Surface Of Cellulose 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.

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.

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.

Cellulose-supported magnetic Fe3O4–MOF composites for enhanced dye removal application

Cellulose micro-fibrils (CMF), which are green, sustainable and are made from abundant renewable biomass, have attracted much attention in the research community for various applications. In this study, we presented a novel magnetic cellulose composite catalyst (HKUST-1/Fe3O4/CMF) for pollution remedy purpose. The main function of CMF is to improve the dispersion of metal organic framework (MOF) crystals (HKUST-1) and Fe3O4 nanoparticles (NPs) so that the catalytic performance of resultant HKUST-1/Fe3O4/CMF composite is enhanced. The as-prepared HKUST-1/Fe3O4/CMF catalyst was characterized by TEM, EDX, BET, XRD, FTIR, TGA and VSM analytical techniques. Results have showed that HKUST-1 and Fe3O4 NPs are anchored onto the surface of CMF. The adsorption efficiency of HKUST-1/Fe3O4/CMF composite has enhanced because of the porous MOF structures. Furthermore, the composite catalyst has a large surface area and exhibits good magnetic and catalytic properties in the Fenton system. When used as a catalyst in the degradation of dye model compound (methylene blue, MB), the composite catalyst shows a high catalytic activity. In addition, the composite catalyst reveals a good reusability, durability in the recycling and reuse testing. These results support to conclude that the as-prepared HKUST-1/Fe3O4/CMF composite is a green, sustainable, effective and potential catalyst system for pollutant remedy.

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.

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.

Xylan decoration patterns and the plant secondary cell wall molecular architecture.

The molecular architecture of plant secondary cell walls is still not resolved. There are several proposed structures for cellulose fibrils, the main component of plant cell walls and the conformation of other molecules is even less well known. Glucuronic acid (GlcA) substitution of xylan (GUX) enzymes, in CAZy family glycosyl transferase (GT)8, decorate the xylan backbone with various specific patterns of GlcA. It was recently discovered that dicot xylan has a domain with the side chain decorations distributed on every second unit of the backbone (xylose). If the xylan backbone folds in a similar way to glucan chains in cellulose (2-fold helix), this kind of arrangement may allow the undecorated side of the xylan chain to hydrogen bond with the hydrophilic surface of cellulose microfibrils. MD simulations suggest that such interactions are energetically stable. We discuss the possible role of this xylan decoration pattern in building of the plant cell wall.

Creation of a new material stream from Japanese cedar resources to cellulose nanofibrils

Japanese cedar is one of the most abundant plantation softwoods in Japan, although it is not effectively utilized as a wood resource. Japanese cedar cellulose was isolated and subjected to one-pot catalytic oxidation and reduction with 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) and NaBH4, respectively. The TEMPO-oxidized and NaBH4-reduced Japanese cedar celluloses (TOCs-NaBH4) had carboxylate content of up to 1.4mmol/g and viscosity-average degrees of polymerization from 2000 to 3000. The X-ray diffraction patterns of the TOCs-NaBH4 showed that the crystal widths were ~3nm, indicating that the C6-OH groups present on the crystalline cellulose microfibril surfaces were selectively oxidized to C6-carboxylate groups. When the TOCs-NaBH4 with carboxylate content of 0.9–1.4mmol/g were mechanically disintegrated in water, transparent TEMPO-oxidized cellulose nanofibril (TOCN) dispersions were obtained. The lengths of the TOCNs, determined from their atomic force microscopy images, varied from 800 to 1500nm, depending on the oxidation conditions. The TOCNs prepared from Japanese cedar cellulose have an average of high aspect ratios (>300), which is greater than that (~150) prepared from wood pulp and thus advantageous.

Wood nanocelluloses: fundamentals and applications as new bio-based nanomaterials

Nanocelluloses, which include nanofibrillated celluloses (NFCs) and cellulose nanocrystals (CNCs) with high and low aspect ratios, respectively, are promising new bio-based nanomaterials, prepared from wood and other plant celluloses by mechanical shearing in water with or without pretreatments. Low degrees of enzymatic hydrolysis, carboxymethylation, acetylation, oxidation, and other position-selective modifications on cellulose microfibril surfaces have been applied as pretreatments to wood celluloses to reduce energy consumption in the mechanical shearing process and to improve the nanofibrillation level of the obtained NFCs. NFCs are convertible to nanocellulose sheets, films, hydrogels, foams, and aerogels with fibril network structures or close-packing structures using coating on base films or filtration process like papermaking, which is advantageous for efficient removal of water predominantly present in the NFC/water dispersions. NFC-containing self-standing films, coated films, and NFC/matrix nanocomposites in most cases show explicitly high mechanical strength and ductility despite being lightweight and having optical transparency, thermal stability, and gas-barrier properties. Because NFCs have aspect ratios and molecular weights higher than those of CNCs, the most promising and challenging end products are NFC-containing nanocomposite materials having higher functionalities than those of the conventional fiber-reinforced composite materials.

How do expansins control plant growth? A model for cell wall loosening via defect migration in cellulose microfibrils

Expansins are plant cell wall-loosening proteins that promote cell growth and are essential for many critical developmental processes and stress responses. The molecular basis for expansin action is uncertain. Recently, it has been proposed that expansins loosen the wall by means of the generation of mobile conformational defects at the surface of cellulose microfibrils. The present work addresses this hypothesis by elaborating three assumptions: (1) microfibril–matrix interfaces cause steep stress gradients on the microfibril surface, (2) stress gradients drive the motion of conformational defects along the microfibril surface toward the microfibril–matrix interfaces, and (3) the approach of the defects to the microfibril–matrix interfaces facilitates the dissociation of matrix polysaccharides from cellulose microfibrils.

Oxidation of wood cellulose using 2-azaadamantane N-oxyl (AZADO) or 1-methyl-AZADO catalyst in NaBr/NaClO system

A wood cellulose was oxidized with catalytic amounts of 2-azaadamantane N-oxyl (AZADO) or 1-methyl-AZADO, in an NaBr/NaClO system, in water at pH 10. The oxidation efficiency, carboxylate/aldehyde contents, and degree of polymerization (DPv) of the oxidized celluloses thus obtained were evaluated in terms of the amount of AZADO or 1-methyl-AZADO catalyst added, in comparison with those prepared using the TEMPO/NaBr/NaClO system. When the AZADO/NaBr/NaClO and 1-methyl-AZADO/NaBr/NaClO oxidation systems were applied to wood cellulose using the same molar amount of TEMPO, the oxidation time needed for the preparation of oxidized celluloses with carboxylate contents of 1.2–1.3 mmol/g was reduced from ≈80 to 10–15 min. Moreover, the molar amounts of AZADO and 1-methyl-AZADO that had to be added for the preparation of oxidized celluloses with carboxylate contents of 1.2–1.3 mmol/g were reduced to 1/32 and 1/16 of the amount of TEMPO added, respectively. The DPv values for the AZADO- and 1-methyl-AZADO-oxidized celluloses after NaBH4 treatment were in the range of 600–800. This indicated that not only C6-carboxylate groups but also C2/C3 ketones were formed to some extent on the crystalline cellulose microfibril surfaces during the AZADO- and 1-methyl-AZADO-mediated oxidation. When the AZADO-oxidized wood cellulose, which had a carboxylate content of 1.2 mmol/g, was mechanically disintegrated in water, an almost transparent dispersion consisting of individually nano-dispersed oxidized cellulose nanofibrils was obtained, with a nanofibrillation yield of 89 %.

TEMPO-Mediated Oxidation of Hemp Bast Holocellulose to Prepare Cellulose Nanofibrils Dispersed in Water

Hemp bast holocellulose fiber (Cannabis sativa L. Subsp. Sativa) was oxidized by TEMPO (2,2,6,6-tetramethylpiperidine-1-oxyl radical)-mediated oxidation at various NaClO addition levels in water at pH 10. When carboxylate contents of the oxidized products were 1.5–1.7 mmol/g, TEMPO-oxidized cellulose nanofibrils almost completely dispersed at the individual nanofibril were obtained by mechanical disintegration of the TEMPO-oxidized hemp bast holocelluloses in water, where the nanofibrillation yields were 98–100 %. The sugar composition analysis revealed that most of hemicelluloses originally present in the hemp bast holocellulose were degraded and removed from the solid oxidized products, providing almost pure TEMPO-oxidized celluloses. X-ray diffraction patterns of all TEMPO-oxidized hemp bast holocelluloses had the same cellulose I crystal structure and similar crystallinity indices and crystal widths, indicating that carboxylate groups formed by the oxidation were selectively present on the crystalline cellulose microfibril surfaces in the holocellulose. However, the weight recovery ratios and viscosity-average degrees of polymerization of the TEMPO-oxidized hemp bast holocelluloses decreased to 69–59 % and 470–380, respectively, when their carboxylate contents increased to 1.5–1.7 mmol/g by the TEMPO-mediated oxidation. Atomic force microscopy height images showed that the nanofibril widths were 2.7–2.9 nm, and the average nanofibril lengths decreased from 590 to 400 nm as the NaClO addition level was increased from 7.5 to 12.5 mmol/g in the TEMPO-mediated oxidation.

Heterogeneous reaction between cellulose and alkyl ketene dimer under solvent-free conditions

Four native celluloses, i.e. hardwood bleached kraft pulp (HBKP), cotton linters, bacterial cellulose and microcrystalline cellulose, were heterogeneously reacted with alkyl ketene dimer (AKD) at 100 °C for 24 h in the presence of a small amount of 1-methylimidazole used as an esterification promoter under solvent-free conditions. AKD molecules were reacted with cellulose hydroxyl groups to form β-ketoester linkages by the above conditions. Each reaction product was separated into chloroform-soluble and -insoluble fractions, and weight ratios and degrees of substitution (DS) of the two fractions were measured. The weight ratios of the CHCl3-insoluble fractions varied from 30 to 95 % of the products, and the DS values from 0.03 to 1.6, depending on the starting cellulose samples. X-ray diffraction and solid-state 13C-NMR analyses of the CHCl3-insoluble fraction with DS 0.75 in the AKD-treated HBKP indicated that β-ketoester substituents were introduced to hydroxyl groups on the cellulose microfibril surfaces. This CHCl3-insoluble fraction had thermoplastic properties, and was convertible to translucent or transparent films by hot pressing at 160–180 °C.

Light-Scattering Analysis of Native Wood Holocelluloses Totally Dissolved in LiCl–DMI Solutions: High Probability of Branched Structures in Inherent Cellulose

Three holocelluloses (i.e., cellulose and hemicellulose fractions) are prepared from softwood and hardwood by the Wise method. These holocelluloses completely dissolve in 8% lithium chloride/1,3-dimethyl-2-imidazolidinone (LiCl/DMI) after an ethylenediamine (EDA) pretreatment. After diluting the holocellulose solutions to 1% LiCl/DMI, they are subjected to size-exclusion chromatography/multiangle laser-light scattering/photodiode array (SEC-MALLS-PDA) analysis. All holocelluloses exhibit bimodal molecular weight distributions primarily due to high-molecular-weight (HMW) cellulose and low-molecular-weight hemicellulose fractions. Plots of molecular weight vs root-mean-square radius obtained by SEC-MALLS analysis revealed that all the wood celluloses comprise dense conformations in 1% LiCl/DMI. In contrast, bacterial cellulose, which was used as a pure cellulose model, has a random coil conformation as a linear polymer. These results show that both softwood and hardwood HMW celluloses contain branched structures, which are probably present on crystalline cellulose microfibril surfaces. These results are consistent with those obtained by permethylation analysis of wood celluloses.

Use of thermogravimetric analysis to monitor the effects of natural laccase mediators on flax pulp

The effects of 1-hydroxybenzotriazole (HBT) and the natural laccase mediators gallic acid, caffeic acid and p-hydroxybenzoic acid, on the enzymatic bleaching of flax pulp were compared. The treatment was performed under atmospheric air and oxygen pressure, and, for the first time, monitored by thermogravimetric analysis (TGA) for comparison with chemical analysis, FTIR and X-ray diffraction (XRD) spectroscopies. Thermogravimetric data were simulated by applying a nucleation kinetic equation to a combustion model based on four pseudo-components (hemicellulose, amorphous and crystalline cellulose, and lignin). The results thus obtained show that the effects of the natural mediators are similar to those of HBT and lead to increased order in cellulose microfibril surfaces. An increase in pulp crystallinity was additionally exposed by the XRD and FTIR techniques, and a reduction in microfibril equatorial size by the XRD patterns. Simulated DTG curves were used to determine the kinetic parameters for thermal degradation.

Wood cellulose nanofibrils prepared by TEMPO electro-mediated oxidation

A softwood bleached kraft pulp (SBKP) was subjected to electro-mediated oxidation in water with TEMPO or 4-acetamido-TEMPO without any chlorine-containing oxidant. Solid recovery ratios of water-insoluble fractions of the oxidized SBKPs were more than 80%, and C6-carboxylate contents increased up to approximately 1 mmol g−1 after oxidation for 48 h. Significant amounts of C6-aldehyde groups (0.17–0.38 mmol g−1) were also formed in the oxidized SBKPs. The degree of polymerization decreased from 2,200 to 520 and 1,400 by the oxidation for 48 h with TEMPO at pH 10 and 4-acetamido-TEMPO at pH 6.8, respectively. The original cellulose I crystal structure and crystallinity of SBKP were maintained after the oxidation, indicating that all C6-oxidized groups were selectively formed on crystalline cellulose microfibril surfaces. The oxidized SBKPs with carboxylate contents of more than 0.9 mmol g−1 were convertible to individual cellulose nanofibrils in yields of more than 80% by disintegration in water.

Quasi-One-Dimensional Arrangement of Silver Nanoparticles Templated by Cellulose Microfibrils

We demonstrate a simple, facile approach to the deposition of silver nanoparticles on the surface of cellulose microfibrils with a quasi-one-dimensional arrangement. The process involves the generation of aldehyde groups by oxidizing the surface of cellulose microfibrils and then the assembly of silver nanoparticles on the surface by means of the silver mirror reaction. The linear nature of the microfibrils and the relatively uniform surface chemical modification result in a uniform linear distribution of silver particles along the microfibrils. The effects of various reaction parameters, such as the reaction time for the reduction process and employed starting materials, have been investigated by transmission electron microscopy (TEM) and ultraviolet-visible spectroscopy. Additionally, the products were examined for their electric current-voltage characteristics, the results showing that these materials had an electric conductivity of approximately 5 S/cm, being different from either the oxidated cellulose or bulk silver materials by many orders of magnitude.