Structural Variations in Hybrid All-Nanoparticle Gibbsite Nanoplatelet/Cellulose Nanocrystal Multilayered Films

Cellulose nanocrystals (CNCs) are promising bio-sourced building blocks for the production of high performance materials. In the last ten years, CNCs have been used in conjunction with polymers for the design of multilayered thin films via the layer-by-layer assembly technique. Herein, polymer chains have been replaced with positively charged inorganic gibbsite nanoplatelets (GN) to form hybrid “nanoparticle-only” composite films. A combination of atomic force microscopy and neutron reflectivity experiments was exploited to investigate the growth and structure of the films. Data show that the growth and density of GN/CNC films can be tuned over a wide range during preparation by varying the ionic strength in the CNC suspension and the film drying protocol. Specifically, thin and dense multilayered films or very thick, more porous mixed slabs, as well as intermediate internal structures could be obtained in a predictable manner. The influence of key physicochemical parameters on the multilayer film build up was elucidated and the film architecture was linked to the dominating interaction forces between components. The degree of structural control over these hybrid nanoparticle-only films is much higher than that reported for CNC/polymer films, which offers new properties and potential applications as separation membranes or flame retardant coatings

Aphanomyces euteiches Cell Wall Fractions Containing Novel Glucan-Chitosaccharides Induce Defense Genes and Nuclear Calcium Oscillations in the Plant Host Medicago truncatula

[EN] N-acetylglucosamine-based saccharides (chitosaccharides) are components of microbial cell walls and act as molecular signals during host-microbe interactions. In the legume plant Medicago truncatula, the perception of lipochitooligosaccharide signals produced by symbiotic rhizobia and arbuscular mycorrhizal fungi involves the Nod Factor Perception (NFP) lysin motif receptor-like protein and leads to the activation of the so-called common symbiotic pathway. In rice and Arabidopsis, lysin motif receptors are involved in the perception of chitooligosaccharides released by pathogenic fungi, resulting in the activation of plant immunity. Here we report the structural characterization of atypical chitosaccharides from the oomycete pathogen Aphanomyces euteiches, and their biological activity on the host Medicago truncatula. Using a combination of biochemical and biophysical approaches, we show that these chitosaccharides are linked to β-1,6-glucans, and contain a β-(1,3;1,4)-glucan backbone whose β-1,3-linked glucose units are substituted on their C-6 carbon by either glucose or N-acetylglucosamine residues. This is the first description of this type of structural motif in eukaryotic cell walls. Glucan-chitosaccharide fractions of A. euteiches induced the expression of defense marker genes in Medicago truncatula seedlings independently from the presence of a functional Nod Factor Perception protein. Furthermore, one of the glucan-chitosaccharide fractions elicited calcium oscillations in the nucleus of root cells. In contrast to the asymmetric oscillatory calcium spiking induced by symbiotic lipochitooligosaccharides, this response depends neither on the Nod Factor Perception protein nor on the common symbiotic pathway. These findings open new perspectives in oomycete cell wall biology and elicitor recognition and signaling in legumes.SIThis work is part of the “Laboratoire d’Excellence” (LABEX) entitled TULIP (ANR -10-LABX-41); it was funded by the Région Midi-Pyrénées, the CNRS (PhD grant INEE 36 to AN), and the French Agence Nationale de la Recherche (ANR-08-BLAN-0208-01 “Sympasignal”)

Current characterization methods for cellulose nanomaterials

International audienc

Elaboration et caractérisation de nanocomposites à base de renforts biosourcés

Les élastomères chargés sont des matériaux nanocomposites présentant un compromis de propriétés unique exploité notamment dans les bandes de roulement des pneumatiques. Ils comprennent une charge renforçante, silice ou noir de carbone, qui doit présenter un module élevé, des dimensions nanométriques, et avoir la capacité de se disperser et de former des liaisons fortes avec la matrice. La nanocellulose est caractérisée par une morphologie anisotrope avec une section de l ordre de 10 nm, et une structure cristalline avec un module d environ 150 GPa. L objectif de la thèse est d évaluer si ce substrat peut être employé comme charge renforçante. Les travaux se divisent ainsi en trois parties portant successivement sur l obtention d aérogels de haute surface spécifique, la modification de leur surface, puis leur emploi comme renfort. La mise au point d un protocole de lyophilisation de suspensions de nanocellulose, et d un procédé d estérification par voie gaz des aérogels obtenus, a permis d obtenir des charges avec une haute surface spécifique et une interface avec un agent hydrophobe ou un agent de couplage. Une attention particulière a été accordée à la topochimie de la réaction dont le suivi a été réalisée par RMN du solide. Ces charges ont ensuite été incorporées au sein d un élastomère, puis les matériaux obtenus ont été caractérisés par MET et par des tests mécaniques. Dans le cas d un aérogel de nanocellulose avec une haute surface spécifique et un agent de couplage, les propriétés des matériaux obtenus sont alors caractéristiques du comportement d un élastomère chargé.Filled elastomers are nanocomposites with specific properties that make them suitable for numerous applications including tyre gum. They include a reinforcing filler, silica or carbon black, with features like a high elastic modulus, a size in the nanometer range, and the ability to be dispersed and to perform strong interactions with the matrix. Nanocellulose is an anisotropic nanoparticule with a crystalline structure whose elastic modulus is estimated around 150 GPa. The goal of this project is to study its ability to be a reinforcing filler. The work is divided into three parts dealing respectively with high specific surface aerogel preparation, their surface modification, and their use as a filler. A specific freeze drying protocol and a specially designed gas phase esterification process were used in order to obtain fillers with a high specific surface and an interface that can be either covered by an hydrophobic or a coupling graft. A special care has been devoted to the topochemistry, which has been monitored all along the reaction thanks to solid state NMR. These fillers have then been introduced in elastomers, the resulting materials being characterized by TEM and mechanical tests. In the case of a high specific surface nanocellulose aerogel with an interface covered by coupling agent, material features appeared then to be typical of filled elastomers.SAVOIE-SCD - Bib.électronique (730659901) / SudocGRENOBLE1/INP-Bib.électronique (384210012) / SudocGRENOBLE2/3-Bib.électronique (384219901) / SudocSudocFranceF

MISE EN EVIDENCE DU ROLE DES INTERACTIONS FIBRE/FIBRE ET FIBRE/MATRICE DANS DES NANOCOMPOSITES A RENFORT CELLULOSIQUE ET MATRICE APOLAIRE (ATACTIQUE ET ISOTACTIQUE)

GRENOBLE1-BU Sciences (384212103) / SudocSudocFranceF

Hydrophobization of cellulose microfibrils with benzylamines by periodic oxidation and subsequent reductive amination

International audienc

Dielectric spectroscopy on a PHBV bio-polymer

International audienc

Elaboration et déformation de systèmes biomimétiques innovants

La déformation des cellules végétales durant leur croissance génère des formes anisotropes variées. L'enveloppe des cellules en croissance, appelée paroi primaire végétales, est une couche fine, flexible et extensible, faite d'un réseau de microfibrilles de cellulose reliées entre elles par des hémicellulose qui ont une extension directionnelle. Le but de ce travail est d'élaborer des microcapsules biomimétiques possédant une structure similaire à la paroi primaire et d'étudier leur déformation sous une contrainte mécanique. Pour cela, nous avons utilisé les fortes interactions entre les nanocristaux de cellulose (sous-unités des microfibrilles) et les xyloglucanes (hémicellulose la plus répandue) déjà utilisée pour construire des multicouches plan [1]. Pour reproduire la géométrie des cellules, nous avons fabriqué des microcapsules multicouches à partir de nanocristaux de cellulose et de xyloglucanes, en combinant une émulsion d'huile dans l'eau, de dimension de 20 m environ, avec un dépôt couche par couche conduisant à des capsules biomimétiques. La régularité du dépôt de couche a été suivit par un marquage fluorescent sélectif, l'épaisseur et l'organisation de la paroi ont été caractérisées en microscopie électronique. Par séchage et évaporation du coeur d'huile, les capsules ainsi dégonflées présentent diverses formes révélées par des reconstructions 3D à partir de coupes de microscopie confocale. La relation entre les formes obtenus, les dimensions caractéristiques et les propriétés mécaniques de la paroi a été étudiée [2]. Le contrôle de la taille et de l'épaisseur de la capsule permet d'explorer diverses situations de déformations. [1] B. Jean*, L. Heux, F. Dubreuil, G. Chambat & F. Cousin, Non-electrostatic building of biomimetic cellulose-xyloglucan multilayers, Langmuir, 25(7), 3920-3923 (2009) [2] C. Quilliet, C. Zoldesi, C. Riera, A. van Blaaderen, and A. Imhof Anisotropic colloids through non-trivial buckling Eur. Phys. J. E, 27, 13{20} (2008)The deformation of plant cells during their growth can generate various anisotropic shapes. The envelop of the growing cells, also called primary wall of plants, is a thin, flexible and extensible layer made of a network of cellulose microfibrils linked by hemicellulose tethers, that can have directional extension. The goal of this work is to elaborate biomimetic microcapsules with structures similar to the plant primary walls and explore their deformation under mechanical stress. For that purpose, we took advantage of the strong interaction of cellulose nanocrystals (the microfibrils sub-elements) with xyloglucan (the most common hemicellulose) already used to build planar multilayer systems [1]. In order to reproduce the cell geometry, we successfully build multilayered microcapsules from cellulose nanocrystals and xyloglucans, by combining oil in water emulsions with dimensions around 20 m with layer-by-layer deposit, leading to biomimetic microcapsules. The regularity of the layer deposition has been followed by selective fluorescent tagging and the wall thickness and organization was characterized by electron microscopy. Upon drying and evaporation of the oily core, the deflated microcapsules exhibited various shapes as revealed by 3D reconstruction from confocal microscopy slices. We have investigate the relationships between the obtained shapes in relation to the characteristic dimensions and the mechanical properties of the wall [2]. The control of the capsule size and thickness allows exploring various situations in terms of deformation behavior. [1] B. Jean*, L. Heux, F. Dubreuil, G. Chambat & F. Cousin, Non-electrostatic building of biomimetic cellulose-xyloglucan multilayers, Langmuir, 25(7), 3920-3923 (2009) [2] C. Quilliet, C. Zoldesi, C. Riera, A. van Blaaderen, and A. Imhof Anisotropic colloids through non-trivial buckling Eur. Phys. J. E, 27, 13{20} (2008)SAVOIE-SCD - Bib.électronique (730659901) / SudocGRENOBLE1/INP-Bib.électronique (384210012) / SudocGRENOBLE2/3-Bib.électronique (384219901) / SudocSudocFranceF

Research data supporting 'Electrohydrodynamic Convection Instabilities Observed in Suspensions of Cellulose Nanocrystals'

The research dataset contains images and sequences of images of the corresponding videos. Please refer to the pdf EC_CNC_OpenData for abstract and details of the Research Data.This work was supported by the ANR (BIOSELF: ANR-08-NANO-0037), the European Cooperation in Science and Technology Action for travel grant (COST-STSM-FP1205-30247), the ERC (CelluNANo: ERC-2020-POC 963872, BiTe: ERC-2020-COG-101001637), the EPSRC (VALUED: EP/W031019/1) and the SKCM2 Hiroshima University WPI

Electrohydrodynamic convection instabilities observed in suspensions of cellulose nanocrystals.

UNLABELLED: Cellulose nanocrystals are slender, negatively charged nanoparticles that spontaneously form a cholesteric liquid crystal in aqueous suspension above a critical concentration. When they are suspended in apolar solvents such as toluene using surfactants, the application of an AC electric field leads to the reorientation and then distortion of the cholesteric order until the cholesteric structure completely unwinds into a nematic-like order, typically above 0.4-0.6 kV/cm at 1kHz. In this work, we show that at much higher electric fields (≥ 4.6 kV/cm at 1 kHz) the sample develops a periodic pattern that varies with the field amplitude. We ascribed this pattern to electrohydrodynamic convection instabilities. These instabilities usually present complex regimes varying with the field, the voltage, the frequency and the geometry. However, the typical geometry where these instabilities were most documented across the literature differs from the geometry used in this work. This work concludes with possible future experimental investigations to clarify the exact regime of instability responsible for these observations. SUPPLEMENTARY INFORMATION: The online version contains supplementary material available at 10.1007/s10570-023-05391-6.ANR (BIOSELF: ANR-08-NANO-0037), the European Cooperation in Science and Technology Action for travel grant (COST-STSM-FP1205-30247), the ERC (CelluNANo: ERC-2020-POC 963872, BiTe: ERC-2020-COG-101001637), the EPSRC (VALUED: EP/W031019/1) and the SKCM2 Hiroshima University WPI