Adsorption Of Xyloglucan Research Articles

Multiscale analysis of hierarchical flax-epoxy biocomposites with nanostructured interphase by xyloglucan and cellulose nanocrystals

Natural biological systems feature hierarchical nanostructured architectures achieving high strength and toughness. In this work, the spontaneous adsorption of xyloglucan (XG) and cellulose nanocrystals (CNC) onto flax fabrics is considered to develop hierarchical interphases with improved interfacial adhesion in epoxy-based biocomposites. A multi-scale analysis is carried out, from the nano & micrometric scale with the characterization of fibre surface topography, work of adhesion and interfacial shear strength (IFSS) between flax fibres and epoxy resin, to the macroscopic scale with the transverse mechanical properties of biocomposites. At the fibre scale, XG and CNC increase the surface roughness of flax fibres, as well as their adhesion to epoxy resin with IFSS improved by 60 %, up to 22.3 MPa. At the composite scale, the treatments have a major influence on the cohesion of flax cell walls and microstructure of the biocomposites. Transverse tensile tests reveal both cohesive and adhesive interfacial failure.

Xyloglucan-cellulose nanocrystal-chitosan double network hydrogels for soft actuators

Hydrogels are materials consisting in a three-dimensional hydrophilic polymer network swollen by a large amount of water. An efficient strategy to elaborate hydrogels consists in establishing double polymer networks in order to achieve high strengthening effect associated with other properties such as transparency or tailored swelling capacities. In this work, we prepared cellulose nanocrystals (CNC)-based hydrogels with double network architecture. The first network, formed by CNC and xyloglucan (XG), takes advantage of entropic adsorption of XG on the CNC surface while the second network relies on electrostatic interactions between cationic Chitosan (Chi) and anionic CNC. Hydrogels with different compositions were successfully prepared. Their rheological properties, stability and swelling capacities in acidic and alkaline solutions were evaluated. Internal organizations of hydrogels were investigated by fluorescence microscopy after polymer labelling and polarized optical microscopy (POM). Finally, hydrogels demonstrated excellent mechanical properties and tuneable swelling capacities that can be leveraged for the implementation of bilayer actuators. Therefore, we further prepared films composed of two hydrogels layers, each one containing a different XG/CNC ratio. Bilayered films bended in water due to the asymmetric swelling of layers and the extent of bending can be modulated by the XG/CNC ratio.

Entropy drives the adsorption of xyloglucan to cellulose surfaces – A molecular dynamics study

The adsorption of nonionic polymers to cellulose is of large importance both in the plant cell wall during synthesis and for the development of sustainable materials from wood. Here, the thermodynamics of adsorption of the polysaccharide xyloglucan (XG) to both native and chemically modified cellulose with carboxyl groups was investigated using molecular dynamics simulations. The free energy of adsorption was calculated as the potential of mean force between an XG oligomer and model cellulose surfaces in a range of temperatures from 298 K to 360 K. It was found that the adsorption near room temperature is an endothermic process dominated by the entropy of released interfacial water molecules. This was corroborated by quantitative assessment of the absolute entropy per water molecule both at the interface and in the bulk. In the case of native cellulose, the adsorption became exothermic at higher temperatures, while the relatively strong interactions between water and the charged groups of the oxidized cellulose impede such a transition. The results also indicate that the extraction of strongly associated hemicelluloses would be facilitated by low temperature.

Adsorption of xyloglucan and cellulose nanocrystals on natural fibres for the creation of hierarchically structured fibres

Green treatment of natural fibres is a major issue in paper, textile and biocomposites industries to design innovative and eco-friendly products. In this work, hierarchical structuring of flax woven fabrics by the adsorption of xyloglucan (XG) and cellulose nanocrystals (CNC) is studied. Indeed, CNC have high mechanical properties, high specific surface area and great potential for functionalization. The adsorption of XG and CNC has been investigated in terms of localization by confocal and scanning electron microscopy (SEM) and quantification through adsorption isotherms. Adhesion force measurements have also been performed by Atomic Force Microscopy (AFM). XG and CNC are homogeneously adsorbed on flax fabric and adsorption isotherms reach plateau values around 20 mg /gfibres for both. The pre-adsorption of XG on flax fabric influences the amount of adsorbed CNC in the high concentrations and also creates entanglements and strong interactions between XG and CNC with the formation of an extensible network.

Adsorption of Xyloglucan onto Thin Films of Cellulose Nanocrystals and Amorphous Cellulose: Film Thickness Effects.

The interaction between cellulose and hemicelluloses is of fundamental importance for understanding the molecular architecture of plant cell walls. Adsorption of xyloglucan (XG) onto regenerated cellulose (RC), sulfated cellulose nanocrystal (s-CNC), and desulfated cellulose nanocrystal (d-CNC) films was studied by quartz crystal microbalance with dissipation monitoring, surface plasmon resonance, and atomic force microscopy. The amount of XG adsorbed onto different cellulose substrates increased in the order RC < s-CNC < d-CNC. The adsorption of XG onto RC films was independent of film thickness (d), whereas XG adsorption was weakly dependent on d for s-CNC films and strongly dependent on d for d-CNC films. However, approximately the same amount of XG adsorbed onto “monolayer-thin” films of RC, s-CNC, and d-CNC. These results suggest that the morphology and surface charge of the cellulose substrate played a limited role in XG adsorption and highlight the importance of film thickness of cellulose nanocrystalline films to XG adsorption.

Xyloglucan adsorption for measuring the specific surface area on various never-dried cellulose nanofibers

Abstract In this paper, we explore xyloglucan adsorption to cellulose nanofibers as a method for the evaluation of their quality (i. e., the degree of disintegration) and the accessible surface area in the wet state and at low ionic strength. This method was shown to be capable of estimating the surface areas of 14 different cellulose nanofiber qualities from both hardwood and softwood with different pretreatments, including enzymatic hydrolysis using a monocomponent endoglucanase, TEMPO-mediated oxidation, and carboxymethylation. The cellulose surface measured using this method showed a correlation with the degree of disintegration expressed as transmittance for different concentrations of xyloglucan.

Adsorption of Xyloglucan onto Cellulose Surfaces of Different Morphologies: An Entropy-Driven Process

The temperature-dependence of xyloglucan (XG) adsorption onto smooth cellulose model films regenerated from N-methylmorpholine N-oxide (NMMO) was investigated using surface plasmon resonance spectroscopy, and it was found that the adsorbed amount increased with increasing temperature. This implies that the adsorption of XG to NMMO-regenerated cellulose is endothermic and supports the hypothesis that the adsorption of XG onto cellulose is an entropy-driven process. We suggest that XG adsorption is mainly driven by the release of water molecules from the highly hydrated cellulose surfaces and from the XG molecules, rather than through hydrogen bonding and van der Waals forces as previously suggested. To test this hypothesis, the adsorption of XG onto cellulose was studied using cellulose films with different morphologies prepared from cellulose nanocrystals (CNC), semicrystalline NMMO-regenerated cellulose, and amorphous cellulose regenerated from lithium chloride/dimethylacetamide. The total amount of high molecular weight xyloglucan (XGHMW) adsorbed was studied by quartz crystal microbalance and reflectometry measurements, and it was found that the adsorption was greatest on the amorphous cellulose followed by the CNC and NMMO-regenerated cellulose films. There was a significant correlation between the cellulose dry film thickness and the adsorbed XG amount, indicating that XG penetrated into the films. There was also a correlation between the swelling of the films and the adsorbed amounts and conformation of XG, which further strengthened the conclusion that the water content and the subsequent release of the water upon adsorption are important components of the adsorption process.

Stabilization of Water-in-Water Emulsions by Polysaccharide-Coated Protein Particles.

The phase diagram of mixtures of xyloglucan (XG) and amylopectin (AMP) in aqueous solution is presented. Water-in-water emulsions prepared from mixtures in the two-phase regime were studied in detail, and the interfacial tension was determined. It is shown that the emulsions can be stabilized by addition of β-lactoglobulin microgels (βLGm), but only at pH ≤ 5.0. Excess βLGm preferentially entered the AMP phase at pH > 5.0 and the XG phase at lower pH. The inversion was caused by adsorption of XG onto βLGm that started below pH 5.5. It is shown that modification of the surface of particles by coating with polysaccharides is a potential lever to control stabilization of water-in-water emulsions.

Kinetic aspects of the adsorption of xyloglucan onto cellulose nanocrystals.

In this work, the adsorption of a neutral flexible polysaccharide, xyloglucan (XG), onto thin cellulose nanocrystal (CNC) surfaces has been investigated to get more insight into the CNC-XG association. Gold-coated quartz crystals were spin-coated with one layer of CNC, and XG adsorption was monitored in situ using a quartz crystal microbalance with dissipation (QCM-D). The adsorption of XG under flow at different concentrations did not result in the same surface concentration, which evidenced a kinetically controlled process. In an attempt to describe the binding of XG to CNCs, adsorption data were fitted to a kinetic model comprising a contribution from XG adsorption onto uncovered CNC surfaces and a contribution from XG adsorption after rearrangement. Kinetic studies evidenced the presence of two adsorption regimes as a function of XG concentration. For low XG concentrations, the kinetic constant for chain rearrangement is comparable to the kinetic constant for adsorption. This fact implies a rearrangement and alignment of XG molecules on CNCs. Differently, for higher XG concentrations, the kinetic constant related to the conformational rearrangement decreases, indicating that XG molecules have no time to laterally rearrange before new XG molecules adsorb.

Molecular dynamics simulation of strong interaction mechanisms at wet interfaces in clay–polysaccharide nanocomposites

The thermodynamics of xyloglucan adsorption to montmorillonite clay in water was studied with molecular dynamics simulations.

Chitin Nanocrystal-Xyloglucan Multilayer Thin Films

For the first time, the adsorption of xyloglucan (XG) on chitin nanocrystals (ChiNC) surface was proved using quartz crystal microbalance with dissipation (QCM-D) and by successfully building up spin-coated assisted layer-by-layer (LbL) structures on solid substrates. Several parameters in the adsorption process, such as ChiNC concentrations (0.5-3.0 g L(-1)), number of layers, or the outmost layer material (ChiNC or XG), were investigated to better understand the fabrication process of multilayer films. The thickness of the homogeneous film increased linearly with the number of bilayers, with an average thickness per bilayer of 12.3 nm. Additionally surface morphology was studied by atomic force microscopy (AFM), which revealed an almost completely covered surface after the adsorption of ChiNC. The final structures were found to have semireflective properties capable of being tuned by adjusting the ChiNC dispersion parameters.

Erratum to: Molecular dynamics simulation study of xyloglucan adsorption on cellulose surfaces: effects of surface hydrophobicity and side-chain variation

Erratum to: Molecular dynamics simulation study of xyloglucan adsorption on cellulose surfaces: effects of surface hydrophobicity and side-chain variation

Molecular dynamics simulation study of xyloglucan adsorption on cellulose surfaces: effects of surface hydrophobicity and side-chain variation

The effect of surface hydrophobicity and side-chain variation on xyloglucan adsorption onto cellulose microfibrils (CMF) is investigated via molecular dynamics simulations. A molecular model of CMF with (100), (010), (1–10), (110) and (200) crystal faces was built. We considered xylogluco-oligosaccharides (XGO) with three repeating units, namely (XXXG)3, (XXLG)3, and (XXFG)3 (where each (1,4)-β-d-glucosyl residue in the backbone is given a one-letter code according to its substituents: G = β-d-Glc; X = α-d-Xyl-(1,6)-β-d-Glc; L = β-d-Gal-(1,2)-α-d-Xyl-(1,6)-β-d-Glc; F = α-l-Fuc-(1,2)-β-d-Gal-(1,2)-α-d-Xyl-(1,6)-β-d-Glc). Our work shows that (XXXG)3 binds more favorably to the CMF (100) and (200) hydrophobic surfaces than to the (110), (010) and (1–10) hydrophilic surfaces. The origin of this behavior is attributed to the topography of hydrophobic CMF surface, which stabilizes (XXXG)3 in flat conformation. In contrast, on the rough hydrophilic CMF surface (XXXG)3 adopts a less favorable random-coil conformation to facilitate more hydrogen bonds with the surface. Extending the xyloglucan side chains from (XXXG)3 to (XXLG)3 hinders their stacking on the CMF hydrophobic surface. For (XXFG)3, the interaction with the hydrophobic surface is as strong as (XXXG)3. All three XGOs have similar binding to the hydrophilic surface. Steered molecular dynamics simulation was performed on an adhesive model where (XXXG)3 was sandwiched between two CMF hydrophobic surfaces. Our analysis suggests that this sandwich structure might help provide mechanical strength for plant cell walls. Our study relates to a recently revised model of primary cell walls in which extensibility is largely determined by xyloglucan located in limited regions of tight contact between CMFs.

Bioinspired and Highly Oriented Clay Nanocomposites with a Xyloglucan Biopolymer Matrix: Extending the Range of Mechanical and Barrier Properties

The development of clay bionanocomposites requires processing routes with nanostructural control. Moreover, moisture durability is a concern with water-soluble biopolymers. Here, oriented bionanocomposite coatings with strong in-plane orientation of clay platelets are for the first time prepared by continuous water-based processing. Montmorillonite (MTM) and a "new" unmodified biological polymer (xyloglucan (XG)) are combined. The resulting nanocomposites are characterized by FE-SEM, TEM, and XRD. XG adsorption on MTM is measured by quartz crystal microbalance analysis. Mechanical and gas barrier properties are measured, also at high relative humidity. The reinforcement effects are modeled. XG dimensions in composites are estimated using atomistic simulations. The nanostructure shows highly oriented and intercalated clay platelets. The reinforcement efficiency and effects on barrier properties are remarkable and are likely to be due to highly oriented and well-dispersed MTM and strong XG-MTM interactions. Properties are well preserved in humid conditions and the reasons for this are discussed.

The adsorption of xyloglucan on cellulose: effects of explicit water and side chain variation

The interaction between para-crystalline cellulose and the cross-linking glycan xyloglucan (XG) plays a central role for the strength and extensibility of plant cell walls. The coating of XGs on cellulose surfaces is believed to be one of the most probable interaction patterns. In this work, the effects of explicit water and side chain variation on the adsorption of XGs on cellulose are investigated by means of atomistic molecular dynamics simulations. The adsorption properties are studied in detail for three XGs on cellulose Iβ 1–10 surface in aqueous environment, namely GXXXGXXXG, GXXLGXXXG, and GXXFGXXXG, which differ in the length and composition of one side chain. Our work shows that when water molecules are included in the theoretical model, the total interaction energies between the adsorbed XGs and cellulose are considerably smaller than in vacuo. Furthermore, in water environment the van der Waals interactions prevail over the electrostatic interactions in the adsorption. Variation in one side chain does not have significant influence on the interaction energy and the binding affinity, but does affect the equilibrium structural properties of the adsorbed XGs to facilitate the interaction between both the backbone and the side chain residues with the cellulose surface. Together, this analysis provides new insights into the nature of the XG–cellulose interaction, which helps to further refine current molecular models of the composite plant cell wall.

Effect of polymer adsorption on cellulose nanofibril water binding capacity and aggregation

Polymer adsorption on cellulose nanofibrils and the effect on nanofibril water binding capacity were studied using cellulose nanofibril films together with quartz crystal microbalance with dissipation (QCM-D) and surface plasmon resonance (SPR). The experiments were performed in the immersed state, and special attention was paid to the effect of polymer properties on the water content and viscoelastic properties of the polymer/fibril layer. The dry mass of the adsorbed polymers was determined using SPR. The type of the adsorbed polymer strongly affected the water content and viscoelastic properties of the nanofibril film. The adsorption of a highly charged flocculating polymer, PDADMAC, caused dehydration of the film, which was also detected as nanofibril film stiffening. The adsorption of xyloglucan introduced a dispersing effect to the nanofibril film, which was detected as a loosening and softening of the nanofibril/polymer layer. A dispersing effect was also achieved with carboxymethyl cellulose (CMC), but CMC did not adsorb irreversibly on the nanofibril surfaces. In addition to the nanofibril film studies, the effect of polymer adsorption on cellulose nanofibril suspension aggregation was demonstrated using confocal laser scanning microscopy (CLSM). Xyloglucan was shown to open the nanofibril aggregate structures and act as a dispersing agent, whereas the other polymers studied did not have as significant an effect on aggregation.

Friction between Cellulose Surfaces and Effect of Xyloglucan Adsorption

The forces and friction between cellulose spheres have been measured in the absence and presence of xyloglucan using an atomic force microscope. The forces between cellulose are monotonically repulsive with negligible adhesion after contact is achieved. The friction coefficient is observed to be unusually high in comparison with other nanotribological systems. We have confirmed that xyloglucan adsorbs strongly to cellulose, which results in a much stronger adhesion, which is dependent on the time the surfaces are in contact. Xyloglucan also increases the repulsion on approach of the cellulose surfaces, and the friction is markedly reduced. The apparently incompatible observations of decreased friction in combination with increased adhesion fulfills many of the necessary criteria for a papermaking additive.

The xyloglucan–cellulose assembly at the atomic scale

The assembly of cell wall components, cellulose and xyloglucan (XG), was investigated at the atomistic scale using molecular dynamics simulations. A molecular model of a cellulose crystal corresponding to the allomorph Ibeta and exhibiting a flexible complex external morphology was employed to mimic the cellulose microfibril. The xyloglucan molecules considered were the three typical basic repeat units, differing only in the size of one of the lateral chain. All the investigated XG fragments adsorb nonspecifically onto cellulose fiber; multiple arrangements are equally probable, and every cellulose surface was capable of binding the short XG molecules. The following structural effects emerged: XG molecules that do not have any long side chains tended to adapt themselves nicely to the topology of the microfibril, forming a flat, outstretched conformation with all the sugar residues interacting with the surface. In contrast, the XG molecules, which have long side chains, were not able to adopt a flat conformation that would enable the interaction of all the XG residues with the surface. In addition to revealing the fundamental atomistic details of the XG adsorption on cellulose, the present calculations give a comprehensive understanding of the way the XG molecules can unsorb from cellulose to create a network that forms the cell wall. Our revisited view of the adsorption features of XG on cellulose microfibrils is consistent with experimental data, and a model of the network is proposed.

The influence of surface chemical composition on the adsorption of xyloglucan to chemical and mechanical pulps

Adsorption kinetics of xyloglucan (XG) onto bleached chemical and mechanical wood pulps were studied to better understand the application of this plant polysaccharide to the modification of key industrial cellulosic materials. Bleached pulps prepared by the kraft process adsorbed significantly larger amounts of xyloglucan than did thermomechanical pulps (TMP) and chemi-thermomechanical pulps (CTMP). The ability of pulps to adsorb xyloglucan was intimately related to the surface amounts of cellulose, lignin and extractives, as determined by electron spectroscopy for chemical analysis (ESCA). The distribution of absorbed XG on bleached pulp fibers was examined with an XG-fluorescein conjugate (XG-FITC), which was prepared by xyloglucan endotransglycosylase (XET, EC 2.4.1.207)-mediated incorporation of fluorescein-labeled xyloglucan oligosaccharides (XGO-FITC) into XG. Fluorescence microscopy revealed that XG-FITC preferentially adsorbed on fiber surfaces, and was adsorbed in higher amounts to chemical pulps than mechanical pulps, as observed for the unmodified parent polysaccharide. Addition of hybrid aspen XET (PttXET16A) and XGO-FITC to bleached and unbleached mechanical pulps indicated that the amount of enzyme-accessible xyloglucan presented on TMP and CTMP surfaces is low.

Evidence for in vitro binding of pectin side chains to cellulose.

Pectins of varying structures were tested for their ability to interact with cellulose in comparison to the well-known adsorption of xyloglucan. Our results reveal that sugar beet (Beta vulgaris) and potato (Solanum tuberosum) pectins, which are rich in neutral sugar side chains, can bind in vitro to cellulose. The extent of binding varies with respect to the nature and structure of the side chains. Additionally, branched arabinans (Br-Arabinans) or debranched arabinans (Deb-Arabinans; isolated from sugar beet) and galactans (isolated from potato) were shown bind to cellulose microfibrils. The adsorption of Br-Arabinan and galactan was lower than that of Deb-Arabinan. The maximum adsorption affinity of Deb-Arabinan to cellulose was comparable to that of xyloglucan. The study of sugar beet and potato alkali-treated cell walls supports the hypothesis of pectin-cellulose interaction. Natural composites enriched in arabinans or galactans and cellulose were recovered. The binding of pectins to cellulose microfibrils may be of considerable significance in the modeling of primary cell walls of plants as well as in the process of cell wall assembly.