Preparation,characterization and the effect of carboxymethylated chitosan–cellulose derivatives hydrogels on wound healing

Oxidized carboxymethyl cellulose (OCMC) was prepared by an oxidation reaction of carboxymethyl cellulose in the presence of sodium periodate. In situ crosslinked hydrogels were obtained through the crosslinking reaction between the active aldehyde of OCMC and the amino groups of the carboxymethyl chitosan (CMCS). The structure of the hydrogels was characterized by FTIR and scanning electron microscopy. Gelation time test showed that the hydrogel had the shortest gelation time of 24 s. The equilibrium fluid content, which represented the swelling degree, was evaluated and we found that the pH increased from 3.0 to 9.0, the equilibrium fluid content increased, and the highest equilibrium fluid content reached 312.83% as pH = 9.0. The wound healing efficacy of the hydrogel was evaluated in experimental deep second degree burns using a rat model. Results indicated that the wound covered with hydrogel was completely filled with new epithelium within 2 weeks, without any significant adverse reactions. The in situ crosslinked hydrogel fulfilled many critical elements in a wound dressing material. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

高碘酸钠氧化棉布纤维反应条件的研究

采用高碘酸钠对棉布纤维进行有限氧化,在棉布表面局部形成了双醛纤维素,为引入壳聚糖提供了活性部位。通过正交试验,初步确定棉布氧化反应最佳条件为:反应温度60℃,反应时间6 h,NaIO4浓度0.08 mol/L,pH值6,醛基含量超过180 mmol/L。     

Periodate oxidation of cellulose by homogeneous reaction

Homogeneous periodate oxidation of cellulose was achieved through methylol cellulose. The dissolution of methylol cellulose into aqueous periodate solution was followed by the gradual decomposition of methylol groups at random sites along the methylol cellulose chain. The recovery of glycol hydroxyl groups at the C₂ and C₃ positions on the glucopyranose ring during the above decomposition process caused uniform cleavage of C₂? C₃ bonds by the periodate ion. The oxidation level reached nearly 100% in 10 h. The reduced product of the resulting dialdehyde cellulose, i.e., dialcohol cellulose, resulted in mechanical properties quite different from those of conventional dialcohol cellulose. Examination of the thermal deformation and tensile properties revealed that no notable cellulose degradation occurred during the reaction. Our dialcohol cellulose gave a clear and transparent film with a flexible nature.     

氨基聚硅氧烷接枝改性纤维素膜对其结构和性能的影响

采用氢氧化锂/尿素/水溶液作为溶剂,通过冷冻-解冻配置稳定的纤维素溶液并制备纤维素膜.利用高碘酸钠选择性氧化纤维素葡萄糖单元临近的两个羟基制备出二醛纤维素,然后用氨基聚硅氧烷对其进行改性制备出憎水性复合纤维素膜.通过傅立叶红外光谱仪、扫描电镜、热重分析、接触角测定和溶胀率测定等表征氧化纤维素和憎水性复合纤维素的结构和性能.研究了不同质量分数的高碘酸溶液对纤维素的氧化程度以及对纤维素膜的结构的影响,通过改变氨基聚硅氧烷的摩尔浓度来制备不同接枝度的憎水性复合纤维素.结果表明,二醛纤维素具有很强的反应活性,改性纤维素膜的憎水性得到明显提高.在纤维素改性及功能化材料制备的研究中,较强的反应活性使其可以应用在更多的领域.     

聚多巴胺改性双醛壳聚糖的制备及其吸附性能

以壳聚糖(CS)为基材，采用高碘酸钠选择性氧化制备了双醛壳聚糖(DCS)，再通过接枝聚多巴胺(PDA)制得了环保型聚多巴胺/双醛壳聚糖(PDA/DCS)。采用SEM、FTIR、N₂吸附-脱附、XRD对两种改性壳聚糖进行了表征，并测试了其对胭脂红的吸附性能。结果表明，CS被高碘酸钠氧化后引入的活性基团醛基可与PDA产生共价结合，选择性氧化有效提高了DCS和PDA/DCS的吸附效果；与原CS相比，DCS结晶度明显下降，孔隙率和比表面积提高，PDA/DCS呈现较密集的多孔结构。DCS和PDA/DCS对胭脂红的吸附过程均遵循准二级动力学模型和Langmuir等温模型；但与DCS相比，PDA/DCS的吸附速率及吸附量明显提升，当染料初始质量浓度为700 mg/L时，PDA/DCS最大单分子层吸附量可达到1194.4 mg/g，且经过5次循环使用后，其吸附量仍达到616.90 mg/g。     

Comparative study of the influence of active groups of chitosan derivatives on antifungal activity

In this study, series of chitosan derivatives containing active groups were synthesized and evaluated for their antifungal activity against three crop‐threatening fungi, Fusarium oxysporum. f. sp. Vasinfectum, Alternaria solani, and Valsa mali. Schiff bases of carboxymethyl chitosan (As: 2‐(2‐hydroxy‐5‐nitrobenzylideneamino)‐6‐carboxymethyl chitosan; Bs: 2‐(2‐hydroxyl‐5‐chlorobenzaldimino)‐6‐carboxymethyl chitosan), N‐substituted carboxymethyl chitosan (An: 2‐(2‐hydroxyl‐5‐nitrobenzylamino)‐6‐carboxymethyl chitosan; Bn: 2‐(2‐hydroxyl‐5‐chlorobenzylamino)‐6‐carboxymethyl chitosan) and 2‐urea‐carboxymethyl chitosan (Au: 2‐(2‐nitrophenylurea)‐6‐carboxymethyl chitosan; Bu: 2‐(2‐chlorophenylurea)‐6‐carboxymethyl chitosan) were synthesized, and their antifungal activity was comparatively studied by hypha measurement in vitro, respectively. Results obtained from this study revealed that the active groups combined with Schiff bases functional groups (C?N) could strengthen the antifungal activity most effectively among the compounds studied in this work. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

双醛纤维素的制备及表征

以微晶纤维素(MCC)为原料,高碘酸钠为氧化剂,用正交实验考察了各种条件对氧化效率的影响。结果表明,影响醛基含量的顺序依次是投料比、反应时间、pH及反应温度。最佳氧化条件为:高碘酸钠和微晶纤维素投料质量比为1.0,反应温度30℃,pH=3,反应时间8 h。通过FTIR,XRD和SEM等对产物双醛纤维素在微粒形态、光谱特征、功能基团含量、晶体结构进行了表征。     

氧化纤维素的制备研究

介绍了氧化纤维素 (DAC)的制备过程 ,用正交法探讨了以NaIO4 作氧化纤维素时反应温度、溶液pH值、氧化剂浓度、反应时间以及交互作用对DAC醛基含量的影响 ,找到了影响醛基含量的主要因素为反应温度、反应温度与NaIO4 的交互作用、反应温度与溶液 pH值的交互作用。初步确定了制备氧化纤维素的反应工艺 ,使醛基含量较高时的最佳反应条件为 :反应温度 3 5℃ ,反应时间 3h ,NaIO4 质量分数 6.78% ,pH值为 2时 ,醛基含量达 68.2 0 %。     

利用二醛木聚糖一锅法制备纳米银抗菌水凝胶

利用二醛木聚糖(DAX)可与羧甲基壳聚糖(CMCS)以及银氨溶液同时反应的特性,即DAX的醛基与CMCS的氨基发生席夫碱反应形成亚胺键,同时,DAX含有的大量醛基与银氨溶液发生银镜反应,在室温条件下很快地还原出银纳米粒子(SNPs),一锅法制备出了具有优异抗菌性能的羧甲基壳聚糖-纳米银抗菌水凝胶。加入生物相容性良好的聚乙烯醇(PVA)并通过冻融法形成了与CMCS互穿的双网络结构,进一步提高了水凝胶的结构稳定性。采用FTIR、热重、TEM、XRD和SEM对DAX,SNPs和水凝胶的形貌、结构进行了表征。结果表明DAX在整个反应中起到了十分有效的双功能作用,成功的与CMCS和PVA发生反应,共同构成了双网络结构的水凝胶,从而提高了水凝胶的力学性能。同时,DAX将银氨溶液中的SNPs还原出来,且粒径在20-80 nm之间,具有较好的分散性,从而显著提高了水凝胶的抗菌性。本文中所制备的水凝胶具有伤口敷料方面的应用潜力。     

Preparation of amphoteric N,O‐carboxymethyl hydroxypropyl chitosan by a two‐step reaction

A novel N,O‐carboxymethyl hydroxypropyl chitosan (HPCMS) derivative was prepared by a two‐step reaction. Water‐soluble hydroxypropyl chitosan (HPCS) with a degree of substitution of hydroxypropyl higher than 0.8 was first synthesized by the reaction of chitosan (CS) with propylene oxide (PO) with alkali as a catalyst. Then, amphoteric chitosan derivatives (HPCMS) with a degree of substitution of carboxymethyl ranging from 0.42 to 1.38 were prepared by the reaction of HPCS with chloroacetic acid in an aqueous solution with alkali as a catalyst. The structures of the polymers were characterized by Fourier transform infrared spectroscopy and NMR; this showed that the hydroxypropylation mainly occurred on the ? OH groups at the C‐6 of CS in the reaction of CS with PO. In the reaction of HPCS with chloroacetic acid, both the ? OH and ? NH₂ groups of HPCS were susceptible to the carboxymethylation. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40460.     

Synthesis and properties of novel hydrogels from oxidized pectin crosslinked gelatin for biomedical applications

Gelatin (G) edible films with a new kind of dialdehyde polysaccharide, oxidized pectin (OP) as crosslinking agent are successfully prepared using casting techniques. FTIR and X-ray diffraction studies demonstrate that crosslinking is achieved through the reaction of aldehyde groups of oxidized pectin with the free amino groups in gelatin with a small affectation of the triple helix of gelatin. The qualitative and quantitative data about structures of films were determined by atomic force microscopy. Thermogravimetric analysis reveals that G/OP film has improved thermal stability in comparison with pure gelatin. Examination of the hemolytic potential showed that the obtained hydrogels are non-hemolytic in nature. These hydrogels are also nontoxic and blood-compatible. This kind of hydrogel is expected to be useful in the biomedical field, e.g., as wound dressing.     

选择性氧化法合成双醛纤维素硫酸酯

为了发展一个新的生物活性物质利用纤维素资源,采用高碘酸钠(NalO4)对微晶纤维素(MCC)进行选择性氧化,又与亚硫酸氢钠(NaHSO3)进行磺化反应,得到了双醛纤维素硫酸酯(OSC)。通过红外光谱(FTIR)分析手段对产品结构进行了表征。并考察了工艺参数对DAC醛基含量和OSC取代度的影响,得出了各合成阶段的关键工艺参数——时间、温度、pH值和反应物配比的最佳控制值。结果表明:当反应物配比为n(NaHSO3)∶n(DAC)=2∶1,产品合成温度为22℃,合成时间为2 h时,所得产品磺酸基取代度最高,并具有明显的表面活性。     

Depolymerization during nitroxide‐mediated oxidation of native cellulose

The kinetics and mechanism of depolymerization during nitroxide‐mediated oxidation of native cellulose has been studied under various conditions. The physical heterogeneity of the native cellulose and its complicated hypermolecular and supramolecular structure exerts a remarkable influence on the kinetics of oxidation and depolymerization. A strong influence of external tension applied on cellulose gauze reactivity during its oxidation has been proven, which is caused by its complicated hypermolecular structure. Celluloronic acids were obtained by the application of external tension during selective oxidation of native cellulose textiles. The cellouronic acids contained the higher amount of carboxyl groups but they also had a lower intrinsic viscosity, i.e., the average degree of polymerization (DP). The mathematical model—so‐called DP‐peeling off model—has been derived to describe the kinetics of cellulose depolymerization based on experimental data obtained. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

The bulk-dyeing of cellulose acetate with disperse aldehyde dyes

Conclusions 1. The possibility of obtaining dyed cellulose acetate by the addition to an acetonic solution of cellulose acetate of acetone-soluble aldehyde dyes which form strong chemical bonds with it has been studied.2. The optimum conditions for bulk-dyeing with aldehyde dyes have been worked out.3. It has been shown that the reaction of an aldehyde dye with cellulose diacetate leads to partial saponification of the acetyl groups. The hypothesis has been put forward of the subsequent acetylation of the hydroxy groups liberated by the aldehyde dyes.Institute of Chemistry, Academy of Sciences of the Tadzhik SSR. Novosibirsk Institute of Organic Chemistry, Siberian Division of the Academy of Sciences of the USSR. Translated from Khimicheskie Volokna, No. 3, pp. 39–41, May–June, 1969.     

新型天然交联剂氧化海藻酸钠制备及其性能研究

用高碘酸钠氧化海藻酸钠(ALG),制备具有二醛结构的部分氧化海藻酸钠(ADA),对醛基化过程中ALG结构、氧化度、醛基含量和粘均分子量进行研究.以剩余NaIO4与KI反应的碘显色法,考察ALG氧化程度,得出氧化动力学曲线;用粘度法得到ADA分子量.结果表明,ALG的氧化度随高碘酸钠量的增加而增加,12 h后在70%左右趋于平缓;氧化反应因为自由基存在,ALG由原来的分子量为28万变为氧化后的1万左右,并不随高碘酸钠用量的变化而变化.制得的ADA与壳聚糖溶液反应.交联生成凝胶,并且凝胶时间与ADA浓度增加而缩短,证明其具有交联作用,为应用于支架材料复合打下基础.     

Folate receptor targeted, carboxymethyl chitosan functionalized iron oxide nanoparticles: a novel ultradispersed nanoconjugates for bimodal imaging

This article delineates the design and synthesis of a novel, bio-functionalized, magneto-fluorescent multifunctional nanoparticles suitable for cancer-specific targeting, detection and imaging. Biocompatible, hydrophilic, magneto-fluorescent nanoparticles with surface-pendant amine, carboxyl and aldehyde groups were designed using o-carboxymethyl chitosan (OCMC). The free amine groups of OCMC stabilized magnetite nanoparticles on the surface allow for the covalent attachment of a fluorescent dye such as rhodamine isothiocyanate (RITC) with the aim to develop a magneto-fluorescent nanoprobe for optical imaging. In order to impart specific cancer cell targeting properties, folic acid and its aminated derivative was conjugated onto these magneto-fluorescent nanoparticles using different pendant groups (-NH(2), -COOH, -CHO). These newly synthesized iron-oxide folate nanoconjugates (FA-RITC-OCMC-SPIONs) showed excellent dispersibility, biocompatibility and good hydrodynamic sizes under physiological conditions which were extensively studied by a variety of complementary techniques. The cellular internalization efficacy of these folate-targeted and its non-targeted counterparts were studied using a folate-overexpressed (HeLa) and a normal (L929 fibroblast) cells by fluorescence microscopy and magnetically activated cell sorting (MACS). Cell-uptake behaviors of nanoparticles clearly demonstrate that cancer cells over-expressing the human folate receptor internalized a higher level of these nanoparticle-folate conjugates than normal cells. These folate targeted nanoparticles possess specific magnetic properties in the presence of an external magnetic field and the potential of these nanoconjugates as T(2)-weighted negative contrast MR imaging agent were evaluated in folate-overexpressed HeLa and normal L929 fibroblast cells.     

Phosphorylation of cellulose with phosphorous acid and thermal degradation of the product

The reaction of cellulose with phosphorous acid in molten urea afforded a white, water-soluble product. The product was a monoester of phosphorous acid, and all the phosphorus residues were in phosphonic form, i.e., cellulose phosphonate. Quantitative addition of acrylonitrile to the P? H bonds in cellulose phosphonate occurred in the presence of sodium ethoxide. By alkali hydrolysis of the adduct, a polyelectrolyte having two different ionization groups, P? OH and COOH, could be prepared. Thermal degradation of three cellulose phosphonates, ammonium cellulose phosphonate (I), ammonium cellulose 2-cyanoethlyphosphonate (II), and ammonium cellulose 2-carboxyethylphosphonate (III), was examined. All three samples decomposed at a temperature around 270°C, but their thermal behaviors were different. Replacement of hydrogen in the phosphonic residue by 2-cyanoethyl and 2-carboxyethyl groups retarded dehydration of cellulose. Sample I had a satisfactory flame retardance; samples II and III were not flame resistant. Reduction of flame retardance may be due to the electron-withdrawing effect of the cyano and carboxyl groups.     

Preparation and release kinetics of carboxymethyl chitosan/cellulose acetate microspheres as drug delivery system

Carboxymethyl chitosan, a water soluble chitosan derivative, was prepared from chitosan using monochloroacetic acid. Carboxymethyl chitosan/cellulose acetate microspheres (CCM) were prepared using the method of W/O/W and emulsification solvent evaporation as drug delivery system. The CCMs prepared were spherical, free‐flowing, and nonaggregated with the smooth appearance and many small pores on the surface. All CCMs prepared had sustained release efficiency for acetaminophen and the optimal formulation was that carboxymethyl chitosan of 2.0% and 1360 KD. In addition, the release rate of drug from CCMs in dilute hydrochloric acid was much slower than that in phosphate buffer saline (pH 6.8) during 24 h. It is illustrated that the drug loaded in CCMs released slower in simulated gastric fluid than that in simulated intestinal fluid. Furthermore, the drug release data showed better fitness with the first order model which indicated that the drug release from CCMs was depended on the drug concentration in the polymeric networks. And the release of drug from CCMs indicated diffusion‐controlled drug release based on Fickian diffusion and accompanied with anomalous transport (i.e., non‐Fickian diffusion) according to the values obtained from Higuchi model and Peppas models. So it was shown that the CCMs might be an ideal sustained release system for acid‐labile drugs both for the solubility of carboxymethyl chitosan and the release media. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42152.     

聚醚砜/N，O-羧甲基两性壳聚糖复合微滤膜的研制及其荷电特性

1INTRODUCTIONCharged membranes have been attracted more attention in membrane processes.Firstly,they have strong anti-fouling potential due to their charged groups.Secondly,they can be used as ion-exchange membranes for protein separations.Chitosan is the second abundant biopolymer after cellulose,and chitosan molecules contain a large number of reactive hydroxyl(-OH)and amine(-NH2)groups,therefore it can be an excellent candidate for affinity membranes[1].Until now,chitosan membranes have been used for reverse osmosis[2],pervaporation[3],and ultrafiltration[4].And attempts have been made to improve blood compatibility of chitosan with physical blends,surface modification and synthesis of blood-compatible derivatives[5].The present work reports the preparation of a carboxymethyl amphoteric chitosan[poly(ethersulfone) (PES)/CM-CS]composite MF membrane and its charged characteristics.     

Oxidation of cellulose in pressurized carbon dioxide

This work presents first results upon oxidation of type II cellulose by nitrogen dioxide dissolved in carbon dioxide at high pressure. This reaction leads to oxidized cellulose, a natural-based bioresorbable fabric used for biomedical applications. The oxidation reaction takes place in a heterogeneous fluid-solid system. Kinetics of oxidation is presented here and effects of operating conditions such as pressure, temperature and initial moisture content of cellulose are investigated. Results are presented in terms of degree of oxidation of cellulose and quality of the final oxidized cellulose, which has been characterized using liquid-state and solid-state ¹³C NMR. The experimental results show the existence of possible secondary reactions which may lead to oxidized cellulose with insufficient mechanical strength. An attempt is made to evidence and understand the role of CO₂ as a solvent in this system. Indeed, although supercritical CO₂ appears to be a suitable candidate as a solvent for oxidation reactions, some inhibiting effect on nitrogen dioxide activity are observed in this case.