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.     

Structure study of cellulose fibers wet-spun from environmentally friendly NaOH/urea aqueous solutions

In this study, structure changes of regenerated cellulose fibers wet-spun from a cotton linter pulp (degree of polymerization approximately 620) solution in an NaOH/urea solvent under different conditions were investigated by simultaneous synchrotron wide-angle X-ray diffraction (WAXD) and small-angle X-ray scattering (SAXS). WAXD results indicated that the increase in flow rate during spinning produced a better crystal orientation and a higher degree of crystallinity, whereas a 2-fold increase in draw ratio only affected the crystal orientation. When coagulated in a H2SO4/Na2SO4 aqueous solution at 15 degrees C, the regenerated fibers exhibited the highest crystallinity and a crystal orientation comparable to that of commercial rayon fibers by the viscose method. SAXS patterns exhibited a pair of meridional maxima in all regenerated cellulose fibers, indicating the existence of a lamellar structure. A fibrillar superstructure was observed only at higher flow rates (>20 m/min). The conformation of cellulose molecules in NaOH/urea aqueous solution was also investigated by static and dynamic light scattering. It was found that cellulose chains formed aggregates with a radius of gyration, Rg, of about 232 nm and an apparent hydrodynamic radius, Rh, of about 172 nm. The NaOH/urea solvent system is low-cost and environmentally friendly, which may offer an alternative route to replace more hazardous existing methods for the production of regenerated cellulose fibers.     

Preparation of cellulose films from solution of bacterial cellulose in NMMO

Bacterial cellulose (BC) was dissolved in N-methylmorpholine N-oxide (NMMO) to prepare regenerated BC films (RBC) with phase inversion. The solubility of BC, supermolecule on structure, morphology, thermal and physical properties of the films were investigated by Fourier transform infrared spectroscopy (FT-IR), solid-state cross polarization/magic angle spinning ¹³C nuclear magnetic resonance (CP/MAS ¹³C NMR), wide-angle X-ray diffraction (WAXD), scanning electron microscope (SEM), and thermogravimetric analysis (TGA). The investigation suggested BC was dissolved completely in NMMO. From the C₆ signal shifts to the amorphous area, the crystallinity of materials decreased from 79.20% to 38.17%, and the transformation from cellulose I to II occurred. It was also found that the banded structure of the native materials was replaced by homogeneous and densified sections, so RBC films had better mechanical and barrier properties, and do thermal stability was similar to that of the native BC.     

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.     

Cross-sectional analysis of the polysaccharide composition in cellulosic fiber materials by enzymatic peeling/high-performance capillary zone electrophoresis

A combined enzymatic, chemical, and analytical approach was used to determine the cross-sectional carbohydrate composition in cellulosic fibers. The outer surface of cellulosic fibers was enzymatically removed layer-by-layer with precise quantitative control, and the monosaccharides in the peelings were subsequently analyzed by high-performance capillary electrophoresis (HPCE) after precolumn derivatization with a UV label. This method was applied to dissolving pulps and regenerated cellulose fibers, with special emphasis on the cross-sectional distribution of hemicelluloses. Commercially available enzyme solutions were used, resulting in a reproducible peeling. Significant differences were found in the hemicellulose distribution across the fiber of different dissolving pulps, dependent on both natural source (beech or spruce) and preparation process (acidic sulfite cook or prehydrolysis kraft cook). Among the dissolving pulps, beech prehydrolysis kraft pulp showed the highest enrichment of surface xylan. Similar, albeit smaller, differences were noticed between various regenerated fibers (viscose, viscose Modal, and Lyocell): a thin hemicellulose-rich outermost layer was found in all the regenerated fibers studied.     

Significantly reinforced composite fibers electrospun from silk fibroin/carbon nanotube aqueous solutions

Microcomposite fibers of regenerated silk fibroin (RSF) and multiwalled carbon nanotubes (MWNTs) were successfully prepared by an electrospinning process from aqueous solutions. A quiescent blended solution and a three-dimensional Raman image of the composite fibers showed that functionalized MWNTs (F-MWNTs) were well dispersed in the solutions and the RSF fibers, respectively. Raman spectra and wide-angle X-ray diffraction (WAXD) patterns of RSF/F-MWNT electrospun fibers indicated that the composite fibers had higher β-sheet content and crystallinity than the pure RSF electrospun fibers, respectively. The mechanical properties of the RSF electrospun fibers were improved drastically by incorporating F-MWNTs. Compared with the pure RSF electrospun fibers, the composite fibers with 1.0 wt % F-MWNTs exhibited a 2.8-fold increase in breaking strength, a 4.4-fold increase in Young's modulus, and a 2.1-fold increase in breaking energy. Cytotoxicity test preliminarily demonstrated that the electrospun fiber mats have good biocompatibility for tissue engineering scaffolds.     

Cross-linking chitosan into UV-irradiated cellulose fibers for the preparation of antimicrobial-finished textiles

Chitosan cross-linked cellulose fibers were prepared using non-toxic procedures in order to confer antimicrobial properties to cellulose fibers. Citric acid was used as the cross-linker and NaH₂PO₄ as catalyst in previously UV-irradiated cellulose fibers. Further heat dried-cure process and washing with detergent, water and acetic acid (0.1 M) gave a maximum incorporation of chitosan of 27 mg per gram of functionalized textile. The thermogravimetric analysis of the material with the highest chitosan content showed an increased thermal stability compared to cellulose and chitosan. The UV-irradiation induced morphological changes, such as less entangled cellulose fibers, as observed by scanning electron microscopy, which was prompted to enhance the chitosan incorporation. The biomass and spore germination percentage of Penicillium chrysogenum and colony forming units per millilitre for Escherichia coli decreased significantly on the composed materials as compared to raw cellulose fiber and it was similar to that obtained with a commercial antimicrobial cellulose fiber.     

Immobilization of Candida rugosa lipase on electrospun cellulose nanofiber membrane

A biocatalyst with high activity retention of lipase was fabricated by the covalent immobilization of Candida rugosa lipase on a cellulose nanofiber membrane. This nanofiber membrane was composed of nonwoven fibers with 200 nm nominal fiber diameter. It was prepared by electrospinning of cellulose acetate (CA) and then modified with alkaline hydrolysis to convert the nanofiber surface into regenerated cellulose (RC). The nanofiber membrane was further oxidized by NaIO₄. Aldehyde groups were simultaneously generated on the nanofiber surface for coupling with lipase. Response surface methodology (RSM) was applied to model and optimize the modification conditions, namely NaIO₄ content (2–10 mg/mL), reaction time (2–10 h), reaction temperature (25–35 °C) and reaction pH (5.5–6.5). Well-correlating models were established for the residual activity of the immobilized enzyme (R² = 0.9228 and 0.8950). We found an enzymatic activity of 29.6 U/g of the biocatalyst was obtained with optimum operational conditions. The immobilized lipase exhibited significantly higher thermal stability and durability than equivalent free enzyme.     

Molecular and crystal structure of the regenerated form of (1→3)-α-d-glucan

The crystal structure of a regenerated form of (1→3)-α-d-glucan, obtained by solid state deacetylation of the triacetate derivative, has been determined by combined X-ray diffraction analysis and stereochemical model refinement. The structure crystallizes in an orthorhombic unit cell with parameters $\text{a = 16.46}\text{A}\text{?}\text{, b = 9.55}\text{A}\text{?}$ and c (fibre repeat)=8.44 Å, and space group P2₁2₁2₁. The chain conformation is nearly completely extended and is very close to a 2/1 helix, even though the dimer residue is the crystallographic repeat unit. An intramolecular O(2)  O(4)′ hydrogen bond stabilizes the conformation and extensive intermolecular hydrogen-bonding abilizes the packing. The resulting structure is sheet-like, with an alternating polarity of chain directions within the sheet. In its sheet-like character, extensive hydrogen-bonding, and insolubility in water, this polymorph of (1→3)-α-d-glucan resembles regenerated cellulose. The reliability of the structure analysis is indicated by the X-ray residual R=0.206.     

The dependence of pyrolysis behavior on the crystal state of cellulose

Cellulose was dissolved in the ionic liquid 1-butyl-3-methylimidazolium chloride, and then regenerated from the solution by using different methods. Thermogravimetric analysis (TG)-Differential Scanning Calorimetry (DSC), X-ray diffraction (XRD), and Scanning Electron Microscopy (SEM) were used to characterize the structure of the original and regenerated cellulose. Cellulose II or amorphous cellulose was obtained by pouring cellulose solution into de-ioned water or pouring de-ioned water into cellulose solution, respectively. The pyrolysis behavior of original and regenerated cellulose was tested in a fixed bed reactor. The pyrolysis of cellulose I gave high content of furfural and 1,4;3,6-dianhydro-alpha-d-glucopyranose in the liquid products, and cellulose II and amorphous cellulose gave high content of furfural and 5-(hydroxymethyl)-2-furancarboxyaldehyde, with 5-(hydroxymethyl)-2-furancarboxyaldehyde the highest for cellulose II and furfural the highest for amorphous cellulose. And the treatment of the cellulose samples favored the removal of oxygen in the form of CO₂ in the pyrolysis.     

Taxonomic significance of cellulosic cell walls in the bangiales (Rhodophyta)

Cellulose has been characterized from isolated cell walls of the conchocelis phases of both Porphyra umbilicalis and P. leucostricta. Evidence for cellulose II (regenerated cellulose) in Schweitzer's reagent extracts was provided by X-ray powder analysis and paper chromatography of partial hydrolyzates. The presence of cellulose in the conchocelis phase of species of Porphyra provides evidence for the continuity of cell wall composition within the Rhodophyta. Adoption of a classification scheme incorporating consolidation of all red algal orders under the single class Rhodophyceae is proposed.     

Green synthesis of a novel biodegradable copolymer base on cellulose and poly(p-dioxanone) in ionic liquid

A new cellulose graft copolymer was synthesized in 1-N-butyl-3-methylimidazolium chloride ([Bmim]Cl) by the ring opening graft polymerization (ROGP) of p-dioxanone (PDO) onto cellulose. The structure of the copolymer was characterized by ¹³C and ¹H NMR, WAXD, DSC as well as SEM. Cellulose graft copolymers with a molar substitution (MS) in the range of 2.08–4.60 were obtained with 24 h at 80 °C in a completely homogeneous procedure. The obtained copolymers exhibited the clear glass transition temperatures (T_g) indicating the inter-molecular and intra-molecular hydrogen bonds in cellulose molecules had been destroyed. The reaction media applied can be easily recycled and reused.     

A Comparative Analysis of in vitro cellulose synthesis from cell-free extracts of mung bean (Vigna radiata,Fabaceae) And Cotton (Gossypium hirsutum,Malvaceae)

A comparison of cellulose synthesized in vitro from primary walls of etiolated mung bean (Vigna radiata) seedlings and secondary walls of cotton fibers (Gossypium hirsutum) was made by applying conditions found to be essential for in vitro cellulose I assembly from cotton (Kudlicka et al., 1995, Plant Physiology, vol. 107, pp. 111–123). Mung bean fractions including the plasma membrane (PM), the first solubilized fraction (SE₁), and the second solubilized fraction (SE₂), incorporated more radioactive UDP-Glc into the total product than the same fractions from secondary walls. A significant difference was found with the mild digitonin solubilized fraction (SE₁), which produced eight times more total product than the SE₁ fraction of cotton. However, the SE₁ fraction from cotton produced a larger quantity of cellulose (32.1%) than from mung bean (6.9%). Treatment of the in vitro product by acetic/nitric acid reagent (AN) for varying periods of time demonstrated that cellulose synthesized in vitro from mung bean was more easily degraded than cellulose from cotton fibers. This would suggest that cellulose I produced in vitro from the cotton SE₁ fraction may have a higher crystallinity and DP than cellulose I produced in vitro from mung bean. The fibrils of cellulose produced by the SE, fraction of mung bean were loosely associated and not arranged into a compact bundle as in case of cellulose I synthesized by the cotton SE₁ fraction. The electron diffraction patterns (ED) of both products show reflections characteristic for cellulose I. Products from the SE₂ fraction of mung bean and cotton reveal similarities with the cellulose II allomorph synthesized, as well as abundant β-1,3-glucan.     

Structure and properties of hydroxyapatite/cellulose nanocomposite films

The aim of this study was to develop a new inorganic-organic hybrid film. Nanohydroxyapaptite (nHAP) particles as the inorganic phase was mixed with cellulose in 7 wt.% NaOH/12 wt.% urea aqueous solution with cooling to prepare a blend solution, and then inorganic-organic hybrid films were fabricated by coagulating with Na₂SO₄ aqueous solution. The structure and properties of the hybrid films were characterized by high resolution transmitting electron microscopy (HRTEM), field emission scanning electron microscopy (FESEM), thermo-gravimetric analysis (TGA), Fourier transform infra-red (FT-IR) spectra, wide angle X-ray diffraction (WAXD) and tensile testing. The results revealed that the HAP nanoparticles with mean diameter of about 30 nm were uniformly dispersed and well immobilized in the hybrid film as a result of the role of the nano-and micropores in the cellulose substrate. A strong interaction existed between HAP and cellulose matrix, and their thermal stability and mechanical strength were improved as a result of good miscibility. Furthermore, the results of 293T cell viability assay indicated that the HAP/cellulose films had excellent biocompatibility and safety, showing potential applications in biomaterials.     

Enhancement of enzymatic saccharification of cellulose by cellulose dissolution pretreatments

Attempts were made to enhance cellulose saccharification by cellulase using cellulose dissolution as a pretreatment step. Four cellulose dissolution agents, NaOH/Urea solution, N-methylmorpholine-N-oxide (NMMO), ionic liquid (1-butyl-3-methylimidazolium chloride; [BMIM]Cl) and 85% phosphoric acid were employed to dissolve cotton cellulose. In comparison with conventional cellulose pretreatment processes, the dissolution pretreatments were operated under a milder condition with temperature <130 °C and ambient pressure. The dissolved cellulose was easily regenerated in water. The regenerated celluloses exhibited a significant improvement (about 2.7- to 4.6-fold enhancement) on saccharification rate during 1st h reaction. After 72 h, the saccharification yield ranged from 87% to 96% for the regenerated celluloses while only around 23% could be achieved for the untreated cellulose. Even with high crystallinity, cellulose regenerated from phosphoric acid dissolution achieved the highest saccharification rates and yield probably due to its highest specific surface area and lowest degree of polymerization (DP).     

Enhanced enzymatic hydrolysis of sugarcane bagasse by N-methylmorpholine-N-oxide pretreatment

The cellulose dissolution solvent used in Lyocell process for cellulose fiber preparation, N-methylmorpholine-N-oxide (NMMO) monohydrate, was demonstrated to be an effective agent for sugarcane bagasse pretreatment. Bagasse of 20wt% was readily dissolved in NMMO monohydrate at 130 degrees C within 1h. After dissolution, bagasse could be regenerated by rapid precipitation with water as a porous and amorphous mixture of its original components. The regenerated bagasse exhibited a significant enhancement on enzymatic hydrolysis kinetic. Not only the reducing sugars releasing rate but also hydrolysis yield was enhanced at least twofold as compared with that of untreated bagasse. The cellulose fraction of regenerated bagasse was nearly hydrolyzed to glucose after 72h hydrolysis with Cellulase AP3. The recycled NMMO demonstrated the same performance as the fresh one on bagasse pretreatment for hydrolysis enhancement. The regenerated bagasse was directly used in simultaneous saccharification and fermentation (SSF) for ethanol production by Zymomonas mobilis. No negative effect on ethanol fermentation was observed and ethanol yield approximately 0.15 g ethanol/g baggasse was achieved.     

Study the biocatalyzing effect and mechanism of cellulose acetate immobilized redox mediators technology (CE-RM) on nitrite denitrification

The biocatalyzing effect of a novel cellulose acetate immobilized redox mediators technology (CE-RM) on nitrite denitrification process was studied with anthraquinone, 1,8-dichloroanthraquinone, 1,5-dichloroanthraquinone and 1,4,5,8-tetrachloroanthraquinone. The results showed that the immobilized 1,4,5,8-tetrachloroanthraquinone presented the best biocatalyzed effect which increased nitrite denitrification rate to 2.3-fold with 12 mmol/L 1,4,5,8-tetrachloroanthraquinone. The unequal biocatalyzing effect was due to the quantity and position of –Cl substituent in anthraquinone-structure. Moreover, the nitrite denitrification rate was increased with the oxidation reduction potential (ORP) values becoming more negative during the biocatalyzing process. The stabilized ORP value with 12 mmol/L immobilized 1,4,5,8-tetrachloroanthraquinone were 81 mV lower than the control. At the same time, the more OH^? was produced with the higher nitrite removal rate achieved in the nitrite denitrification process. In addition, a positive linear correlation was found between the nitrite removal reaction constants k [gNO₂ ^?–N/(gVSS d)] and immobilized 1,4,5,8-tetrachloroanthraquinone concentration (C _{1,4,5,8-tetrachloroanthraquinone}), which was k = 1.8443 C _{1,4,5,8-tetrachloroanthraquinone} + 33.75(R ² = 0.9411). The initial nitrite concentration of 179 mgNO₂ ^?–N/L resulted in the maximum nitrite removal rate, which was 6.526[gNO₂ ^?–N/(gVSS d)]. These results show that the application of cellulose acetate immobilized redox mediators (CE-RM) can be valuable for increasing nitrite denitrification rate.     

Effect of cellulose physical characteristics, especially the water sorption value, on the efficiency of its hydrolysis catalyzed by free or immobilized cellulase

Cellulase, an enzymatic complex that synergically promotes the degradation of cellulose to glucose and cellobiose, free or adsorbed onto Si/SiO₂ wafers at 60 °C has been employed as catalyst in the hydrolysis of microcrystalline cellulose (Avicel), microcrystalline cellulose pre-treated with hot phosphoric acid (CP), cotton cellulose (CC) and eucalyptus cellulose (EC). The physical characteristics such as index of crystallinity (I_C), degree of polymerization (DP) and water sorption values were determined for all samples. The largest conversion rates of cellulose into the above-mentioned products using free cellulase were observed for samples with the largest water sorption values; conversion rates showed no correlation with either I_C or DP of the biopolymer. Cellulose with large water sorption value possesses large pore volumes, hence higher accessibility. The catalytic efficiency of immobilized cellulase could not be correlated with the physical characteristics of cellulose samples. The hydrolysis rates of the same cellulose samples with immobilized cellulase were lower than those by the free enzyme, due to the diffusion barrier (biopolymer chains approaching to the immobilized enzyme) and less effective contact between the enzyme active site and its substrate. Immobilized cellulase, unlike its free counterpart, can be recycled at least six times without loss of catalytic activity, leading to higher overall cellulose conversion.     

Carboxymethylation of cellulose using reactive extrusion

Carboxymethyl cellulose was prepared using a continuous, reduced solvent, reactive extrusion process with a short reaction time. The effects of the amounts of NaOH (30 g, 40 g and 50 g), water:ethanol ratio (100%, 70%, 50%, 30% and 10% H₂O) and their interactions on the physical, chemical and morphological properties of carboxymethyl cellulose were studied. Experiments were conducted using to a 5 × 3 blocked factorial design. X-ray diffraction analyses revealed higher degrees of crystallinity and fractions of cellulose-II crystalline structure when 100% H₂O was used as compared to that for 70%, 50%, 30% and 10% H₂O and a commercially available brand of carboxymethyl cellulose, AQUASORB A500. Statistical analysis revealed a significant interaction between the effects of NaOH and H₂O on the degrees of substitutions. The degrees of substitutions decreased with increasing amounts of NaOH and tended to increase with increasing alcohol concentrations. Liquid uptake measurements revealed that the extent of saline uptake, measured at intervals of 1 min, 5 min and 10 min, by carboxymethyl cellulose prepared with 100% H₂O, especially when 40 g and 50 g NaOH was used, was higher than that for 70%, 50%, 30% and 10% H₂O and AQUASORB A500. This may have been because of the higher crystallinity in carboxymethyl cellulose prepared with 100% H₂O. Carboxymethyl cellulose prepared with 70% H₂O and 30 g and 50 g NaOH had the highest saline absorption, using the soak method, before and after centrifugation, respectively. Scanning electron microscopy for carboxymethyl cellulose prepared with 100% and 10% H₂O, through images at 120X magnification, revealed fibers 100 μ to >800 μ in length and 0.8-3.3 μ in breadth. Some non fibrous particles, 0.8-6.7 μ in dimensions, also were observed for 100% H₂O. Images at 900× magnification revealed partially damaged fiber surfaces.