In vivo and in vitro blood compatibility of polyelectrolyte complexes formed between cellulose derivatives

The blood compatibility of cellulosic polyelectrolyte complexes (PECs) and the effect of excess charge in PEC on the blood compatibility were examined in detail by both in vivo and in vitro blood tests. For this purpose, two types of quaternary ammonium cellulose derivatives were prepared by treating cellulose or hydroxyethyl cellulose with glycidyl trimethylammonium chloride. In vivo blood tests were made by implanting the polymer-coated suture into a jugular and femoral vein of a dog. In vitro blood tests include the measurement of whole blood coagulation time on polymer-coated glass tubes, platelet adhesion measurements using a column packed with polymer-coated glass beads, and a measurement of activation of the intrinsic coagulation system. It was found that among the PECs examined, the PECs containing quaternary ammonium derivatives as polycation components have an excellent blood compatibility. The experiments on the effect of excess charge in PEC revealed that (i) the relative coagulation time of whole blood is almost independent of the mole ratio of polycation to polyanion component within the mole ratios examined, being in good agreement with those by in vivo blood tests, but (ii) platelet adhesion increases with increasing the mole ratio of polycation/polyanion in the PEC, and (iii) the activation of the intrinsic coagulation system increases with decreasing the mole ratio.     

Preparation of cellulosic drug‐loaded hydrogel beads through electrostatic and host–guest interactions

Cyclodextrin‐grafted cellulosic hydrogel beads (CD⁺@HEC‐CMC‐gel) were prepared through electrostatic and host–guest interactions. β‐Cyclodextrin (CD⁺) modified with quaternary ammonium groups was used as the electropositive binding site, and carboxymethyl cellulose (CMC) in a double‐network hydrogel structure was used as the electronegative binding site. The double‐network structure was obtained by controlling the crosslinking of CMC and hydroxyethyl cellulose (HEC) in the presence of epichlorohydrin. The electrostatic interaction was used to graft CD⁺ onto the electronegative double‐network structure. Scanning electron microscopy indicated an obvious change in the cellulosic double network after grafting of CD⁺. The grafting content of CD⁺ in CD@HEC‐CMC‐gel is determined as 93.10 ± 0.74% by the photometric titration method. In order to evaluate the assembling and releasing ability, ibuprofen (IBU) was selected to be encapsulated in CD⁺@HEC‐CMC‐gel by host–guest interaction. In addition, the release of IBU by the hydrogel beads was explained by several kinetic models. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46593.     

Water‐Soluble Amphiphilic O‐(Carboxymethyl)cellulose Derivatives – Synthesis and Properties

Summary: Water‐soluble, partially hydrophobized derivatives of O‐(carboxymethyl)cellulose (CMC) were prepared by esterification of CMC in its ‘gel suspension’ form. The classical esterification method (A) using stearoyl chloride/pyridine as well as two unconventional methods based on reaction with mixed anhydrides (B) and transesterification with vinyl laurate (C) respectively, were compared in terms of the structural, molecular and performance properties of the obtained derivatives. The classical esterification and method B yielded water‐soluble simple fatty acid esters, whereas mixed acetic‐fatty acid esters were obtained by method C. In all cases, molecular degradation of CMC was observed. ¹H and ¹³C NMR spectroscopy of the acetyl‐lauroyl derivatives of CMC with a degree of esterification DS_E of 0.20 indicated a prevalence of the lauroyl groups (DS_Ac:DS_La = 0.03:0.17). Most of the water‐soluble derivatives exhibited excellent emulsifying efficiency. They represent polysaccharide‐based surfactants with effective anti‐redeposition properties as well as good washing power. Suitable derivatives can be prepared under mild reaction conditions by both unconventional methods which implies that they have potential as substitutes for the expensive and invasive conventional method.

Preparation of CMC derivatives.     

纤维素化学的现状与发展趋势

本文综述了纤维素化学的研究现状和发展趋势，包括近10年来纤维素结构、纤维素衍生物如纤维素磷酸酯、纤维素醋酸酯、纤维素硝酸酯、羧甲基纤维素、羟丙基纤维素和乙基纤维素等，以及纤维素的裂解与能源、纤维素液晶及其复合材料、新型纤维素衍生物及其功能材料的合成、生物技术在纤维素化学中的应用等主要研究领域。探讨了未来20年的研究课题：（1）纤维素制品的高质和高值化；（2）食用纤维素及纤维素保健食品；（3）新型纤维素功能材料的制备及应用；（4）生物技术应用的工业化。     

改性纤维素和壳聚糖共混膜的制备及性能研究

将水溶性的纤维素衍生物——羟乙基纤维素与壳聚糖乙酸水溶液用溶液浇铸法制得羟乙基纤维素/壳聚糖(HEC/CS)共混膜。确定了该共混膜的最佳制备条件,并测试了其力学性能和生物降解性能。结果表明:HEC/CS共混膜具有好的抗菌性。     

Preparation of cellulose graft copolymers having polypeptide side chains and their blood compatibility

Blood compatibility of cellulose graft copolymers with poly(γ-benzyl-L -glutamate) and poly(N⁵-2-hydroxyethyl-L -glutamine) (Cell-g-PBLG and Cell-g-PHEG) was examined in vivo blood tests. For this purpose, Cell-g-PBLG graft copolymers with PBLG contents ranging from 7 to 60 mol % were prepared by polymerizing N-carboxy-γ-benzyl-L-glutamate(γ-BLG NCA) using aminoethyl cellulose (AE-Cell) with degree of substitution of 0.05 as macroinitiator. Graft copolymerization was carried out under a variety of conditions at 20°C in dimethyl-sulfoxide. Monomer conversion higher than 60% were obtained for all the polymerization runs. The solubility tests revealed that all of the AE-Cell and the polypeptides formed were grafted. The Cell-g-PHEG graft copolymers were prepared by treating Cell-g-PBLG graft copolymers with 2-amino-1-ethanol. Characterization of these graft copolymers were carried out by IR spectroscopy, DSC, and water content measurement. Tests for blood compatibility, in vivo, were made by a method of peripheral vein indwelling suture which was developed by one of the authors. The coating of graft copolymers on the polyester suture was made by casting either from formic acid solution of LiCl/dimethylacetamide solutions using water as the regenerating medium, and the polymer-coated sutures were implanted into a jugular and femoral vein of a dog. The results showed that the graft copolymers examined have excellent antithrombogenic properties.     

Polyelectrolyte complexes based on chitosan and poly(L‐glutamic acid)

Polyelectrolyte complexes (PECs) were prepared by mixing aqueous solutions of chitosan (CS) and poly(L ‐glutamic acid) (PLGA) at various pH. It was found that the stoichiometry of the PECs depends on pH. An investigation of the PECs using Fourier transform infrared spectroscopy proved that the formation of the complexes is due to electrostatic interaction between ? NH₃⁺ groups of CS and ? COO^? groups of PLGA. The solid PECs were characterized using wide‐angle X‐ray diffraction, which suggested that a strong interaction occurs between the two polymers at pH = 4 or 5 and relatively weak interaction at pH = 3. These results were further confirmed by thermogravimetric analysis data. Transmission electron microscopy showed that the complexes have a spherical shape. The effect of ionic strength on the size of the PECs was also studied using dynamic light scattering. It was found that the size of the PECs is dependent on pH. Copyright © 2007 Society of Chemical Industry     

Carboxymethylation of cellulosic material (average degree of polymerization 2600) isolated from cotton (Gossypium) linters with respect to degree of substitution and rheological behavior

Carboxymethylation of cellulosic material (average degree of polymerization 2600) containing 76.5% cellulose and 23.6% xylose isolated from cotton (Gossypium) linters was studied under varying reaction conditions with respect to maximum degree of substitution (DS). The influence of reaction conditions on the apparent viscosity of the prepared derivatives was also studied. The conditions optimized were sodium hydroxide concentration 3.75M, monochloroacetic acid concentration 2.05 mol/AGU, carboxymethylation time 3.5 h, and temperature 55°C, to yield carboxymethyl cellulose of DS 0.77. Rheological studies of 1 and 2% solutions of the optimized product revealed their non‐Newtonian pseudoplastic behavior. Repeating units of the optimized product were also determined by HPLC after complete depolymerization of the polymer. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 1477–1482, 2005     

Preparation and characterization of tetracycline‐loaded interpenetrating polymer networks of carboxymethyl cellulose and poly(acrylic acid): water sorption and drug release study

Tetracycline (TC)‐loaded ionic interpenetrating polymer networks (IPNs) of carboxymethyl cellulose (CMC) and crosslinked poly(acrylic acid) (PAA) were prepared and characterized by infrared spectral analysis, differential scanning calorimetry and scanning electron microscopy techniques. The prepared IPNs were evaluated for in vitro blood compatibility by clot formation and hemolysis methods and their water imbibitions capacity was determined. Fractional release dynamics of tetracycline was also investigated from loaded IPNs of CMC and PAA. The entrapped drug was examined for antibacterial activity and structural integrity and effects of various parameters such as percentage loading of the drug, chemical composition of the carrier IPN, pH and temperature of the release medium were investigated on the release profiles of TC. The drug was also released in different simulated biological fluids. Copyright © 2005 Society of Chemical Industry     

Nanosized cellulose derivatives as green reinforcing agents at higher loadings in natural rubber

Cellulose nanoparticles (CelNPs) prepared by an acid hydrolysis process were acetylated under ambient conditions to retain the nanosize and to obtain hydrophobic nanosized derivatives. Green nanocomposites of natural rubber (NR) with more than 50 phr of cellulosic fillers were successfully developed by a commercial dry mixing process. The incorporation of cellulose acetate nanofiller up to 40 phr led to an almost linear increase in both the tensile and elongation properties, which were higher than even those of a composite with the conventional filler carbon black (CB). This was further supported by the almost uniform single‐phase morphology of the nanobiocomposite revealed by scanning electron microscopy and the high thermal stability. The results indicate the high degree of compatibility between the hydrophobic nanosized filler and the NR matrix. Although a drop in the mechanical strength was observed above 50 phr, the cellulose derivatives were expected to prove to be promising substitutes for the hazardous filler CB even at higher loadings. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40632.     

Water-absorbing characteristics of acrylic acid-grafted carboxymethyl cellulose synthesized by photografting

Cellulosic absorbents for water were synthesized by photografting (λ > 300 nm) acrylic acid (AA) onto fiberous carboxymethyl cellulose (CMC, degree of substitution [DS] = 0.1–0.4) at 30°C in the presence of N,N′-methylenebisacrylamide as a crosslinker. The CMC sample was pretreated with hydrogen peroxide in the presence of sulfuric acid to prepare CMC peroxides with a peracid type as a polymeric photoinitiator. The peroxides were active for the photografting and AA could be grafted onto CMC with percent graftings higher than 150% by photoirradiation of 10 min at 30°C. The amount of water absorbed increased with increasing percent grafting of AA and DS of CMC. The amount was reduced considerably when the absorbents were prepared by the photografting of AA onto crosslinked CMC in the absence of the crosslinker. Graft copolymers which display a decreasing water absorbency as a function of temperature were prepared by two methods: In the first synthesis method, AA and N-isopropylacrylamide (NIPAAm) binary monomers were graft-copoly-merized onto CMC samples using photoinitiation. In the second method, photografting of AA was followed by a second-step photografting of NIPAAm to produce a terpolymer with two types of side chains of differing repeat unit composition on the CMC substrate. Graft copolymers formed by both methods showed decreasing water absorbency as temperature increased with losses in water absorbency of up to about 60% as the temperature was increased above 30°C. Effects of NIPAAm composition and corsslinker content in the graft copolymers on the decreasing water absorbency as a function of temperature were also examined. © 1996 John Wiley & Sons, Inc.     

Bonding performance of melamine-urea-formaldehyde and phenol-resorcinol-formaldehyde adhesives in interior grade glulam

Wood moisture content (MC) affects the glued laminated beam (glulam) bonding strength. Selected adhesives were Phenol-Resorcinol-Formaldehyde (PRF) and Melamine-Urea-Formaldehyde (MUF) adhesives with 1, 1.5 and 2% (w/w) carboxymethyl cellulose (CMC) formic acid solutions. Douglas fir (pseudotsuga menziesii) from North America was used in the test. The bonding behavior of these adhesives with wood at 12 and 18% MC were investigated. The study focused on the effect of 18% MC on shear strength performance of MUF and PRF adhesives and optimizing the formula of CMC formic acid solution. Compressive shear strength of wood with MUF adhesive with 2% (w/w) formic acid solution at 12 and 18% MC stabilized at 10.6 and 10.0 MPa, respectively, which were 17 and 16% higher than that with PRF adhesive at the same condition. At 12–18% MC, MC had a little effect on bonding strength. However, 18% MC wood with PRF adhesive had 52.2% less initial strength increasing rate than that of 12% MC wood. 18% MC wood with MUF adhesives with 1, 1.5 and 2% (w/w) CMC formic acid solutions had 16.0, 15.5 and 27.0% less initial strength increasing rates than that of 12% MC wood, respectively. MUF adhesive using 2% CMC formic solution required the shortest press time at 12 and 18% MC about 1.6 and 2.7 h, respectively. The strength of PRF adhesive was significantly affected by wood MC and enough press time is essential for the proper bonding strength.     

Preparation,evaluation, and in vitro release study of O‐carboxymethyl chitosan nanoparticles loaded with gentamicin and salicylic acid

To inhibit the ototoxicity of gentamicin (GM) and overcome the drawback related to chitosan (CS) nanoparticles preparation in acid solution, O‐carboxymethyl chitosan (O‐CMC) nanoparticles loaded with GM and salicylic acid (SA) were prepared by ionic cross‐linking method using calcium chloride as crosslinking agent. The Fourier transform infrared (FTIR) spectroscopy and X‐ray diffraction (XRD) were used to analyze the reaction of O‐CMC and crosslinking agent. The parameters of preparation of the compound nanoparticles including the concentration of O‐CMC, the mass ratio of O‐CMC to calcium chloride, and the feed ratio of SA to GM were investigated. The results showed that the obtained nanoparticles had a high zeta potential and drug‐loading capacity. The nanoparticles were characterized by a spherical morphology, with average size ranging from 148 to 345 nm and a narrow particle size distribution. In vitro release studies in phosphate buffer saline (pH 7.4) evidenced a burst release in the first 1 h, followed by a sustained release in the residual time. The release amount of SA and GM were approximately equal in 24 h, which indicated that the SA‐ and GM‐loaded O‐CMC nanoparticles are a promising carrier system for inhibiting the ototoxicity of GM. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Nitrate permeability of semi‐permeable membranes prepared from binary blends of cellulose triacetate and chitosan

Semi‐permeable membranes of binary polymer blends of cellulose triacetate (CTA) and chitosan (CS) were produced to harvest microalgal biomass for biofuels. Relatively thick membranes of polymer blends containing more than 70% CTA were prepared via solution blending in formic acid. Various characterization methods revealed that both polymers are immiscible at the molecular level at room temperature. However, they were macroscopically compatible and exhibited uniform physical properties due to the molecular interactions between CTA and CS with the same cellulosic backbone containing two linear polysaccharides through a β‐1,4 glycosidic bond. Careful visual inspection revealed that these membranes are transparent and their light transmittance was greater than 90% at all blend compositions. All membranes showed excellent tensile strength at all compositions and the maximum tensile strength was 52.4 MP from the membrane with a CTA/CS weight ratio of 9:1. The permeability of these blend films increased with increasing CS content and the maximum value was 44.28 mg/m²/day. To improve the permeability or transfer rate of the CTA/CS membranes, the porous CTA/CS membranes were also prepared using various amounts of silica nanoparticles. POLYM. ENG. SCI., 58:192–197, 2018. © 2017 Society of Plastics Engineers     

Acylation of iminochitosan: Its effect on blending with cellulose acetate

Chitosan has many similarities to cellulose, but there are few good direct solvents for codissolving them. Cellulose is cheaper than chitosan, and a blend film of the two would be expected to exhibit the desirable properties of both these polysaccharides. The formation of chitosanic and cellulosic acyl derivatives is an attractive route for the preparation of these fibers and films. They are soluble in common organic solvents, and in many cases it is not difficult to regenerate cellulose or chitosan from these derivatives. However, it may be desirable to protect the amino group from these reactions. Iminochitosan was used in the present study for that purpose. Chitosan at four molecular weights was prepared using an HCl/isopropanol binary system. The hydrolyzed chitosan was allowed to react with salicylaldehyde via Schiff base formation. Acylation of iminochitosan was carried out by its reaction with different acid halides containing a varied number of carbon atoms in the presence of a catalyst. The main factors that affected the dissolution of acylated iminochitosan in different organic solvents are described. Films from blends of n‐butyryl iminochitosan with cellulose acetate were prepared and are described. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 727–734, 2007     

Synthesis and properties of carboxymethyl cellulose‐graft‐poly(acrylic acid‐co‐acrylamide) as a novel cellulose‐based superabsorbent

A new cellulose‐based superabsorbent polymer, carboxymethyl cellulose‐graft‐poly(acrylic acid‐co‐acrylamide), was prepared by the free‐radical grafting solution polymerization of acrylic acid (AA) and acrylamide (AM) monomers onto carboxymethyl cellulose (CMC) in the presence of N,N′‐methylenebisacrylamide as a crosslinker with a redox couple of potassium persulfate and sodium metabisulfite as an initiator. The influences of reaction variables such as the initiator content, crosslinker content, bath temperature, molar ratio of AA to AM, and weight ratio of the monomers to CMC on the water absorbency of the carboxymethylcellulose‐graft‐poly(acrylic acid‐co‐acrylamide) copolymer were investigated. The copolymer's structures were characterized with Fourier transform infrared spectroscopy. The optimum reaction conditions were obtained as follows: the bath temperature was 50°C; the molar ratio of AA to AM was 3 : 1; the mass ratio of the monomers to CMC was 4 : 1; and the weight percentages of the crosslinker and initiator with respect to the monomers were 0.75 and 1%, respectively. The maximum water absorbency of the optimized product was 920 g/g for distilled water and 85 g/g for a 0.9 wt % aqueous NaCl solution. In addition, the superabsorbent possessed good water retention and salt resistance. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 1382–1388, 2007     

壳聚糖/纤维素复合微球对Cu2+的吸附

制备壳聚糖/纤维素(CS/CE)和交联壳聚糖/纤维素(ECS/CE)复合微球,用于吸附重金属离子,考察了微球对Cu2+的吸附性能。溶解性测试表明交联反应可提高微球在酸性介质中的化学稳定性。静态吸附表明,CS/CE和ECS/CE均能有效吸附Cu2+,pH 6附近吸附容量最大。吸附等温线与Langmuir和Freundlich模型均吻合,由Lang-muir模型得到的Cu2+饱和吸附容量分别为38.76 mg/g(CS/CE)和34.13 mg/g(ECS/CE)。CS/CE和ECS/CE对Cu2+的吸附初期为内扩散控制,但后期为配合反应控制。FTIR和X-射线光电子能谱(XPS)分析表明,壳聚糖中的N为Cu2+的主要吸附位,发生表面配合吸附。     

Isolation and identification of residual chromophores in cellulosic materials

A general procedure was developed for the isolation of residual chromophores in or on cellulosic material, which were hitherto inaccessible to structure elucidation due to their extremely low content in the ppb concentration scale. It is applicable to cellulosic pulp, cellulosic fibers (viscose, Lyocell) and cellulose derivatives (acetate, carbonyl-labeled cellulose) as well. The chromophore identification comprises treatment of the cellulosic material with boron trifluoride-acetic acid complex (BF₃·2HOAc) containing sulfite, chromatographic separation of the resulting chromophore-containing mixture, and structure determination of the main constituents by NMR/MS and comparison to authentic samples. Both adsorbed and covalently bound aromatic and quinoid compounds are selectively released by the treatment. Covalent ester, ether and secondary alkyl links between chromophore and cellulose are broken.Four cellulosic example substrates have been analyzed for their chromophore content: Lyocell fibers, cellulose triacetate, pulp after thermal treatment in N,N-dimethylacetamide, and pulp containing carbonyl-selective labels, and up to 11 chromophores per sample have been identified.     

Grafting Study and Antifungal Activity of a Carboxymethyl Cellulose Derivative

Graft copolymerization of appropriate monomers onto cellulose and its derivatives can enhance their characteristics and consequently expand their potential applications. Carboxymethyl cellulose (CMC) was prepared and characterized by FTIR spectroscopy and XRD. Graft copolymerization of acrylic acid sodium salt (AAs) onto CMC using ammonium persulfate (APS) as a free radical initiator was carried out under nitrogen atmosphere in aqueous solution. Occurrence of grafting was confirmed by comparison of FTIR spectra of CMC and the graft copolymers as well as the XRD patterns and thermal analysis. The effects of concentration of AA, temperature, concentration of APS and reaction time on the grafting yield were investigated by determining the grafting percentage and grafting efficiency. With other conditions kept constant, the obtained optimum grafting conditions were: CMC = 0.2 g, [AAs] = 2 mM, [APS] = 7.5 mM, temperature = 70°C and reaction time = 2 h. A preliminary study was then carried out to evaluate the antifungal activity of the prepared graft copolymer. This preliminary investigation of the prepared graft copolymers showed that they may be tailored and exploited to expand the utilization of these systems in medical applications.     

水溶性改性纤维素对粘土水化的抑制作用

为探索水溶性改性纤维素聚合物作为钻井用页岩水化抑制剂的可能性，本文以工业棉纤维为基本原料，在会成条件相当的情况下制备了羧甲基纤维素钠（CMC－Na）、羧甲基纤维素钾（CMC－K）、阳离子化羧甲基纤维素钠（CCMC－Na）与阳离子化波甲基纤维素钾（CCMC－K）四种结构不同的水溶性改性纤维素聚合物；以X-射线衍射、膨胀性试验及造浆试验考察了它们对粘土水化的抑制作用和机理。研究表明，在本试验条件下，四种改性纤维素聚合物对粘土水化均有一定的抑制效果；而合成时引入钾离子或季接阳离子则可使产物的抑制能力明显增强．