Preparation and characterization of bionanocomposite fiber based on cellulose and nano-SiO2 using ionic liquid

Microcrystalline cellulose (MCC)/nano-SiO₂ composite fibers were processed from solutions in 1-allyl-3-methylimidazolium chloride (AMIMCl) by the method of dry-jet wet spinning. The oscillatory shear measurements demonstrated that the gel network formed above 10 wt% nano-SiO₂ and the complex viscosity increased with increasing nano-SiO₂. Remarkably, the shear viscosity of the nanofluids was even lower than solutions without nano-SiO₂ under high shear rates. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) images revealed that well-dispersed particles exhibit strong interfacial interactions with cellulose matrix. Measurements on wide-angle X-ray diffraction (WAXD) indicated that the regenerated cellulose and nanocomposite fibers were the typical cellulose II crystalline form, which was different from the native cellulose with the polymorph of Type I. The tensile strength of the nanocomposite fibers was larger than that of pure cellulose fiber and showed a tendency to increase and then decrease with increasing nano-SiO₂. Furthermore, the nanocomposite fibers exhibited improved thermal stability.     

Importance of Small Pores in Microcrystalline Cellulose for Controlling Water Distribution during Extrusion–Spheronization

The purpose of this research was to investigate the effects of particle size on the wet massing behavior of microcrystalline cellulose (MCC). In this study, a series of six fractionated MCC grades were customized and specially classified to yield different particle size varieties of the standard grade, Comprecel M101. All seven MCC grades were extensively characterized for the physical properties and wet massing behavior using mixer torque rheometry. Effects of MCC physical properties on the maximum torque (Torque_max) were determined using partial least squares (PLS) analysis. Most physical properties varied systematically with particle size and morphological changes. Marked differences were observed in the small pore volumes (V _highP) and BET surface areas of the MCC grades. Variables that exerted dominant influences on Torque_max were identified. In particular, the significance of V _highP in governing wet mass consistency was established. The role of V _highP has not been reported in any study because this small but significant variation is likely to be obliterated or compensated by variation in other physical properties from MCC grades from different suppliers. The findings demonstrated the role of small pores in governing the wet mass consistency of MCC and provide a better understanding of MCC’s superior performance as a spheronization aid by the ability to fulfill the function as a molecular sponge to facilitate pellet formation during wet granulation processes.     

Cellulose-binding domain of endoglucanase III from Trichoderma reesei disrupting the structure of cellulose

The DNA fragment encoding the cellulose binding domain of endoglucanase III (CBD_{EG III}) from Trichoderma reesei was subcloned and expressed in E. coli. The CBD_{EG III} had a high affinity for cellulose. The morphological and structural changes of cellulose after treatment with CBD_{EG III} indicated a 17% decrease in number of hydrogen bonds and a 16.5% decrease in crystalline index. X-ray diffraction and IR spectra analyses indicated that the destabilization and breakage of the hydrogen bonds in crystalline cellulose accounted for the non-hydrolytic disruption of the structure of cellulose.     

Green composite films prepared from cellulose,starch and lignin in room-temperature ionic liquid

A series of novel biobased composite films derived from cellulose, starch and lignin were prepared from an ionic liquid (IL), 1-allyl-3-methylimidazolium chloride (AmimCl) by coagulating in a nonsolvent condition. The ionic liquid can be recycled with a high yield and purity after the green film was prepared. The uniform design method was applied to investigate mechanical properties of the biobased composite films. The effect of each component and their associated interactive effects were investigated. The experimental results showed that contents of cellulose, lignin and starch had a significant influence on the mechanical properties of composite films. The composite films showed relatively excellent mechanical properties in dry and wet states owing to the mutual property supplement of different components. The composite films were characterized via FT-IR, X-ray diffraction (XRD) and scanning electron microscope (SEM). Their thermal stability and gas permeability were also investigated, and the results showed that the composite films had good thermal stability and high gas barrier capacity and give a CO₂:O₂ permeability ratio close to 1.     

Almost Pure Iα Cellulose in the Cell Wall of Glaucocystis

Crystalline features of cellulose microfibrils in the cell walls of Glaucocystis (Glaucophyta) were studied by combined spectroscopy and diffraction techniques, and the results were compared with those of Oocystis (Chlorophyta). Although these algae are grouped into two different classes, by the composition of their chloroplasts for instance, their cell walls are quite similar in size and morphology. The most striking features of their cellulose crystallites are that they have the highest cellulose I_α contents reported to date. In particular, the I_α fraction of cellulose from Glaucocystis was found to be as high as 90% from ¹³C NMR analysis. The mode of preferential orientation of cellulose crystallites in their cell walls is also interesting; equatorial 0.53-nm lattice planes were oriented parallel to the cell surface in the case of Glaucocystis, while the 0.62-nm planes were parallel to the Oocystis cell surface. Such a structural variation provides another link to the evolution of cellulose structure, biosynthesis, and its biocrystallization mechanism.     

A high-temperature water vapor equilibration method to determine non-exchangeable hydrogen isotope ratios of sugar,starch and cellulose

The analysis of the non-exchangeable hydrogen isotope ratio (δ²H_ne) in carbohydrates is mostly limited to the structural component cellulose, while simple high-throughput methods for δ²H_ne values of non-structural carbohydrates (NSC) such as sugar and starch do not yet exist. Here, we tested if the hot vapor equilibration method originally developed for cellulose is applicable for NSC, verified by comparison with the traditional nitration method. We set up a detailed analytical protocol and applied the method to plant extracts of leaves from species with different photosynthetic pathways (i.e., C₃, C₄ and CAM). δ²H_ne of commercial sugars and starch from different classes and sources, ranging from ?157.8 to +6.4‰, were reproducibly analysed with precision between 0.2‰ and 7.7‰. Mean δ²H_ne values of sugar are lowest in C₃ (?92.0‰), intermediate in C₄ (?32.5‰) and highest in CAM plants (6.0‰), with NSC being ²H-depleted compared to cellulose and sugar being generally more ²H-enriched than starch. Our results suggest that our method can be used in future studies to disentangle ²H-fractionation processes, for improving mechanistic δ²H_ne models for leaf and tree-ring cellulose and for further development of δ²H_ne in plant carbohydrates as a potential proxy for climate, hydrology, plant metabolism and physiology.     

Nutzung cellulosehaltiger Abprodukte bei der Biosynthese von Cellulasen

It was analysed the influence of different pretreatment methods of cellulosic materials to increase the productivity of the cellulase biosynthesis. The most effective pretreatment method for cotton cellulose is the thermomechanical destruction in a worm extruder (5–15 minutes) with hydrolysis catalysts. The enzymatic saccharification degree was increased about 4 fold. Utilizing a pretreated cellulose an increase of 70–120% in C₁-activity was found besides their level was stabilized in higher values. It was demonstrated that enzymatic hydrolysis parameters would be applied as model for biochemical utilization of cellulosic materials in the biosynthesis of cellulases.     

Anaerobic digestion of cellulose by pure and mixed bacterial cultures

Summary By enrichment technique, nine anaerobic mixed bacterial cultures were isolated, five of which showed stable cellulolysis. All cultures fermented cellulose and produced different fermentative products. Mixed culture BOC 25 yielded major levels of acetate and ethanol (39.6 and 12.0 mmol/l, respectively) and minor levels of propionate (2.5 mmol/l) and digested filter paper cellulose to the extent of 32.5% w/v. BOC 25 digested cellulosic and lignocellulosic substrates and produced filter paper cellulase, carboxymethyl cellulase, Avicelase and -glucosidase. Strain DC 25, a cellulolyticClostridium was purified from one of the mixed cultures. The fermentation products of DC 25 from cellulose, cellobiose or glucose were ethanol, acetate, formate, H₂ and CO₂.     

Influence of avocado (Persea americana) Cx-cellulase on the structural features of avocado cellulose

Avocado (Persea americana Mill.) fruit produce copious quantities of the enzyme Cx-cellulase (EC 3.2.1.4) during ripening. The possibility that Cx-cellulase is able to disrupt cellulose microfibril oranization was investigated using molecular weight (M_r), x-ray diffraction, and ultrastructural analyses of cell walls from unripe avocado fruit incubated with the purified enzyme. Results indicate that Cx-cellulase causes a downshift in the M_r of unbranched cell-wall polymers in the M_r range of 10⁶–10⁷ Da. There is an increase in the proportion of crystalline cellulose, and cellulose fibrils appear to lose cohesiveness in response to enzyme activity. We propose that Cx-cellulase attacks avocado cellulose at accessible sites in the peripheral and integral noncrystalline regions of the microfibril, resulting in a loss of cohesiveness within the fibril structure and an alteration in the binding of associated cell-wall matrix polysaccharides. The initial loss of avocado mesocarp firmness during fruit ripening may be linked to the onset of Cx-cellulase activity.Abbreviations CMC carboxymethylcellulose - DMAC dimethylacetamide - DS developmental stage - M molecular weight - XG xyloglucan     

Physico-Mechanical Properties of Chemically Treated Bacterial (Acetobacter xylinum) Cellulose Membrane

Bacterial cellulose obtained through fermentation by the Acetobacter xylinum is of superior functional quality in comparison to plant cellulose. Various alkali treatment methods were used to process bio-chemically complex pellicle into a clean cellulose membrane/sheet. The effect of potassium hydroxide, sodium carbonate and potassium carbonate was found to be milder on the final cellulose product in contrast to the widely used sodium hydroxide treatment. These novel treatment methods also caused improvement in the tensile strength of the membranes in comparison to sodium hydroxide. The overall quality of the 0.1 M sodium carbonate- and potassium carbonate-treated cellulose was superior, as the membranes displayed maximum tensile strength and elongation next to the native membrane. The low tensile strength of sodium hydroxide-treated membrane is attributed to its higher swelling characteristics in alkali. Further, the low swelling property of sodium carbonate- and potassium carbonate-treated membranes resulted in their high oxygen transmission rates (low oxygen barrier). Hunter lab colour parameters were determined to assess the effect of different alkali treatments on the colour characteristics of the membranes. Further, based on the high mechanical strength and comparatively low oxygen transmission rates, the processed cellulose membranes may find application as a bio- packaging material for controlled atmosphere packaging, where hydrophilic membranes with high oxygen barrier and water vapour permeation are desirable.     

The effect of pH, sucrose and ammonium sulphate concentrations on the production of bacterial cellulose (Nata-de-coco) by Acetobacter xylinum

The effect of pH, sucrose and ammonium sulphate concentrations on the production of nata-de-coco, a form of bacterial cellulose, by Acetobacter xylinum was studied. Comparisons for physical properties like thickness, wet weight, water-holding capacity (WHC), moisture content and hardness, a textural parameter were done on nata-de-coco grown in tender coconut water medium supplemented with varying concentrations of sucrose and ammonium sulphate at different pH values. The results were analysed by fitting a second-order polynomial regression equation. Response surface methodology was used to study the effect of the three variables. The study showed that A. xylinum could effectively use sucrose as the sole carbon source in coconut water medium and that cellulose production was more dependent on pH than either sucrose or ammonium sulphate concentrations. Maximum thickness of nata was obtained at pH 4.0 with 10% sucrose and 0.5% ammonium sulphate concentrations. These conditions also produced good quality nata-de-coco with a smooth surface and soft chewy texture. The study will enable efficient utilization of coconut water, a hitherto wasted byproduct of coconut industry and will also provide a new product dimension to the aggrieved coconut farmers who are not getting the right price for their product.     

A convenient method to study fungal spores retention on a porous preformed support

A method was developed to determine engineering parameters of a preformed porous cellulose carrier, commercially known as Microcube. It demonstrated a high water retention (20 g g^–1 dry support) connected to a wet support density slightly higher than that of water (1.005 g ml^–1), making this material suitable for use in stirred vessels; a high porosity (96%) was also evidenced. Ungerminated spores of Aspergillus niger reversibly adsorbed on the carrier according to a Langmuir-type isotherm, while germinating conidia irreversibly attached to particles, allowing a further pellet-like development.     

Alkaline peroxide assisted wet air oxidation pretreatment approach to enhance enzymatic convertibility of rice husk

Pretreatment of rice husk by alkaline peroxide assisted wet air oxidation (APAWAO) approach was investigated with the aim to enhance the enzymatic convertibility of cellulose in pretreated rice husk. Rice husk was presoaked overnight in 1% (w/v) H₂O₂ solution (pH adjusted to 11.5 using NaOH) (equivalent to 16.67 g H₂O₂ and 3.63 g NaOH per 100 g dry, untreated rice husk) at room temperature, followed by wet air oxidation (WAO). APAWAO pretreatment resulted in solubilization of 67 wt % of hemicellulose and 88 wt % of lignin initially present in raw rice husk. Some amount of oligomeric glucose (?8.3 g/L) was also observed in the APAWAO liquid fraction. APAWAO pretreatment resulted in 13‐fold increase in the amount of glucose that could be obtained from otherwise untreated rice husk. Up to 86 wt % of cellulose in the pretreated rice husk (solid fraction) could be converted into glucose within 24 hours, yielding over 21 g glucose per 100 g original rice husk. Scanning electron microscopy was performed to visualize changes in biomass structure following the APAWAO pretreatment. Enzymatic cellulose convertibility of the pretreated slurry at high dry matter loadings was also investigated. © 2011 American Institute of Chemical Engineers Biotechnol. Prog., 2011     

Assessing the Relative Efficiency of Termite Sampling Methods along a Rainfall Gradient in African Savannas

Although termites are ecosystem engineers in tropical and sub‐tropical environments, the study of termite ecology is often constrained by sampling difficulties and a lack of established sampling protocols, particularly for savannas. The efficiency and relevance of different methods along climatic gradients, even within a single biome, is largely unknown. Here, we compare the relative contribution of two commonly used sampling methods, cellulose baits and active searching transects, in quantifying savanna termite diversity along a rainfall gradient in South Africa; sampling was conducted during the wet season across four markedly different savanna types. We also assessed the usefulness of different forms of baiting techniques. The relative efficiency of sampling method varied with annual rainfall. In arid savannas, baiting was as effective as active searching transects at sampling termite diversity and we recommend the use of baiting rather due to it being less labor intensive. In savannas of moderately low to intermediate rainfall, baiting and transects sampled different termite species and so both are deemed necessary for an accurate assessment of termite diversity. In contrast, in wetter savannas transects gave a better assessment of diversity, with cellulose baits not contributing much to diversity assessment. The efficiency of baiting techniques differed across the rainfall gradient, with baits needing to be left in the field for a longer period in more arid savannas. We conclude that habitat type, even within a single biome, will determine the sampling method or methods necessary to quantify termite diversity accurately.     

Spirochaeta caldaria sp. nov., a thermophilic bacterium that enhances cellulose degradation by Clostridium thermocellum

Two strains of obligately anaerobic, thermophilic spirochetes were isolated from cyanobacterial mat samples collected at freshwater hot springs in Oregon and Utah, USA. The isolates grew optimally between 48° and 52°C, and did not grow at 25° or 60°C. Both strains fermented various pentoses, hexoses, and disaccharides. Amino acids or cellulose did not serve as fermentable substrates for growth. H₂, CO₂, acetate, and lactate were end products of d-glucose fermentation. On the basis of physiological characteristics, guanine + cytosine content of DNA, and comparisons of 16S ribosomal RNA sequences, it was concluded that the two isolates were representatives of a novel species of Spirochaeta for which the name Spirochaeta caldaria is proposed. One of the two strains was grown in coculture with a thermophilic cellulolytic bacterium (Clostridium thermocellum) in a medium containing cellulose as the only fermentable substrate. In the coculture cellulose was broken down at a faster rate than in the clostridial monoculture. The results are consistent with the suggestion that interactions between cellulolytic bacteria and non-cellulolytic spirochetes enhance cellulose breakdown in natural environments in which cellulose-containing plant material is biodegraded.     

Application of bacterial cellulose pellets in enzyme immobilization

Over recent years, there has been a growing interest in the use of cellulose materials in bioprocessing technologies. Bacterial cellulose which is the pure cellulose has unique physical properties which differ from those of plant cellulose and has therefore attracted attention as a new functional material. The applications of bacterial cellulose rarely use the pellet type but it has potential in enzyme immobilization since pellet form is usually used in this field. In this research, Glucoamylase which is widely used in the food industry was immobilized on bacterial cellulose beads after testing using various activation procedures. The results showed that the epoxy method with glutaraldehyde coupling was the best method. After comparison of the different types of bacterial cellulose beads for glucoamylase immobilization, the wet bacterial cellulose beads of the smallest size (0.5–1.5 mm) were the best support. The immobilization of enzyme enhances its stability against changes in the pH value and temperature especially in the lower temperature region. The relative activity of the immobilized glucoamylase was still above 77% at pH 2.0 and it was the highest value in the literature. The relative activities were more than 68% in the lower temperature region even at 20 °C. Thus, bacterial cellulose beads are a practical potential support for the preparation of immobilized enzymes in industrial applications.     

Purification and properties of ascorbate free-radical reductase from potato tubers

Ascrobate free-radical reductase (EC 1.6.5.4) from potato tubers was purified to apparent homogencity by a method which included ammonium-sulfate precipitation, gel filtration and chromatography on diethylaminoethyl cellulose and hydroxylapatite. Gel filtration and gel electrophoresis showed that the purified enzyme was monomeric with a molecular weight of about 42 000. Enzyme activity was heat lable and severely inhibited by thiol reagents. The K_m values for enzyme substrates were estimated.Abbreviations AFR ascorbate free radical - AsA ascorbic acid - DE-32(52) diethylaminoethyl cellulose - Tricine N-[2-hydroxy-1,1-bis(hydroxymethyl)ethyl]-glycine     

An integrated spectroscopic and wet chemical approach to investigate grass litter decomposition chemistry

The chemical transformations that occur during litter decomposition are key processes for soil organic matter formation and terrestrial biogeochemistry; yet we still lack complete understanding of these chemical processes. Thus, we monitored the chemical composition of Andropogon gerardii (big bluestem grass) litter residue over a 36 month decomposition experiment in a prairie ecosystem using: traditional wet chemical fractionation based upon digestibility, solid state ¹³C nuclear magnetic resonance (NMR) spectroscopy and Fourier transform infrared (FTIR) spectroscopy. The goals of this study were to (1) determine the chemical changes occurring during A. gerardii litter decomposition, and (2) compare the information obtained from each method to assess agreement. Overall, we observed a 97 % mass loss of the original litter, through a two-stage decomposition process. In the first stage, within 12 months, non-structural, cellulose and hemicellulose fractions not encrusted in lignin were preferentially and rapidly lost, while the acid unhydrolyzable residue (AUR) and microbial components increased. During the second stage, 12–36 months, all wet chemical fraction masses decreased equivalently and slowly with time, and the AUR and the lignin-encrusted cellulose fractions decomposition rates were comparable to each other. Method comparisons revealed that wet chemical fractionation did not accurately follow the initial litter structures, particularly lignin, likely because of chemical transformations and accumulation of microbial biomass. FTIR and NMR were able to determine bulk structural characteristics, and aid in elucidating chemical transformations but lacked the ability to measure absolute quantities of structural groups. As a result, we warn from the sole use of wet chemical methods, and strongly encourage coupling them with spectroscopic methods. Our results overall support the traditional chemical model of selective preservation of lignin, but shows that this is limited to the early stages of decomposition, while lignin is not selectively preserved at subsequent stages. Our study also provides important evidence regarding the impact of chemically different litter structures on decomposition rates and pathways.     

Cellulose and xylans in the interface capsule in symbiotic cells of actinorhizae

Summary Enzyme-gold affinity labeling was used to show that in mature infected cells of actinorhizal symbioses the capsule on the plant host side of the symbiotic interface contained cellulose and xylans. Host species examined for cellulose wereAlnus rubra, Casuarina equisetifolia, C. glauca, Ceanothus cuneata, C. velutinus, Elaeagnus pungens, andMyrica cerifera.. Cellulose was in the capsule throughout the infected cell, implying that during development cellulose synthase was present in the host cell membrane component of the symbiotic interface. Any possible degradation of capsule cellulose by the microsymbiont was either incomplete or transient, because the polymer was present in mature infected cells. Cellulose labeling inCeanothus andElaeagnus was less consistent than in the other species. Dual labeled capsules inCasuarina glauca andAlnus rubra showed a similar distribution of xylans and cellulose. Cytochemical studies indicate that the capsule contains three major classes of cell wall polysaccharides: cellulose, hemicellulose (xylans), and pectins (shown previously). This suggests that the capsule is essentially a thin, internal, tubular plant cell wall.Abbreviations Au₅ Au₁₅ colloidal gold particles with mean diameter of 5 and 15 nm, respectively - CBHI cellobiohydrolase I - CBHII cellobiohydrolase II - PBS phosphate-buffered saline     

Image analysis of modified cellulose fibers from sugarcane bagasse by zirconium oxychloride

Surface modification of natural fibers has been made using different methods. In this paper, cellulose fibers from sugarcane bagasse were bleached and modified by zirconium oxychloride in situ. The chemically modified cellulose fibers were compared to those of bleached ones. Cellulose fibers were modified with ZrO₂·nH₂O nanoparticles through the use of zirconium oxychloride in acidic medium in the presence of cellulose fibers using urea as the precipitating agent. The spatial distribution characterization of hydrous zirconium oxide on cellulose fibers was carried out by combining both processing and image analyses obtained by SEM and statistical methodologies. Scanning electron microscopy (SEM), X-ray diffraction (XRD), and thermogravimetric analysis (TG) were also used to characterize the nanocomposite. Results indicated that ZrO₂·nH₂O nanoparticles of about 30-80 nm diameter deposited on cellulose fibers were heterogeneously dispersed.