Preparation of the water-soluble chitosan-coated oxidized regenerated cellulose gauze

A water-soluble chitosan-coated oxidized regenerated cellulose (ORC) gauze was prepared by the oxidation of a viscose gauze with NO₂/CCl₄ and subsequent treatment with a solution of chitosan in aqueous acetic acid and finally neutralization with NaOH/C₂H₅OH solution. A series of C6 ORC samples with different –COOH content were prepared and coated by chitosans (CTS) with different molecular weight (Mw) of 2,000, 50,000, 100,000 (denoted as CTS1, CTS2, CTS3). FT-IR and TG suggested the formation of the amide bond between the carboxyl group of ORC and the amino group of CTS. Kjeldahl nitrogen analysis of ORC gauze treated with CTS (CTS-ORC) showed that the percentage of chitosan with the lowest Mw of 2,000 introduced on ORC surface was highest and increased with oxidation time, while chitosans with medium and high Mw showed that the maximum percentage of chitosan introduced on ORC surface occurred at the oxidation time of 8 h. The neutralized chitosan-coated ORC gauze could still maintain its original morphological form and was water-soluble, and could form a transparent gel quickly for 5 s in water. The prepared water-soluble gauze could be anticipated to possess the improved hemostatic and antibacterial properties.     

Topochemical modification of cotton fibres with carboxymethyl cellulose

Adsorption of carboxymethyl cellulose (CMC) as a method to introduce charged (ionizable) groups onto cellulose cotton fibre surfaces was investigated. The method was based on application of a previously published method used for wood fibres. The amount of adsorbed ionizable groups was determined indirectly by analysis of CMC in solution by the phenol–sulphuric acid method and directly by conductometric titration of the fibres. Results from the two methods correlated well. The molecular weight and purity of the CMC had an influence on its adsorption onto cotton; high molecular weight CMC was preferentially adsorbed. The adsorbed charge correlated linearly with the amount of CMC adsorbed. The total charge of the cotton fibres could be increased by more than 50% by adsorption of CMC. It is expected that this modification procedure can be used in a wide spectrum of practical applications. Lidija Fras Zemljič and Karin Stana-Kleinschek are the members of the European Polysaccharide Network of Excellence (EPNOE).     

Hydrogels produced from cotton cellulose

Hydrogels with high water retention can be produced from cotton cellulose. Treating aqueous suspensions of microcrystalline cellulose, lint, and powdered cellulose with mechanical pulses of various frequencies, amplitudes, and shear stresses turns them into gels.Nizami Tashkent State Pedagogical University, fax (3712)-54-92-17. Translated from Khimiya Prirodnykh Soedinenii, No. 1, pp. 71–73, January–February, 2000.     

Periodate oxidative decrystallization of cotton cellulose

Cotton cellulose is decrystallized by periodate oxidation to essentially zero crystallinity index (CI) at 100% oxidant consumption. The decrease in CI is pseudo zero-order over 60% of the reaction and consistent with a diffusion-controlled mechanism. The attack on regions of high order is indicated to be 100% in the latter phase of oxidation and 13% in the initial phase. Data allow an estimate that approximately 60% of the structural segments of the cotton cellulose under investigation lies in highly ordered arrangements.     

Active antibacterial coating of cotton fabrics with antimicrobial proteins

The prevention of bacteria colonization by immobilizing proteins with antimicrobial activity onto cotton fabrics was investigated. Such coatings have potential applications in medical dressing materials used in wound care and healing. Two antimicrobial proteins lysozyme and hydramacin-1 (HM-1) were surface immobilized through two linkers (3-aminopropyl) triethoxysilane (APTES) and citric acid in the presence of the water soluble carbodiimide coupling reagent 1-cyclohexyl-3-(2-morpholinoethyl)carbodiimide metho-p-toluenesulfonate. Surface composition analysis by attenuated total reflection-Fourier transform infrared and X-ray photoelectron spectroscopies confirmed formation of the protein-cellulose conjugates. Antimicrobial activities of the different functionalized surfaces were found to vary between APTES and citric acid directed coatings. Citric acid immobilized lysozyme treated samples demonstrated superior activity against Gram-positive Bacillus subtilis, whereas APTES immobilized HM-1 treated samples demonstrated an advantage in inhibiting the growth of Gram-negative Escherichia coli. The antibacterial activity and stability of citric acid immobilized protein fabrics following sonication, boiling and chemical treatment were noticeably higher than that of the corresponding APTES immobilized protein fabrics. The dual coating of fibers with both antimicrobial proteins afforded efficient antimicrobial activities against both bacterial species. The results suggest that coating cotton fibers with antimicrobial proteins and peptides represents a feasible approach for developing active surfaces that prohibit growth and colonization of bacterial strains and can be potentially used in medical cotton-based fabrics.

     

Synthesis and properties of fluorescent cotton cellulose labeled with norfloxacin

To expand the application of cellulose in the field of fluorescence techniques, the cotton cellulose was labeled with norfloxacin (Cell-NF) via a three-step reaction, involving alkali treatment, epoxy activation, and opening of the epoxy rings with norfloxacin molecules. And the coordination complexes of Cell-NF with rare earth ions terbium (Cell-NF-Tb) and europium (Cell-NF-Eu) were obtained. The products were detected by IR, TG, XPS, UV and fluorescence spectra. Results showed that the norfloxacin content of the labeled cellulose was about 6.73 w% and the start temperature of decomposition of the Cell-NF was raised by 40°C compared with the stock cotton cellulose. When excited at 340 nm, the Cell-NF, Cell-NF-Tb, and Cell-NF-Eu in the solid state could emit violet (430 nm), green (549 nm) and red (620 nm) light, respectively.     

The nature of accessible surfaces in the microstructure of cotton cellulose

The accessible regions in cotton cellulose were tagged by the introduction of diethyl-aminoethyl (DEAE) substituents at DS = 0.034 without other substantial changes in structure. Evidence from rates of hydrolysis of this DEAE cotton to hydrocelluloses and from the composition and structure of the solubilized and insoluble fractions provides the basis for considerable detail regarding two types of accessible regions in the cotton fiber; these are identified as accessible surfaces of elementary fibrils. One type of accessible surface is characterized by molecular chain segments which are distorted and disordered by tilt/twist strain that is concentrated in this segment of the elementary fibril; the second type of accessible surface is characterized by a relatively high degree of order which reflects the high level of crystallinity within the interior of this unstrained segment of the elementary fibril. Substantial differences between these accessible surfaces are discussed. It is estimated that chain segments on accessible surfaces of the first type are substantially disordered, i.e., approximately 60–90% of the D -glucopyranosyl units are dislocated from positions of perfect crystalline order. Accessible surfaces of the second type are quite highly ordered, i.e., only 5–30% of the D -glucopyranosyl units dislocated.     

Preparation of superhydrophobic electroconductive graphene-coated cotton cellulose

A simple and versatile method based on cotton cellulose coated with graphene is reported for the fabrication of superhydrophobic and electroconductive textiles. Graphene oxide was deposited on cotton fibers by a dip-pad-dry method followed by reduction with ascorbic acid to yield a fabric with a layer of graphene. The fabric was then reacted with methyltrichlorosilane to form polymethylsiloxane (PMS) nanofilaments on the fibers surface. The surface chemistry and morphology were characterized by UV–visible reflectance spectrophotometry, Fourier transform infrared spectroscopy, energy-dispersive X-ray spectroscopy and scanning electron microscopy. The water contact angle (CA)/shedding angle (SHA) and resistivity measurements were used for assessing hydrophobicity and conductivity, respectively. The graphene-coated fabric showed hydrophobicity with the CA of 143.2° ± 2.9° and SHA of 41°. The formation of PMS nanofilaments displayed superhydrophobicity with CA of 163° ± 3.4° and SHA of 7°, which indicated the self-cleaning ability. Conductivity of the graphene-coated fabric was confirmed by the electrical resistivity of 91.8 kΩ/sq which increased to 112.5 kΩ/sq after the formation of PMS nanofilaments.     

Structural inhomogeneity in cotton cellulose upon its interaction with water

Comparative analysis of the characteristics of supramolecular structures of dry and swollen cotton fibers makes it possible to differentiate structural regions accessible to water. The revealed features of water desorption from cotton cellulose (exceptionally low rates at the final stages, presence of residual moisture) are related to the removal of water, which is localized in the regions of the crystalline phase disorganized upon drying. The fact of incomplete moisture removal from cotton fibers at < 325 K is interpreted from the stand-point of the frozen molecular mobility in the microsurroundings of sorption sites, which are located at the defects of crystallites, at the final stage of the desorption process. A marked contribution from the recrystallization of disorganized regions in the surface layer of crystallites to the thermal effect of the interaction between water and cotton cellulose at low water content is established.     

Comparing microcrystalline with spherical nanocrystalline cellulose from waste cotton fabrics

Microcrystalline cellulose (MCC) and spherical nanocrystalline cellulose (SNCC) were successfully prepared from waste cotton fabrics through acid hydrolysis. The comparative analysis of the morphology and structure between the obtained MCC and SNCC was carried out. The SNCC suspension exhibited higher stability than the MCC suspension. Transmission electron microscopy in combination with atomic force microscopy showed that the cellulose nanospheres with average size of 35?nm were achieved, while the average particle size of MCC was 49?μm. The MCC and SNCC had similar functional groups and crystalline structure as confirmed by Fourier transform infrared spectroscopy and X-ray diffraction analysis, respectively. Viscometric average molecular weight measurement and thermo gravimetric analysis indicated that the degree of polymerization and thermal stability of SNCC was lower than that of MCC. These results should improve understanding of the characteristics of MCC and SNCC derived from waste cotton fabrics and lead to many new applications.     

Kinetics of heterogeneous cellulose reactions. I. Cyanoethylation of cotton cellulose

Sakurada's equation and fundamental kinetic laws were applied to the heterogeneous cyanoethylation of cellulose, performed by reacting fiber with liquid acrylonitrile, with sodium hydroxide as the catalyst. The data fit Sakurada's equation better at higher temperatures; deviation occurs at the initial stage, and the rate of reaction falls abruptly at a later stage. The degree of substitution at which the abrupt rate change occurred decreased as the temperature increased from 31 to 60°C. and also as the crystallinity of the fiber decreased. Diluting the reagent with different solvents decreased the rate of reaction and changed its transition points, but did not change the essential nature of the reaction, each segment of which fits Sakurada's equation very well. A uniform distribution of the catalyst (sodium hydroxide) throughout the fiber was attempted, and then the reaction was studied at 50°C. Diffractograms of the samples provided further evidence that the position of the rate change is associated with the change of cellulose (I) crystalline structure. Approximate energy of activation has been calculated, from the specific rate constants, between 31 and 40°C. as 10.6 kcal. and between 45 and 50°C. as 16.7 kcal. At other temperatures the determination was handicapped, due to temperature dependence of the order of reaction. An empirical relation between the constants of Sakurada's equation and the reaction temperature has been sought and correlated with the Arrhenius equation. Energies of activation, determined from this relationship, have been found to be very close to the above values. The change of order of reaction with temperature suggests that the reaction is affected by diffusion and the mechanism is interpreted as a diffusion-controlled reaction where hydrogen bonds play a significant role in diffusion.     

Kinetic characterization of the synthesis of cotton cellulose

The influence of the temperature, pH, and inhibitors on the synthesis of cellulose from cottonplant shoots has been investigated. The maximum activity of glucan synthetase was exhibited at 27°C, pH 8. O. The greatest inhibition of the formation of cellulose was shown by EDTA.A. S. Sadykov Institute of Bioorganic Chemistry, Academy of Sciences of the Republic of Uzbekistan, Tashkent, fax (3712) 62 70 71. Translated from Khimiya Prirodnykh Soedinenii, No. 2, pp. 300–302, March–April, 1995. Original article submitted October 24, 1994.     

Study of the partial O-alkylation of cotton cellulose

The O-alkylation of cotton cellulose with monochloroacetic acid has been studied. A change in the sequence of addition of the components to the reaction mixture enables the course of the reaction to be regulated and weakly substituted fibrous carboxymethylcellulose with valuable physicochemical and medicobiological properties to be obtained.Institute of the Chemistry and Physics of Polymers, Academy of Sciences of the Republic of Uzbekistan, Tashkent, fax (3712) 44 26 61. Translated from Khimiya Prirodnykh Soedinenii, No. 3, pp. 436–439, May–June, 1997.     

Ce(IV)-induced polymerization of allyl methacrylate with cotton cellulose

Ce(IV)-induced polymerization of allyl methacrylate (AMA) with cotton cellulose was investigated under a variety of conditions. Polymer add-on was directly related to AMA concentration. The same holds good for Ce(IV) ion concentration up to a certain concentration (30 mmol/L), after which it decreases. Polymer add-on was higher at 60 than at 50 and 70°C. A methanol/water mixture (20/80) offers the best medium for polymerization. Addition of nitric acid (up to 400 mol equivalent/L) or perchloric acid (up to 800 mol equivalent/L) to the polymerization system caused significant enhancement in polymer add-on. The reverse was the case with sulphuric acid irrespective of the concentration used. A comparison between polymer add-on values based on increase in weight and those based on estimated allyl double bonds indicated that the latter undergo partial homopolymerization.     

Substrate role in coating of microfibrillated cellulose suspensions

Interest in nanocellulose-based coatings for packaging applications has been growing due to their excellent oil and gas barrier properties combined with their sustainable, recyclable, biodegradable, and non-toxic nature. Coating of nanocellulose materials such as microfibrillated cellulose (MFC) on paper/paperboard is challenging compared to traditional paper coating materials due to excessively high viscosity and yield stress of MFC suspensions at rather low solids content, typically below 5%. Possessing large amounts of water and a distinct rheological behavior such suspensions set tough demands on the substrate to be coated. It is important to understand and quantify substrate requirements in order to coat these suspensions successfully and achieve a satisfactory coating quality. A custom-built slot geometry is used herein to enable coating of highly viscous MFC suspensions on different paper-based substrates in a roll-to-roll process. The impact of substrate properties, such as surface chemistry and surface energy, surface roughness and surface porosity, and water absorption capacity on MFC coatability and coating quality is reported. Coating adhesion to the substrate was quantified with surface strength testing of MFC coated substrates. Various techniques, such as Scanning Electron Microscopy, IGT print penetration tests, and air permeability tests were employed for measuring coating coverage and surface porosity. MFC coating was found to adhere best to a highly hydrophilic surface, whereas the most uniform and defect-free film at low coat weights was formed on a smooth surface. It was also found that the MFC coat weight needed for full coverage, and therefore potentially good barrier, needs to exceed the surface roughness volume of the substrate. Water absorption capacity of the substrate also determines the final MFC coating quality obtained. The results clearly highlight the role of paper-based substrate for successful and effective coating of the micro and nanocellulose suspension.     

Hydrophobic thin fluoropolymer coating on cotton surfaces

We report a simple novel procedure to prepare hydrophobic cotton textiles by admicellar polymerization. By in situ introducing fluoropolymer on cotton fibers to generate a dual-size surface roughness, followed by hydrophobization with a little amount of fluoromonomer Octafluoropentamethyl methacrylate (OFPM) with short time, normally hydrophilic cotton has been easily turned into hydrophobic. Hydrophobic cotton textile exhibits a static water contact angle of 124° for a 10?µl droplet. When an octa fluoroalkyl chain is introduced to the cotton surface, the originally smooth surface changed immediately to rough surface which is the key factor for hydrophobicity like lotus leaves.     

Effect of bentonite clay on biosynthesis of cotton cellulose

Bentonite clay affects biochemical processes occuring during synthesis of cotton-fiber cellulose by increasing the activity of glucansynthetase, peroxidase, and cellulase at 20% clay concentration. The content of soluble proteins increases and their composition changes. Academician A. S. Sadykov Institute of Bioorganic Chemistry, Academy of Sciences of the Republic of Uzbekistan, Tashkent. Translated from Khimiya Prirodnykh Soedinenii, No. 6, pp. 789–794, November–December, 1999.     

Structures of reagent residues resulting from reactions of divinyl sulfone with cotton cellulose

Cotton cellulose in fabric form was crosslinked with divinyl sulfone by catalysis with solutions of sodium hydroxide of normalities ranging from 0.1 to 4.0. The molecular chains of cellulose were hydrolyzed with sulfuric acid to yield hydrolyzates from which simple substituted glucoses (i.e., those bonded to a single unit of DVS), the simple crosslinked glucoses (i.e., those joined together by a single unit of DVS), and complex structures (i.e., those substituted or crosslinked with more than one unit of DVS in the chain) were isolated and measured. The fractions of the reagent residues in the forms of the structures noted above were found to change substantially with the concentration of base employed to catalyze the reaction. The constitution of the reagent residues resulting from reaction in 0.1N base was remarkably simple: 82% of the DVS residues in the form of simple crosslinks and 18% in the form of simple substituents. Complex structures accounted for as much as 70% of the DVS residues under other conditions of reaction.