Comparative study of samples of powdered and microcrystalline celluloses of different natural origins: Supermolecular structure and the chemical composition of powdered samples

Methods of wide-angle X-ray scattering (WAXS), high resolution solid-state ¹³C NMR, and Fourier transform IR-spectroscopy are applied to study supermolecular structures and functional compositions of lignocellulose samples of wood and grass origins and powdered celluloses (PC) obtained from them under identical hydrolysis conditions. It was shown by WAXS that the structure of cellulose I is preserved in samples of powdered celluloses, however, an increased degree of crystallinity and cross-section sizes of crystallites are observed in PC samples. Specific features of changes in the supermolecular structure of cellulose occurred after the hydrolysis, i.e., an increase in the content of cellulose I_β in PC compared to the initial samples, are established by ¹³C NMR method. It was shown by means of ¹³C NMR and Fourier transform IR-spectroscopy that the functional chemical composition of lignocelluloses is weakly affected by the hydrolysis. The presence of residual lignin functional groups in the samples is confirmed.     

New cellulose sulfate derivatives and applications

The preparation of water-soluble cellulose sulfates having a degree of substitution (d.s.) of 0.3–2.0 by a homogeneous method is reported. Instead of sulfating cellulose directly, a reactive intermediate, namely, cellulose nitrite, was used, thereby permitting sulfation to proceed under homogeneous conditions. Products obtainable via the homogeneous method differ substantially from those prepared via the heterogeneous method used at present for the production of water-soluble cellulose derivatives. Principal chemical differences are the uniform distribution of the substituents, the exceptionally high molecular weight of the sulfate esters, and in the location of the substituents on the glucosyl residues. The differences result in a number of chemical and physical properties that are unique and not exhibited by other cellulose derivatives. Performance in application areas, such as oil recovery, paints, paper, textiles, cosmetics, and the like, is indicated by these properties.     

Synthesis and Antiradical Activity of Hindered Phenol Derivatives of Flax Cellulose

Russian Journal of Bioorganic Chemistry - The modification of powdered ultradisperse cellulose by hindered phenol fragments was carried out. The modification was carried out by reacting cellulose...     

Preparation and UV-protective properties of functional cellulose fabrics based on reactive azobenzene Schiff base derivative

Azobenzene Schiff base possesses excellent photochromic or thermochromic properties based on intermolecular proton transfer or cis-trans isomerization. The azobenzene Schiff base containing two reactive groups, N, N-bis{p-[(2′-sulphatoethyl)sulphonyl phenylazo] salicylidene}-1,2-ethylenediamine (BSPEA), was applied to modify cellulose materials. The functional cellulose fabrics containing azobenzene Schiff base groups were prepared. The chemical and morphological structures of functional cellulose fabrics were characterized by element analysis, FT-IR spectrum, and scanning electron microscopy (SEM). The UV-protection properties of the fabrics were investigated by the ultraviolet transmittance spectra and ultraviolet protection factor (UPF). The results show that the functional cellulose fabrics had excellent UV-protection properties with higher UPF value (UPF value reached 31.7) and lower ultraviolet transmittance (less than 5%). The modified cellulose fabrics had not significant influence on the physical properties. The functional cellulose fabrics based on reactive azobenzene Schiff base would have potential application in textile and functional materials.     

Increased yield and selected properties of bacterial cellulose exposed to different modes of a rotating magnetic field

Rotating magnetic field (RMF) is an interesting alternative to conventional bacterial cellulose (BC) production methods. The BC synthesis processes may be affected by RMF, which facilitates the transfer of oxygen and nutrients from the media to the microbial cells. RMF may also directly influence the various physical and chemical properties of BC. The main aim of the present study was to evaluate the impact of the RMF on the BC in regard to its yield and material properties. The correlation between the efficiency of polymer production and the different time of exposure to the RMF was also analyzed to determine the conditions of lower energy consumption during the cellulose formation process. It was found that the Gluconacetobacter xylinus cultures exposed to the RMF for a half of the time of the entire cellulose production process (72 h), considering the results obtained in controls, synthesized BC more effectively than bacteria continuously exposed to the RMF for 144 h. Furthermore, the application of the RMF, regardless of the exposure mode, did not negatively affect the polymer material properties. It was concluded that the use of the RMF may provide a novel technique for altering cellulose biogenesis and may be used in multiple biotechnological applications.     

Hydrothermal and pulp processing of Eucalyptus

Hydrothermal processing of Eucalyptus wood was performed at operation temperature of 181 degrees C, processing time or 37.5 min and solid water ratio of 1/6 to ensure a maximum loss of xylan recuperation with minimum cellulose fibre degradation. Under those conditions, the loss of xylan was 22% less than that achieved with the conditions 196 degrees C, 50.6 min and 1/8 (solid/water). IN In addition, an experimental design was used to study the influence of process variables: temperature (145-175 degrees C), pulping time (40-120 min) and ethanol concentration (40-70% weight concentration), on the properties of pulps (yield, kappa number, viscosity, cellulose, xylan, lignin acetyl groups contents and brightness) and paper sheets (stretch index, burst index and tear index) obtained from the solid fraction after hydrothermal treatment of Eucalyptus globulus. Pulps with acceptably high physical and chemical properties can be obtained operating at 175 degrees C for 90 min with 55% ethanol concentration.     

Preparation and characterization of durable antibacterial cellulose biomaterials modified with triazine derivatives

Cellulose fabric was chemically modified with the triazine derivatives containing the multi-cationic benzyl groups. The novel durable antibacterial cellulose biomaterial containing the multi-cationic benzyl groups was prepared. The chemical structure and thermal property of the antibacterial cellulose biomaterial were investigated with FT-IR spectra, nitrogen content analysis, and differential scanning calorimetry (DSC). The results show that the thermal stability of the novel antibacterial cellulose was slightly decreased. Physical properties of the novel antibacterial cellulose had not significant change. The novel antibacterial cellulose imparted excellent durable antibacterial properties.     

Cellulolytic and Pectolytic Activity of Cylindrocarpon destructans (Zins.) Scholt. Isolates Pathogenic and Non-Pathogenic to Fir (Abies alba Mill.) and Pine (Pinus sylvestris L.)*

In studies on cellulolytic and pectolytic activity of C. destructans, it was found that only one of the twenty isolates studied exhibited cellulolytic activity. The total activity of this isolate was similar in media with CMC and powdered cellulose. The specific activity was, however, two times higher with powdered cellulose. All isolates identified as pathogenic to fir and to pine produced pectolytic enzymes. Not all of them, however, exhibited exo- and endo-PMG activity. In general, an increase of total activity of exo-PMG was accompanied by an increase in the specific, activity. Of the non-pathogenic isolates, only one did not show pectolytic activity. The results of our studies have revealed that there exist no significant differences in pectolytic activity between the isolates pathogenic and non-pathogenic to fir and pine. Also, the isolates belonging to both groups were not cellulolytic except one non-pathogenic.     

Photoelectron spectroscopic studies of cellulose, starch and their oxidation products, in powdered form

The use of X-ray photoelectron spectroscopic techniques (XPS or ESCA) in the characterization of cellulose, starch and their oxidation products is discussed. The ESCA results obtained from these materials in the finely powdered state are presented and compared to the results obtained with celluloses in the fibrous form. A far greater amount of surface impurities were found to be present for the powdered polysaccharides due to their greater surface area. Also, it has been shown that a high full-width at half-maximum (f.w.h.m.) value for the C_1s signal is obtained with 100% periodate oxidized maize starch, while a smaller value was found for 11% periodate oxidized cellulose powder. Finally, cellulosic powders seem to produce the O_1s signal 0·8 eV downfield (i.e. higher binding energy value) as compared to the starches and this may be related to the rigid, crystalline and linear structure of the cellulose molecule as compared to the more amorphous and branched structure of the starches.     

细菌纤维素在医学方面的应用

细菌纤维素是由木葡糖酸醋杆菌等细菌合成的纤维素,在化学组成、分子结构上与植物纤维素相近,但具有传统的纤维素所无法比拟的优势,如高亲水性、持水性、生物适应性、可调控性以及高纯度、高透明度等,因而在医学上显示出了巨大的应用潜力。细菌纤维素可用作人造皮肤、外科敷料、人造血管、软骨组织、震动膜、缓释载体等,是最有前途的生物聚合材料之一。     

Regioselective esterification and etherification of cellulose: a review

Deep understanding of the structure-property relationships of polysaccharide derivatives depends on the ability to control the position of the substituents around the monosaccharide ring and along the chain. Equally important is the ability to analyze position of substitution. Historically, both synthetic control and analysis of regiochemistry have been very difficult for cellulose derivatives, as for most other polysaccharide derivatives. With the advent of cellulose solvents that are suitable for chemical transformations, it has become possible to carry out cellulose derivatization under conditions sufficiently mild to permit increasingly complete regiochemical control, particularly with regard to the position of the substituents around the anhydroglucose ring. In addition, new techniques for forming cellulose and its derivatives from monomers, either by enzyme-catalyzed processes or chemical polymerization, permit us to address new frontiers in regiochemical control. We review these exciting developments in regiocontrolled synthesis of cellulose derivatives and their implications for in-depth structure-property studies.     

Effect of microwave irradiation on the physical properties and morphological structures of cotton cellulose

Microwave heating has been proved to be more rapid, uniform and efficient, and easily penetrate to particle inside. To investigate the effect of microwave irradiation on the physical property and morphological structure of cotton cellulose, cellulose fabric was treated with microwave irradiation at different conditions. The physical properties of the treated cellulose fabric were investigated. The morphological structures and thermal stabilities of the untreated and treated cellulose were investigated with differential scanning calorimetry (DSC) and X-ray diffraction. The results show that the physical properties of the treated cellulose fabrics were improved and the recoverability had not significant change. The thermal stability of the treated cellulose was changed. The crystallinity and preferred orientation of the treated cotton cellulose increased.     

Carboxymethylcellulose from totally chlorine-free-bleached milox pulps

High purity cellulose pulp was obtained from Eucalyptus globulus wood by using an environmentally friendly delignification technique (Milox pulping) and subsequent bleaching by totally chlorine free technology. The pulp obtained under optimised experimental conditions was used for the manufacture of carboxymethylcellulose in a heterogeneous medium. By means of an experimental design, the effects of selected operational variables on the composition and chemical properties of reaction products from the carboxymethylation reaction were assessed for optimisation purposes. The distribution of the different carboxymethylglucose mole fractions (un-, mono-, di- and tri-substituted) was determined and compared with theoretical predictions. The maximum average degree of substitution (1.26) was determined at a NaOH/cellulose mole ratio of 4.8 and at a MCA/cellulose mole ratio of 2.0.     

Preparation of Nanocellulose from Nonwood Plant Raw Materials

Russian Journal of Bioorganic Chemistry - Abstract—The purpose of this work was to study the possibility of obtaining nanocellulose (NS) by ultrasonic (US) processing of powdered cellulose in...     

Esterification of cellulose-enriched agricultural by-products and characterization of mechanical properties of cellulosic films

Two agricultural by-products, wheat bran and maize bran have been examined for their suitability to be transformed into biomaterials by esterification by lauroyl chloride. Influence of biochemical characteristic of cellulose (cellulose content, viscosity-average degree of polymerization, crystallinity) was studied on eight samples enriched in cellulose after chemical removal of heteroxylans and lignin. After an acidic pre-treatment, esterification was carried out with lauroyl chloride and an optimized reaction time of 8 h was used.

Chemical compositions were similar for all cellulose esters obtained, but cellulose content of initial material had a marked influence on the amount of esterified product. A film was easily obtained by casting and the mechanical (tensile strength and elongation), thermomechanical and calorimetric properties were determined. The possible role of grafted fatty acid as internal plasticizer was finally discussed.     

Triplet quantum yields in light-scattering powder samples measured by laser-induced optoacoustic spectroscopy (LIOAS)

In recent years, different methods and techniques have been applied to study the primary photophysical processes occurring in dye-loaded light-scattering powdered samples. In spite of this, there are still no reliable methods for the determination of triplet quantum yields for this kind of systems. Laser-induced optoacoustic spectroscopy (LIOAS) has been extensively used for the determination of triplet quantum yields of dyes in solution. In a previous work, LIOAS was applied to the measurement of absolute emission quantum yields of highly fluorescent powdered samples. Excellent agreement was found with values obtained from reflectance data. In this work, we apply the same technique for the determination of triplet quantum yields of Rose Bengal and Erythrosine B adsorbed on microcrystalline cellulose. In contrast to water and other solvents, internal conversion cannot be neglected in the cellulose environment. The triplet quantum yield for both dyes is around 0.55 and does not change with dye concentration.     

Chemical procedures for enzyme immobilization on porous cellulose beads.

In a previous article, the method of preparation and the physical properties of porous (75 to 80% porosity) cellulose beads were described (Biotechnol. Bioeng., 18, 1057 (1976). The present article reports that the chemical procedures employed for immobilizing enzymes on ordinary cellulose can be applied to the porous cellulose beads. The results showed more enzyme loading on the beads than ordinary cellulose. The choice of the procedures might also affect the mechanical strength of the cellulose beads.     

Cellulase digestibility of pretreated biomass is limited by cellulose accessibility

Attempts to correlate the physical and chemical properties of biomass to its susceptibility to enzyme digestion are often inconclusive or contradictory depending on variables such as the type of substrate, the pretreatment conditions and measurement techniques. In this study, we present a direct method for measuring the key factors governing cellulose digestibility in a biomass sample by directly probing cellulase binding and activity using a purified cellobiohydrolase (Cel7A) from Trichoderma reesei. Fluorescence-labeled T. reesei Cel7A was used to assay pretreated corn stover samples and pure cellulosic substrates to identify barriers to accessibility by this important component of cellulase preparations. The results showed cellulose conversion improved when T. reesei Cel7A bound in higher concentrations, indicating that the enzyme had greater access to the substrate. Factors such as the pretreatment severity, drying after pretreatment, and cellulose crystallinity were found to directly impact enzyme accessibility. This study provides direct evidence to support the notion that the best pretreatment schemes for rendering biomass more digestible to cellobiohydrolase enzymes are those that improve access to the cellulose in biomass cell walls, as well as those able to reduce the crystallinity of cell wall cellulose.     

Inactivation of shiga toxin-producing Escherichia coli (STEC) and degradation and removal of cellulose from STEC surfaces by using selected enzymatic and chemical treatments

Some Shiga toxin-producing Escherichia coli (STEC) strains produce extracellular cellulose, a long polymer of glucose with β-1-4 glycosidic bonds. This study evaluated the efficacies of selected enzymatic and chemical treatments in inactivating STEC and degrading/removing the cellulose on STEC surfaces. Six cellulose-producing STEC strains were treated with cellulase (0.51 to 3.83 U/15 ml), acetic and lactic acids (2 and 4%), as well as an acidic and alkaline sanitizer (manufacturers' recommended concentrations) under appropriate conditions. Following each treatment, residual amounts of cellulose and surviving populations of STEC were determined. Treatments with acetic and lactic acids significantly (P < 0.05) reduced the populations of STEC, and those with lactic acid also significantly decreased the amounts of cellulose on STEC. The residual amounts of cellulose on STEC positively correlated to the surviving populations of STEC after the treatments with the organic acids (r = 0.64 to 0.94), and the significance of the correlations ranged from 83 to 99%. Treatments with cellulase and the sanitizers both degraded cellulose. However, treatments with cellulase had no influence on the fate of STEC, and those with the sanitizers reduced STEC cell populations to undetectable levels. Thus, the correlations between the residual amounts of cellulose and the surviving populations of STEC caused by these two treatments were not observed. The results suggest that the selected enzymatic and chemical agents degraded and removed the cellulose on STEC surfaces, and the treatments with organic acids and sanitizers also inactivated STEC cells. The amounts of cellulose produced by STEC strains appear to affect their susceptibilities to certain sanitizing treatments.     

Chemical force microscopy of cellulosic fibers

Atomic force microscopy with chemically modified cantilever tips (chemical force microscopy) was used to study the pull-off forces (adhesion forces) on cellulose model surfaces and bleached softwood kraft pulp fibers in aqueous media. It was found that for the –COOH terminated tips, the adhesion forces are dependent on pH, whereas for the –CH₃ and –OH terminated tips adhesion is not strongly affected by pH. Comparison between the cellulose model surfaces and cellulosic fibers under our experimental conditions reveal that surface roughness does not affect adhesion strongly. X-ray photoelectron spectroscopy (XPS) and Fourier Transformed Infrared (FTIR) spectroscopy reveal that both substrate surfaces have homogeneous chemical composition. The results show that chemical force microscopy can be used for the chemical characterization of cellulose surfaces at a nano-level.