Surface Of Microfibrils Research Articles

Distribution of carboxy groups in TEMPO-oxidized cellulose nanofibrils prepared from never-dried Japanese cedar holocellulose, Japanese cedar-callus, and bacterial cellulose

We prepared 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO)-oxidized samples from never-dried Japanese cedar (JC) holocellulose, JC-callus, and bacterial cellulose (BC). The original never-dried samples and their TEMPO-oxidized products were characterized by neutral sugar composition analysis. TEMPO-oxidized cellulose nanofibrils (TEMPO-CNFs) were prepared from the TEMPO-oxidized samples by ultrasonication in water. The carboxy groups in TEMPO-CNFs were position-selectively esterified with 9-anthryl diazomethane (ADAM) to prepare TEMPO-CNF-COOCH2-C14H9 samples, which had UV absorption peak at 365 nm. The mass-average degree of polymerization (DPw) values of 1% lithium chloride/N,N-dimethylacetamide (LiCl/DMAc) solutions of the original samples were determined by size-exclusion chromatography in combination with multi-angle laser-light scattering, ultraviolet absorption, and refractive index detection (SEC/MALLS/UV/RI), and were 5490, 2660, and 2380 for the JC holocellulose, JC-callus, and BC samples, respectively. The TEMPO-CNF-COOCH2-C14H9 sample solutions in 1% LiCl/DMAc were analyzed by SEC/MALLS/UV/RI to obtain SEC elution patterns. The patterns corresponded to the molar mass and carboxy group distributions of the samples, which were detected by RI and UV absorption of anthryl groups, respectively. The carboxy groups existed in the entire molar mass distribution regions of all the TEMPO-CNF samples, although their lower molar mass regions contained higher carboxy group densities. The obtained results indicate that random depolymerization occurred on the cellulose microfibril surfaces at the initial stage of TEMPO-catalyzed oxidation and/or ultrasonication in water. This depolymerization mechanism can explain all the obtained SEC-elution patterns of the TEMPO-CNFs, without considering the presence of periodically disordered regions in the cellulose microfibrils of the never-dried cellulose samples.Graphical abstract

Electromediated Oxidation of Hydrolysed Bacterial Cellulose

The state-of-the-art method to isolate cellulose nanofibres employs a 2,2,6,6-Tetramethylpiperidinyloxyl (TEMPO)/NaBr/NaClO system, where the primary alcohols on the surface of cellulose microfibrils are oxidised. However, the large consumption of hypochlorite in this system makes it problematic for industrial implementation. Previously, electrochemical oxidation with a TEMPO catalyst has been reported for the preparation of cellulose nanofibres. Here, we present a study on the electromediated oxidation of bacterial cellulose (BC), the purest form of cellulose. BC has been used in a hydrolysed form, enabling the electromediated preparation of cellulose nanocrystals (CNCs), which is generally deemed even more costly than the preparation of cellulose nanofibres.In this work, the electromediated oxidation and cyclic voltammetry were performed in an electrochemical cell, which featured three electrodes: A Hg|Hg2SO4|K2SO4 reference electrode, a titanium net counter electrode, and a carbon foam working electrode, offering a high surface area. A static potential of 0.5 V was applied during the chronoamperometry and explored oxidation times were 3, 5, 9, 12 and 24 h.Using a TEMPO catalyst, the electromediated oxidation was applied to hydrolysed and non-hydrolysed BC fibres in a pH 10 buffer. The C6 primary hydroxyls of BC were successfully converted to sodium carboxylate groups. By the application of the TEMPO electro-mediated oxidation to hydrolysed BC for 9 h, high carboxylate and aldehyde concentrations of 1.4 and 0.3 mmol/g, respectively, were formed in the oxidized fibre. The carboxylate and aldehyde content was determined by a conductometric titration method. Surface morphologies after oxidation were investigated, showing alteration of the microfibril morphology for BC and the production of cellulose nanocrystals for hydrolysed BC. Hence, we present an effective and environmentally friendly route, which is particularly suitable for the preparation of cellulose nanocrystals.

The crystal structure of RsSymEG1 reveals a unique form of smaller GH7 endoglucanases alongside GH7 cellobiohydrolases in protist symbionts of termites.

Glycoside hydrolase family 7 (GH7) cellulases are key enzymes responsible for carbon cycling on earth through their role in cellulose degradation and constitute highly important industrial enzymes as well. Although these enzymes are found in a wide variety of evolutionarily distant organisms across eukaryotes, they exhibit remarkably conserved features within two groups: exo-acting cellobiohydrolases and endoglucanases. However, recently reports have emerged of a separate clade of GH7 endoglucanases from protist symbionts of termites that are 60-80 amino acids shorter. In this work, we describe the first crystal structure of a short GH7 endoglucanase, RsSymEG1, from a symbiont of the lower termite Reticulitermes speratus. A more open flat surface and shorter loops around the non-reducing end of the cellulose-binding cleft indicate enhanced access to cellulose chains on the surface of cellulose microfibrils. Additionally, when comparing activities on polysaccharides to a typical fungal GH7 endoglucanase (Trichoderma longibrachiatum Cel7B), RsSymEG1 showed significantly faster initial hydrolytic activity. We also examine the prevalence and diversity of GH7 enzymes that the symbionts provide to the termite host, compare overall structures and substrate binding between cellobiohydrolase and long and short endoglucanase, and highlight the presence of similar short GH7s in other organisms.

Thermal-degradation characteristics of mechanically nanofibrillated bleached pulps from hardwood and softwood

Nanofibrillated cellulose (NFC) consists of ultrafine cellulose structures in which the fibrils can have widths in the range from about 5 to 100 nm. NFC has been studied and developed in the paper industry, using bleached pulp from wood as the raw material. One of the issues in the application of NFC is their heat resistance to thermal degradation. The production process of NFC results in a decrease in their pyrolysis temperature during the nanofibrillation of bleached pulp; however, the details behind the reason and mechanisms are still unclear. In this study, NFC was prepared from bleached hardwood and softwood pulp by mechanical nanofibrillation using a grinder, and the pyrolysis behavior was investigated. For both bleached pulps, a decrease in the pyrolysis temperature was observed after nanofibrillation. The results suggest that the decrease in the pyrolysis temperature from nanofibrillation is not due to damage of the crystalline cellulose by nano fibrillation, but the damage of the hemicellulose components in the surface of the cellulose microfibrils or the interface between the crystalline cellulose and hemicellulose. If the hemicellulose on the surface of crystalline cellulose could be removed from the NFC, then the decrease in the pyrolysis temperature could be suppressed.

Evolution of the Cellulose Microfibril through Gamma-Valerolactone-Assisted Co-Solvent and Enzymatic Hydrolysis

Biomass recalcitrance during deconstruction remains a key bottleneck to affordable biomass processing technologies. A clear connection between the cell wall structure and biomass deconstruction is necessary to understand how lignocellulosic material is broken down to valuable monomeric components. Here, we monitor changes in the cellulose microfibril domains of poplar, sorghum, and switchgrass throughout gamma-valerolactone (GVL)–water co-solvent pretreatment and enzymatic hydrolysis using solid-state 13C cross-polarization magic angle spinning nuclear magnetic resonance spectroscopy (CP/MAS 13C-NMR) and wide-angle X-ray scattering (WAXS). Spectral fitting of NMR peaks corresponding to different cellulose microenvironments at the C4 carbon center suggests that a mildly acidic GVL–water co-solvent pretreatment of poplar leads to nearly full removal of xylan–cellulose linkages, which primes the cellulose for enzymatic attack. The spectral fitting also suggests that the pretreatment causes significant depletion of the inaccessible fibril surface domains with an increase in more thermally stable crystalline resonances (Iβ). WAXS confirmed a decrease in the lattice spacing between (200) crystalline planes with increasing co-solvent pretreatment severity. These results are interpreted as an opening of bound microfibril surfaces previously inaccessible to the co-solvent system, which leaves behind a more thermally stable, crystalline domain that is potentially prone to relaxation and recrystallization. Full conversion of residual GVL-pretreated biomass was achieved after the GVL co-solvent pretreatment at 140 °C using a commercial enzyme cocktail, CTec2, which contains different cellulases and other enzymes. Spectral fitting of enzymatically hydrolyzed samples by a single engineered cellulase, CelR, suggests that the residual cellulose recalcitrance is mainly due to the inability of CelR to digest the Iβ crystalline domain present in pretreated samples. This work helps to provide new information regarding the structure of the cell wall and recalcitrance throughout GVL–water mild acidolysis and CelR enzymatic biomass deconstruction by tracking the evolution of structural domains within the cellulose microfibril. This work further directs recommendations for improving the conversion and sugar yields in future studies. Our findings inform inquiry into larger questions of cellulose recalcitrance through GVL pretreatment and CelR enzymatic hydrolysis and give insight into subsequent required steps for full cellulose conversion with attention to the most recalcitrant cellulose structures.

Changes in water-vapor-adsorption isotherms of pulp fibers and sheets during paper recycling, including drying of wet webs, and disintegration and sonication of dried sheets in water

Abstract A never-dried (ND) fines-free softwood bleached kraft pulp was converted to air-dried and thermally dried handsheets, which were then disintegrated or sonicated in water under various conditions. These disintegrated or sonicated pulps were converted to handsheets and used to obtain fundamental data on paper recycling. The water-vapor-adsorption isotherms of the pulp and sheet samples after super-critical-point drying showed clear differences between the water volumes adsorbed by the ND pulp, once-dried pulp, and dried sheets at the same relative humidities above 50%. These differences are caused by hornification of the pulp and sheet samples during drying and recycling. Air and thermal drying of wet webs decreased the adsorbed-water-vapor volume by 7%–9% and 14%–18%, respectively, relative to that adsorbed by the original ND pulp. We hypothesize that the decrease in water-vapor-adsorption volume from that of the original ND pulp at relative humidities >50% reflects the degree of irreversible formation of hydroxyl groups in the originally hydrophilic hemicelluloses and crystalline cellulose microfibril surfaces in the pulp and sheet samples during drying and paper recycling. The water-vapor-adsorption isotherms of pulp and sheet samples can be used to quantify the degree of hornification or the amount of irreversible hydrogen bonds formed during paper recycling.

Surface sulfation of crab chitin for anisotropic swelling and nanodispersion

Crab chitin was sulfated under heterogeneous conditions using sulfamic acid in N’N-dimethylformamide to selectively sulfate the microfibril surface. The degree of sulfation followed a first order kinetics assuming a limited available reaction sites on the surface, and leveled off at a bulk degree-of-substitution of 0.4, corresponding to 2 mol/kg of sulfate groups. The reaction rate was proportional to the square of sulfamic acid concentration, suggesting involvement of two sulfamic acid molecules in a reaction. When washed with water after sulfation, the crab shell chitin fragments swelled anisotropically in the helicoidal axis direction, revealing regular alternating birefringence under optical microscope. Further mechanical treatment with high-pressure homogenizer led to slender nanofibrils, whose diameters were of the order of 6 nm according to turbidimetric analysis, in agreement with the Scherrer size estimated from X-ray diffraction line broadening. Both atomic force microscopy and transmission electron microscopy measurement showed presence of further smaller fragments with diameter of 3–4 nm and contour length of 0.5–1 \(\upmu \hbox {m}\) with a few kinks. The current approach presents a rapid and efficient modification to chitin, and a strategy for the preparation of stable nanochitin suspension.

Cell wall modifications by α-XYLOSIDASE1 are required for control of seed and fruit size in Arabidopsis.

Cell wall modifications are of pivotal importance during plant development. Among cell wall components, xyloglucans are the major hemicellulose polysaccharide in primary cell walls of dicots and non-graminaceous monocots. They can connect the cellulose microfibril surface to affect cell wall mechanical properties. Changes in xyloglucan structure are known to play an important role in regulating cell growth. Therefore, the degradation of xyloglucan is an important modification that alters the cell wall. The α-XYLOSIDASE1 (XYL1) gene encodes the only α-xylosidase acting on xyloglucans in Arabidopsis thaliana. Here, we showed that mutation of XYL1 strongly influences seed size, seed germination, and fruit elongation. We found that the expression of XYL1 is directly regulated in developing seeds and fruit by the MADS-box transcription factor SEEDSTICK. We demonstrated that XYL1 complements the stk smaller seed phenotype. Finally, by atomic force microscopy, we investigated the role of XYL1 activity in maintaining cell stiffness and growth, confirming the importance of cell wall modulation in shaping organs.

Array-based microfibril surface assessment (AMSA): a method for probing surface-exposed polysaccharides on cellulose nanofibres

Small amounts of polysaccharides remaining tightly bound to cellulose microfibrils in the plant cell wall are significant to cell wall architecture and of importance to the rheological properties of plant-derived cellulose nanofibres (CNFs). A method for detecting these polysaccharides is presented. The method, Array-based Microfibril Surface Assessment (AMSA), uses monoclonal antibodies to probe polysaccharides that are exposed on fibrous material. Microfluidised alcohol insoluble residue from sugar beet pulp was used as control and baseline, representing a minimally processed material. To test the utility of AMSA, CNF prepared from sugar beet pulp were analysed. Surprisingly, nanofibrillation did not enhance binding of CBM3a (specific to crystalline cellulose) which indicates that bare cellulose is not easily made. However, nanofibrillation exposed a large amount of unbranched mannan, implying that mannan is closely associated with cellulose in these cell walls. Additional treatment of the CNF suspensions with pectinases removed the majority of homogalacturonan and rhamnogalacturonan I, which caused flocculation of the samples. This highlights the importance of preserving small quantities of these polysaccharides to promote CNF-water interactions and obtain well-dispersed fibres. In conclusion, it is demonstrated how AMSA has a utility in both biotechnological applications involving CNF as well as for exploring plant cell wall architecture.

Detailed Structural Analyses of Nanofibrillated Bacterial Cellulose and Its Application as Binder Material for a Display Device.

Nanofibrillated bacterial cellulose (NFBC) is produced by culturing a cellulose-producing bacterium under agitated aerobic conditions in a carboxymethylcellulose (CMC)-supplemented medium. Detailed structural analyses revealed that NFBC fiber widths varied with the degree of substitution of the CMC used, and zeta potential values decreased with the increment of CMC concentration in the medium. Transmission electron microscopy observation after immunostaining demonstrated that CMC molecules were present on the NFBC microfibril surfaces. We tested NFBC for utility as a binder for a display device that uses electrochromic (EC) material. Introduction of a quaternary ammonium group into the EC molecules enhanced their interactions with the negatively charged NFBC microfibrils. A casting process homogeneously adsorbed the EC molecules onto the surface of a transparent electrode with NFBC. A homogeneous color change was successfully observed upon applying an electric field, suggesting that NFBC could be used as a binder material for uniform surface adsorption.

Molecular architecture of softwood revealed by solid-state NMR

Economically important softwood from conifers is mainly composed of the polysaccharides cellulose, galactoglucomannan and xylan, and the phenolic polymer, lignin. The interactions between these polymers lead to wood mechanical strength and must be overcome in biorefining. Here, we use 13C multidimensional solid-state NMR to analyse the polymer interactions in never-dried cell walls of the softwood, spruce. In contrast to some earlier softwood cell wall models, most of the xylan binds to cellulose in the two-fold screw conformation. Moreover, galactoglucomannan alters its conformation by intimately binding to the surface of cellulose microfibrils in a semi-crystalline fashion. Some galactoglucomannan and xylan bind to the same cellulose microfibrils, and lignin is associated with both of these cellulose-bound polysaccharides. We propose a model of softwood molecular architecture which explains the origin of the different cellulose environments observed in the NMR experiments. Our model will assist strategies for improving wood usage in a sustainable bioeconomy.

Preparation of oxidized celluloses in a NaBr/NaClO system using 2-azaadamantane N-oxyl (AZADO) derivatives in water at pH 10

Catalytic oxidation using N-oxyl radicals in water at pH 10 was applied to wood cellulose to determine the influence of different N-oxyl radical chemical structures on the reaction kinetics and structures of oxidized celluloses. 2,2,6,6-Tetramethylpiperidine-1-oxyl (TEMPO), 2-azaadamantane N-oxyl (AZADO), 1-methyl-AZADO (1-Me-AZADO), 9-azanoradamantane N-oxyl (Nor-AZADO), and 1,5-dimethyl-9-azanoradamantane N-oxyl (DMN-AZADO) were used as oxidation catalysts in a NaBr/NaClO system in water at room temperature and pH 10. The reaction time required for complete oxidation of wood cellulose by 5 mmol/g of NaClO using AZADO, 1-Me-AZADO, or Nor-AZADO was less than 20 min, while DMN-AZADO and TEMPO required 70 min and 120 min, respectively. The sodium carboxylate contents of the oxidized celluloses prepared using TEMPO and DMN-AZADO were 1.41 and 1.45 mmol/g, respectively, which were higher than those of oxidized celluloses prepared using other AZADO derivatives. The original cellulose I crystal structure, crystallinity, and crystal size of wood cellulose were mostly maintained in all oxidized celluloses, with oxidation selectively occurring at C6–OH groups on the crystalline cellulose microfibril surfaces. Oxidized celluloses prepared using DMN-AZADO and post-reduced with NaBH4 showed high carboxylate contents of ~ 1.41 mmol/g and the heist viscosity-average degrees of polymerization of ~ 800.

Effect of drying conditions on cellulose microfibril aggregation and “hornification”

Drying of chemical pulps results in a decreased swelling of the fibres, leading to lower density and strength properties of paper sheets. To investigate how variation of pulp pH, drying process temperature, and final moisture content affect this phenomenon, structural studies were performed on a cellulose-rich pulp. Interrupting the drying at moisture contents of around 20%, using drying temperatures of 80 °C and 140 °C, resulted in a more severe degree of hornification than if the pulp was completely dried at the same temperatures. This increased loss of swelling was accompanied by increased cellulose microfibril aggregation. No change of the cellulose microfibril size or of the cellulose crystallinity, as determined by NMR, could be seen. Further, the accessibility of the cellulose microfibril surfaces, including surfaces between microfibrils, was unaffected by the drying. Thus, hornification should not primarily be related to a reduction of accessible cellulosic surfaces.

Comparison of the surface constitutions of hemicelluloses on lignocellulosic nanofibers prepared from softwood and hardwood

Lignocellulose nanofibers (LCNFs) were directly prepared from the wood powders of softwood from cryptomeria and hardwood from eucalyptus, and differences in the surface constitutions of the prepared LCNFs were studied via quartz crystal microbalance (QCM). QCM analyses indicated different results in the enzymatic hydrolysis of these LCNFs with a multicomponent cellulase mixture in the initial stage of the reaction, suggesting that LCNFs prepared from cryptomeria and eucalyptus had different surface constitutions. A QCM analysis of the enzymatic hydrolysis of LCNFs with a multicomponent cellulase mixture after individual treatments with xylanase and mannanase were also conducted, where the results suggested differences in the laminated structure of hemicelluloses located around the cellulose microfibrils composing the LCNFs of cryptomeria and eucalyptus. According to the QCM results, the cellulose microfibrils composing LCNFs prepared from the softwood of cryptomeria are likely integrally surrounded by glucomannan, meanwhile the cellulose microfibrils composing the LCNFs prepared from the hardwood of eucalyptus exhibited low numbers of hemicelluloses surrounding the cellulose microfibrils, where a portion of the surface of the cellulose microfibrils is likely to be exposed.

Xyloglucan in the primary cell wall: assessment by FESEM, selective enzyme digestions and nanogold affinity tags.

Xyloglucan has been hypothesized to bind extensively to cellulose microfibril surfaces and to tether microfibrils into a load-bearing network, thereby playing a central role in wall mechanics and growth, but this view is challenged by newer results. Here we combined high-resolution imaging by field emission scanning electron microscopy (FESEM) with nanogold affinity tags and selective endoglucanase treatments to assess the spatial location and conformation of xyloglucan in onion cell walls. FESEM imaging of xyloglucanase-digested cell walls revealed an altered microfibril organization but did not yield clear evidence of xyloglucan conformations. Backscattered electron detection provided excellent detection of nanogold affinity tags in the context of wall fibrillar organization. Labelling with xyloglucan-specific CBM76 conjugated with nanogold showed that xyloglucans were associated with fibril surfaces in both extended and coiled conformations, but tethered configurations were not observed. Labelling with nanogold-conjugated CBM3, which binds the hydrophobic surface of crystalline cellulose, was infrequent until the wall was predigested with xyloglucanase, whereupon microfibril labelling was extensive. When tamarind xyloglucan was allowed to bind to xyloglucan-depleted onion walls, CBM76 labelling gave positive evidence for xyloglucans in both extended and coiled conformations, yet xyloglucan chains were not directly visible by FESEM. These results indicate that an appreciable, but still small, surface of cellulose microfibrils in the onion wall is tightly bound with extended xyloglucan chains and that some of the xyloglucan has a coiled conformation.

Different Conformations of Surface Cellulose Molecules in Native Cellulose Microfibrils Revealed by Layer-by-Layer Peeling.

Layer-by-layer peeling of surface molecules of native cellulose microfibrils was performed using a repeated sequential process of 2,2,6,6-tetramethylpiperidine-1-oxyl radical-mediated oxidation followed by hot alkali extraction. Both highly crystalline algal and tunicate celluloses and low-crystalline cotton and wood celluloses were investigated. Initially, the C6-hydroxy groups of the outermost surface molecules of each algal cellulose microfibril facing the exterior had the gauche-gauche (gg) conformation, whereas those facing the interior had the gauche-trans (gt) conformation. All the other C6-hydroxy groups of the cellulose molecules inside the microfibrils contributing to crystalline cellulose I had the trans-gauche (tg) conformation. After surface peeling, the originally second-layer molecules from the microfibril surface became the outermost surface molecules, and the original tg conformation changed to gg and gt conformations. The plant cellulose microfibrils likely had disordered structures for both the outermost surface and second-layer molecules, as demonstrated using the same layer-by-layer peeling technique.

The massive formation of hybrid shish‐kebab structures in HDPE/PA6 microfibril blend subjected to melt second flow

ABSTRACTDuring the melt second flow process, the synergetic effect of intense shear and polyamide 6 (PA6) microfibrils finally results in the massive formation of highly oriented crystalline structures in the entire thickness of high‐density polyethylene (HDPE)/PA6 microfibril blend. Interestingly, not only does the small microfibril induce HDPE crystallization to form typical hybrid shish–kebab structure, but the large microfibril (about 2 μm in diameter) also induces the formation of local hybrid shish–kebab structure. For the small PA6 microfibril, the oriented HDPE chains caused by the intense shear are absorbed on the whole surface of the microfibril and then a complete polymer underlayer is formed. Subsequently, the crystal nuclei appear on the underlayer, and then the other oriented HDPE chains overgrow from the nuclei in the form of folded chains and grow perpendicular to the microfibril. Finally, the typical hybrid shish–kebab structure is formed. While for the large PA6 microfibril, a few HDPE chains can be still absorbed on the microfibril surface due to the high surface energy of PA6. However, the driving force is insufficient to absorb largely oriented HDPE chains to form complete hybrid shish but only local adsorption layer, so the local hybrid structure is formed. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017, 134, 45274.

Effective in situ polyamide 6 microfibrils in isotactic polypropylene under microinjection molding: significant improvement of mechanical performance

Microparts of isotactic polypropylene (iPP)/polyamide 6 (PA6) blends were prepared with a particular injection molding method known as microinjection molding (MIM). Continuous and strong shear action exerted on the melts of iPP/PA6 directly promoted the formation of in situ PA6 microfibril in MIM. Moreover, hierarchical structures, namely, spherulite, cylindrites, and transcrystallization, were observed in the microparts. The synergetic effect of PA6 in situ microfibrils, β-nucleating agent (β-NA), and strong shear action even induced more oriented β-crystals around the surface of PA6 microfibrils in the core layer and markedly increased the β-crystal content. Results showed that adding PA6 and β-NA markedly raised the crystallization temperature of iPP, and the effect of PA6 microfibrils was evidently more pronounced than that of PA6 spherical particles in conventional blends which implies more nucleation sites on the microfibrils. Moreover, strong orientation of iPP molecular chain was also confirmed by 2D-WAXD. It is well worth mentioning that the mechanical property was remarkably improved by these special morphology and crystalline structures.

Evolution of Xylan Substitution Patterns in Gymnosperms and Angiosperms: Implications for Xylan Interaction with Cellulose.

The interaction between cellulose and xylan is important for the load-bearing secondary cell wall of flowering plants. Based on the precise, evenly spaced pattern of acetyl and glucuronosyl (MeGlcA) xylan substitutions in eudicots, we recently proposed that an unsubstituted face of xylan in a 2-fold helical screw can hydrogen bond to the hydrophilic surfaces of cellulose microfibrils. In gymnosperm cell walls, any role for xylan is unclear, and glucomannan is thought to be the important cellulose-binding polysaccharide. Here, we analyzed xylan from the secondary cell walls of the four gymnosperm lineages (Conifer, Gingko, Cycad, and Gnetophyta). Conifer, Gingko, and Cycad xylan lacks acetylation but is modified by arabinose and MeGlcA. Interestingly, the arabinosyl substitutions are located two xylosyl residues from MeGlcA, which is itself placed precisely on every sixth xylosyl residue. Notably, the Gnetophyta xylan is more akin to early-branching angiosperms and eudicot xylan, lacking arabinose but possessing acetylation on alternate xylosyl residues. All these precise substitution patterns are compatible with gymnosperm xylan binding to hydrophilic surfaces of cellulose. Molecular dynamics simulations support the stable binding of 2-fold screw conifer xylan to the hydrophilic face of cellulose microfibrils. Moreover, the binding of multiple xylan chains to adjacent planes of the cellulose fibril stabilizes the interaction further. Our results show that the type of xylan substitution varies, but an even pattern of xylan substitution is maintained among vascular plants. This suggests that 2-fold screw xylan binds hydrophilic faces of cellulose in eudicots, early-branching angiosperm, and gymnosperm cell walls.

Surfactant-free emulsions stabilized by tempo-oxidized bacterial cellulose

In order to seek a safe, biodegradable, and sustainable solid stabilizer for food, topical and pharmaceutical emulsions, individualized cellulose nanofibers were prepared by oxidizing bacterial cellulose (BC) in a Tempo-mediated system; their ability to stabilize oil/water interface was investigated. Significant amounts of C6 carboxylate groups were selectively formed on each cellulose microfibril surface, so that the hydrophilicity was strengthened, leading to lower contact angles. Meanwhile, both the length and width of fibrils were decreased significantly, by partial cleavage of numerous numbers of inter- and intra-fibrillar hydrogen bonds. Tempo-oxidized BC (TOBC) was more effective than BC in stabilizing oil-water interface, attributing to the much smaller size. Fibril dosage and oxidation degree exerted a great influence on the stability and particle size distribution of emulsion samples. When the fibril dosage was 0.7wt.%, the sample was so stable that it did not experience creaming and coalescence over 8 months. The 2-TOBC coated droplets showed the greatest stability, although both the zeta potential and the electric repulsion were the largest for the 10-TOBC analogue, which was manipulated by the wettability of fibrils. In addition, the stability of samples was analyzed from the viewpoint of particle size distribution. Consequently, fibril size and wettability are two counterbalanced factors influencing the stability of TOBC-stabilized emulsions; a combination of suitable wettability and size imparts TOBC-stabilized emulsion high stability. As a kind of biomass-based particle stabilizer, TOBC showed great potential applications in food, topical and pharmaceutical formulations.