report in this contribution that while low molecular weight hemicellulosic building blocks are known not to interact with cellulosic materials, their multivalent presentation on a polymeric scaffold significantly enhanced the binding interactions that are remarkably in the same range as those usually observed for lectin-carbohydrate interactions. We developed a poly(propargyl methacrylate) scaffold on which we conjugated, by "post-click" reaction, a variety of azide reducing-end functionalized xyloglucan oligosaccharides with controlled enzymatic-mediated rate of degalactosylation. Bottlebrush-like xyloglucan oligosaccharide glycopolymers (poly(XGO n)) were obtained and their self-assemblies in aqueous solution were investigated using dynamic light scattering (DLS). We demonstrated that increasing the extent of degalactosylation promoted self-association of poly(XGO n), which we attribute to the appearance of hydrophobic domains. A sharp thermoresponsiveness, which corresponds to a decrease in aggregate size with increasing temperature, was observed when the extent of degalactosylation was 30% or greater. Importantly, isothermal titration calorimetry (ITC) and polarized/depolarized DLS revealed that poly(XGO n) exhibit a significant capacity to interact with nanocrystalline cellulose (NCC) surfaces particularly for the nondegalactosylated form, emphasizing the important role of galactosyl residues in the binding mechanism and in the 3-dimensional structures of glycopolymers

Self-assembly of phosphorous containing oligomers: morphological features and pHsensitiveness in suspension.

International audienceMethacrylamide-based oligomers bearing phosphonate pending groups at the end of a long alkyl chain and originating from undecylenic acid synthons were subjected to direct oligomer dissolution. Size improvement towards much smaller objects was reached using the nanoprecipitation method: the oligomers were first dissolved in an organic solvent, and then precipitated in water using a syringe pump. Dynamic light scattering (DLS) showed phosphorous containing monomodal and quite narrow-sized self-assemblies in water with hydrodynamic diameters (DH) ranging from 80 to 280 nm (depending on the oligomer system). Direct visualization using transmission electron microscopy (TEM) and atomic force microscopy (AFM) showed filled and almost individual particles with spherical shape. They were considerably shrunk, suggesting the highly swollen character of the self-assemblies in suspension. Morphological information on the multi-scale self-assembled structures was complementarily obtained using static light scattering (SLS). Thus, at a low length-scale, highly segregated sub-units having sharp boundaries surrounded by water (Porod behaviour) were observed, whereas at a high length-scale random non-compact organization of these sub-units via weak interactions was found, forming a chaplet-like structure (Gaussian behaviour). Furthermore, the pH-sensitiveness of the suspensions obtained after the nanoprecipitation method was studied. Particularly, at pH = 12, the characteristic size drastically increased within few hours from typically ~280 nm to 2 mm due to electrostatic repulsion between deprotonated hydroxyl groups. At longer times, the observed peculiar behaviour corresponded to the model of diffusion-limited cluster aggregation (DLCA) where the particles stuck easily together upon contact

UV-responsive amphiphilic graft copolymers based on coumarin and polyoxazoline

International audienc

Synthesis and self-assembly of amphiphilic polymers based on polyoxazoline and vegetable oil derivatives

International audienceThe synthesis and self-assembly of amphiphilic polymers based on unsaturated vegetable oils and poly(2-methyl-2-oxazoline) (POx) are reported. Two architectures of lipopolymers were explored starting from fatty methyl esters and raw vegetable oils. These latter were converted into macroinitiators for cationic ring-opening polymerization (CROP) of 2-methyl-2-oxazoline. Firstly, a thiol-ene coupling reaction in the presence of mercaptoethanol under UV irradiation was performed to introduce hydroxyl groups that were further transformed into initiating species used for cationic polymerization. According to this strategy, various lipopoly(2-methyl-2-oxazoline)s (LipoPOx)s with different lipidic/POx ratios were successfully obtained and characterized by 1H NMR, SEC and MALDI-Tof analyses. Finally, the self-organization of the LipoPOx was studied using dynamic light scattering (DLS). Well-shaped nanoparticles were obtained with characteristic radii of 4.3 and 10.2 nm for the fatty ester- and triglyceride-based lipopolymers, respectively. The latter value is about twice the former one due to the higher lipidic fraction of the triglyceride-based polymer that promotes hydrophobic interactions. The relaxation time distributions of both systems were found to be monomodal indicating monodisperse colloidal suspensions

Solubilized Enzymatic Fuel Cell (SEFC) for Quasi-Continuous Operation Exploiting Carbohydrate Block Copolymer Glyconanoparticle Mediators

International audienceEnzymatic biofuel cells are ecofriendly power sources that can deliver μW−mW outputs from renewable substrates, but their stability is a major issue owing to enzyme fragility. The vast majority of reported biofuel cells can only generate power continuously for relatively short periods of time. Here we report a novel "solubilized enzymatic fuel cell (SEFC)" concept for continuous long-term operation. Avoiding surface immobilization techniques allows bio- catalytic activity to be easily restored or replenished. The biofuel cell exploits freely diffusing enzymes and β-cyclodextrin-coated glycona- noparticles with entrapped quinone and thiazoline redox mediators, for mediated glucose and oxygen conversion. The cell was designed with permselective membranes to enable substrate and proton diffusion while trapping the enzymes and glyconanoparticles in separate compartments. The SEFC exhibited a peak power loss of only 26.3% after 7 days of continuous charge−discharge cycling at 50 μA; thus, SEFCs may be envisaged to power lab-on-a-chip devices for periods of several weeks