H2O2氧化降解海藻酸钠

研究了清洁高效的氧化剂H2O2对海藻酸钠的降解,探讨了溶液pH值、反应温度、H2O2用量及金属离子浓度对降解速度的影响. 结果表明,随着溶液pH值的降低、反应温度的升高及H2O2用量的增加,降解速度加快. 当反应pH=5.3、反应温度50 ℃、H2O2用量0.5%时,反应2 h即可降低海藻酸钠的分子量. 4 mg/L的Cu2+或Fe2+可明显加快降解速度,反应30 min的粘度变化相当于不加Cu2+或Fe2+时300 min的变化. GPC结果表明,海藻酸钠被氧化降解后,分子量下降,分布变宽;FTIR显示降解前后海藻酸钠的糖环结构没有改变,主要是糖苷键的断裂.     

球形纤维素吸附剂对Cu~(2+)的吸附动力学与热力学研究

以离子液体([Bmim]Cl)为反应介质,丙烯酸为单体,对纤维素进行均相接枝共聚,并采用油包水反相悬浮技术制得球形纤维素吸附剂。采用静态吸附实验方法研究了该吸附剂对水溶液中Cu2+的吸附性能,包括各种因素(溶液pH值,溶液初始浓度,吸附时间,吸附温度)对吸附效果的影响。研究结果表明,适当提高溶液pH值,增加溶液初始浓度,以及延长吸附时间都有利于改善吸附效果;球形纤维素吸附剂对Cu2+的吸附符合Langmuir吸附等温式,吸附过程是自发的放热过程;吸附剂对Cu2+的吸附符合二级吸附动力学模型,吸附过程由膜扩散和颗粒内扩散联合控制。球形纤维素吸附剂对Cu2+的具有很好的吸附性并具有良好的再生性能,可以循环使用。     

盐酸羟胺-电位滴定法测定氧化海藻酸钠上的醛基浓度

本文建立了一种测定被氧化海藻酸钠上醛基浓度的方法。盐酸羟胺可与醛基反应生成肟,同时释放出HCl,通过滴定HCl的量可计算出醛基的浓度。据此,本文采用盐酸羟胺-电位滴定法测定被氧化海藻酸钠上的醛基浓度,并考察了该方法的测定条件、精密度及准确度。结果,当盐酸羟胺与样品之间的反应时间≥2 h时,被氧化海藻酸钠上的醛基浓度与氧化反应时的投料比(≤80%)基本一致,该方法的RSD<10%;当以戊二醛溶液为标准品时,其测量值和真实值之间的误差<1%。本方法可快捷准确地测定小分子或大分子多糖上的醛基浓度。     

H2O2氧化降解海藻酸钠的研究

低分子量海藻酸钠在生物医学领域显示出越来越多的优势,以H2O2为氧化剂对海藻酸钠进行了降解研究。结果表明：随着溶液pH值的降低、反应温度的升高及H2O2用量的增加,氧化产物的表观粘度下降,降解速度加快,Cu2+和Fe2+等金属离子的存在加快了海藻酸钠的降解。GPC结果表明海藻酸钠被氧化降解后,分子量下降,分布变宽。FTIR显示,降解前后海藻酸钠的糖环结构没有改变,主要是开裂海藻酸钠的β-(1,4)糖苷键。     

相转移催化下复合高铁酸钾氧化甲苯的研究

制备了高稳定性的复合高铁酸钾氧化剂,并进行了表征.研究了高铁酸钾溶液的pH值和浓度对高铁酸钾稳定性的影响,并确定了高铁酸钾稳定存在的溶液环境.以复合高铁酸钾为氧化剂,采用相转移催化氧化甲苯法合成苯甲酸.考察了相转移催化剂种类、催化剂用量、反应时间以及反应温度等因素对苯甲酸收率的影响.结果表明,以十六烷基三甲基溴化铵作相...     

多醛基海藻酸钠交联剂的制备及性能

采用水/乙醇为反应溶剂,用高碘酸钠氧化海藻酸钠,制备了多醛基海藻酸钠(multi-aldehyde sodium alginate,MASA)。采用费林试剂、盐酸羟胺-NaOH电位滴定法、乌氏粘度计、与明胶的交联反应分别对氧化后的海藻酸钠进行表征。结果发现,氧化的海藻酸钠溶液可与费林试剂反应生成砖红色沉淀;海藻酸钠的氧化度随高碘酸钠用量及反应时间的增加而增加。投料比为80%时,氧化度最高可达约80%,收率约58.7%。MASA的粘度随反应时间、高碘酸钠浓度的增加而急剧下降。氧化度分别为20%、40%、60%的MASA,37℃下可使明胶在5min内生成凝胶。因此,水/乙醇作为反应介质、通过控制氧化剂的用量和反应时间,可以得到产率较高、分子量及氧化度可控的多醛基海藻酸钠多糖交联剂。     

磷酸化油菜秸秆纤维素吸附剂的制备及对溶菌酶的吸附

以天然产物油菜秸秆纤维素粉作为基质,二甲基甲酰胺为交联剂,磷酸为修饰剂,制备了新型磷酸化油菜秸秆纤维素生物吸附剂。用红外光谱、透射电子显微镜及X射线光电子能谱,对油菜秸秆纤维素和磷酸化油菜秸秆纤维素吸附剂进行表征。研究了油菜秸秆纤维素粉改性前后对溶菌酶的吸附,包括吸附溶液的pH值、溶菌酶的初始浓度、吸附时间、温度及NaCl的浓度等因素对吸附的影响。结果表明,在温度25℃,pH值7.4,吸附时间10h的条件下,磷酸化油菜秸秆纤维素粉微球对溶菌酶的吸附容量为451.71 mg·g-1,而未修饰油菜秸秆纤维素粉微球对溶菌酶的吸附容量只有332.43mg·g-1。在优化条件下用修饰吸附剂从鸡蛋清中分离纯化溶菌酶,纯化倍数为19.8,收得率为51.3%。     

羟丙基甲基纤维素的接枝共聚及其在复合材料中的应用研究

在水溶液中以KMnO4／草酸／硫酸(氧化-还原引发体系)引发甲基丙烯酸甲酯在羟丙基甲基纤维素上的乳液接枝共聚。研究了引发剂组成、反应温度、反应介质的H^ 浓度等对接枝率的影响。结果表明：反应温度和引发剂组成对接枝率有显著影响。接枝纤维素经IR和DTA表征。用接枝纤维素填充聚氯烯(PVC)所得PVC复合材料的拉伸强度提高了20％。     

羧酸纤维素的制备及其抗凝血性能的研究

采用高碘酸盐作氧化剂，以一步法和两步法制备羧酸纤维素，并对氧化反应的条件及氧化产物的抗凝血性能进行了研究。实验表明：加入添加剂后，氧化反应的反应条件温和，反应速度加快，反应可在数十小时内进行完全，所得到羧酸纤维素［－ＣＯＯＨ］≥５４．３％）具有优良的抗凝血性能，是一种很有应用前景的医用材料。     

纳米银在细菌纤维素凝胶膜中的原位合成及性能表征

在细菌纤维素纳米纤维网络结构中采用吐伦试剂与含醛基化合物原位反应生成纳米银颗粒, 制备了纳米银/细菌纤维素(n-Ag/BC)复合凝胶膜, 研究了不同反应条件对复合材料的银含量、 化学结构和晶体结构的影响以及n-Ag/BC的微观结构和纳米银在纤维素网络中的存在形态; 探讨了纳米银颗粒在纤维素网络中的形成机理; 采用伤口常见细菌之一金黄色葡萄球菌测试了n-Ag/BC的抑菌性能; 将n-Ag/BC与胎鼠表皮细胞共培养考察了材料的生物相容性. 研究结果表明, 在细菌纤维素纳米网络结构中可生成直径约为几十纳米的单质纳米银粒子; n-Ag/BC的银含量随着吐伦试剂浓度的增加而增加, 同时银含量还取决于含醛基化合物的用量; 原位反应生成纳米银粒子后细菌纤维素的晶型和结晶度没有发生变化; 纳米银颗粒在细菌纤维素纳米网络结构的交叉处生成, 复合材料n-Ag/BC对金黄色葡萄球菌的抑菌率达到99%以上, 不影响细胞的增殖和分化过程, 具有良好的生物相容性, 是一种有广阔应用前景的创伤修复抗感染材料.     

纤维素固定化血红蛋白研究

纤维素是一种重要的化工原料,由于来源广泛、价廉以及良好的再生性、反应性和通用性,被广泛用做载体材料．在酶的分离纯化,蛋白质分离纯化,亲合色谱固定相,拆分手性化合物等应用领域,往往采用球形纤维素或膜状纤维素形式．而在水吸附剂,分离回收金属离子,从海水中...     

固定化血红蛋白氧载体的研究(Ⅱ)——氧化纤维素共价键联血红蛋白

以纤维素为载体,经高碘酸钠氧化后共价键联血红蛋白,制备氧载体.研究了氧化条件对血红蛋白固定量的影响.纤维素只有经过预氧化、碱处理和再氧化三步活化反应,才能使血红蛋白大量固定化,每克纤维素固定血红蛋白量达1.0g.氧载体稳定性好,血红蛋白不脱落.经铁氰化钾氧化,氧载体放氧效率为33.1%.     

Viscometric determination of dialdehyde content in periodate oxycellulose. Part I. Methodology

Periodate oxycellulose was subjected to alkaline hydrolysis at room temperature in both homogeneous (cupriethylenediamine) and heterogeneous (sodium hydroxide) medium, and the degradation kinetics was followed for nearly three months. By comparing the obtained results with the degradation kinetics of both hydrocellulose and periodate oxycellulose reduced with tert-butylamine borane, it was demonstrated that the -alkoxy fragmentation of oxidised sites is a very fast reaction, which reaches completeness during the preparation of samples for viscometric analyses. The subsequent degradation is due to other mechanisms, such as autoxidation and peeling. A comparison between the degrees of polymerisation of periodate oxycellulose before and after its reduction allows the quantitative determination of dialdehyde groups, without the interference of reducing end groups. Although this technique might not be valid for other kinds of oxycellulose, it supplies a simple and fast method for the analysis of mildly oxidised cellulose.     

Graft copolymerization of cellulose initiated by ceric salts: Effect of reaction conditions on the consumption of ceric ion

A soluble monomer [methyl acrylate (MA)] and an insoluble monomer [butyl methacrylate (BMA)] were grafted onto cellulose by three types of ceric salts under both oxygen-free conditions and in the presence of oxygen. For comparison, Ce(IV) consumption during cellulose oxidation was also determined under similar reaction conditions. Slightly more Ce(IV) was consumed during cellulose oxidation in the presence of oxygen. During graft copolymerization of MA under oxygen-free conditions, the consumption of Ce(IV) was much lower than during cellulose oxidation regardless of the type of ceric salt employed. The opposite was observed in the presence of oxygen: much more Ce(IV) was consumed during grafting than during cellulose oxidation. The consumption of Ce(IV) in the graft copolymerization of BMA by ceric sulfate was nearly independent of reaction conditions and it was approximately the same as in cellulose oxidation. In the reaction initiated by ceric ammonium nitrate under oxygen-free conditions, less Ce(IV) was once again used up during grafting than during cellulose oxidation. However, the difference was much smaller than in the case of MA.     

Green and combinational method towards clickable alkynylated cellulose fibers (ACFs)

This paper presents an environmentally friendly strategy to obtain alkynylated cellulose fibers (ACFs), a versatile platform for tailoring cellulose by robust click reaction. This strategy is based on the integration of two efficient reactions: selective oxidation of cellulose fibers by sodium periodate (NaIO₄) generating dialdehyde cellulose fibers and subsequent Schiff base reaction with 3-ethynylaniline yielding alkynylated cellulose fibers (ACFs). The alkynyl moieties introduced into ACFs were simply transferred with azido compounds under Cu(I) catalysis and mild conditions. The content of alkynyl groups of ACFs was found to be as high as 3.0 mmol/g. Fourier transform infrared spectroscopy (FTIR) showed that the selective oxidation of cellulose fibers generated aldehyde groups and the Schiff base reaction resulted in the incorporation of ethynyl groups and benzene rings into cellulose fibers. FTIR and X-ray photoelectron spectroscopy results confirmed the successful click reaction between ACFs and 4-azidobenzoic acid. This clickable platform would serve as a versatile starting precursor for finely tuning cellulose fibers for advanced applications.     

Optimization of cellouronic acid synthesis by TEMPO-mediated oxidation of cellulose III from sugar beet pulp

Microfibrillated cellulose from purified sugar beet pulp was converted into cellulose III by immersion in liquid ammonia. When freed from ammonia, this product was oxidized in water at pH-10 using NaBr, NaOCl and 2,2,6,6-tetramethylpiperidine-1-oxyl radical (TEMPO) under various conditions and concentrations. The resulting water-soluble cellouronic acid—i.e. cellulose oxidized at the C6 position- was analyzed by high performance size exclusion chromatography (HPSEC) together with ¹³C NMR spectroscopy. The oxidation parameters, namely reaction time, temperature, NaBr and TEMPO concentrations were varied to determine the optimum reaction conditions. A low TEMPO concentration, a rather fast reaction time and the conducting of the oxidation at 0 °C were critical to obtain pure cellouronic acid in high yield, high purity and high DP.     

Morphological changes of sterically stabilized nanocrystalline cellulose after periodate oxidation

Periodate oxidation breaks the C2–C3 bond in the glucose repeat units of cellulose, forming two vicinal aldehyde groups. When the cellulose is partially oxidized, three products were generated after periodate oxidation: fibrous cellulose, sterically stabilized nanocrystalline cellulose (SNCC) and dialdehyde modified cellulose. Thus, by periodate oxidation alone, we can produce nanocellulose. SNCCs were produced after 26, 42 and 84 h periodate oxidation. Their morphologies were examined by transmission electron microscopy, which show that the three SNCCs have similar diameters (5–10 nm). In contrast, the average length of SNCC decreases with aldehyde content: from approximately 590 nm after 26 h of oxidation to 100 nm for an oxidation period of 84 h. It indicates that the morphology of SNCC can be well controlled by the degree of periodate oxidation, which depends on the amount of periodate and the reaction time. Equivalent spherical diameters of SNCCs were also examined by dynamic light scattering, and the results correspond closely to the ones observed by TEM. The viscosities of SNCCs were measured by an Ubbelohde viscometer and compared with theory. Because the length of SNCC particles gradually reduces while their diameters remain almost the same, we propose that periodate reacts preferentially with the amorphous region of cellulose. After most of the amorphous regions have reacted, the reaction proceeds at the boundary of amorphous and crystalline regions, creating a reaction front that advances towards the crystalline regions, thus continually shortening them. Dynamic light scattering experiments on SNCC suspensions when adding cosolvents into them proved that SNCCs were sterically stabilized in water.     

The gastroprotective effect of oxycellulose pellets on gastric ulcers

Oxycellulose belongs to the wide range of pharmaceutically and medically used cellulose derivatives unique in its properties of biodegradability, non-toxicity, antioxidative activity, haemostasis supporting, tissue healing improvement, etc. Glycyrrhizin (Gly) represents the most prominent licorice triterpenoid glycoside, which is responsible for its pharmacological activity, and is closely linked to increasing levels of gastroprotective prostaglandins. In order to study the anti-ulcer activity of oxycellulose sodium and Gly, pellets containing only oxycellulose, or in combination with glycyrrhizin, were prepared using an extrusion/spheronization method. The physical properties and in vitro release rate of the prepared pellets were tested. Based on the obtained results, one sample prepared from oxycellulose only, and one containing glycyrrhizin were chosen for in vivo testing. The healing effect of the prepared pellet formulations was evaluated in the acetic acid induced gastric ulcers in rats. The improvement in gastric ulcer healing was documented for myeloperoxidase activity, alkaline phosphatase activity and gastric wall mucin levels using the Alcian blue binding capacity. The tested pellets significantly reduced myeloperoxidase and alkaline phosphatase activity, and increased gastric wall mucus levels compared to the non-treated group. The in vivo tests showed that oral administration of the prepared pellets accelerated the healing of gastric ulcers in rats.     

Reversible crosslinking in cellulose. III. Factors controlling the oxidation behavior of mercapto groups in cotton derivatives

The oxidation behavior of mercaptocellulose prepared from tosylated cotton and of cellulose β-mercaptoethylaminocarboxylate (RDTC), which was prepared by reduction of a cotton derivative made by the reaction with bis-β-isocyanatoethyl disulfide, was studied, and the factors controlling the oxidation behaviors of solid polymeric mercaptans were discussed. RDTC was converted quantitatively to the corresponding disulfide by oxidation under mild conditions. Repeated oxidation–reduction cycles were applied to RDTC to demonstrate complete reversibility of disulfide crosslinking. On the other hand, only a portion of the mercaptan in mercaptocellulose could form disulfide by oxidation. It is considered that the mobility of the mercapto groups necessary for the oxidation coupling is restricted because they are attached directly to rigid cellulose chains. The oxidation of RDTC with air in alkaline medium was studied kinetically. It was found that the oxidation of the mercaptan in paired placement in the cellulose matrix proceeded more than ten times faster than that of the randomly placed mercaptan.     

Comparison study of TEMPO-analogous compounds on oxidation efficiency of wood cellulose for preparation of cellulose nanofibrils

The effect of chemical structures of TEMPO (2,2,6,6-tetramethylpiperidinyl-1-oxy radical) derivatives and its analogous compounds on oxidation efficiency of C6 primary hydroxyls of wood cellulose was investigated using the NaClO/NaBr system at pH 10. Because the oxidation takes place selectively on the surfaces of cellulose microfibrils, individualized and surface-oxidized cellulose nanofibrils can be obtained by simple mechanical treatment in water, when sufficient amounts of carboxylate groups are formed homogeneously in cellulose microfibrils. 4-acetamide-TEMPO and 4-methoxy-TEMPO showed efficient catalytic behavior with short reaction times (<4 h) and high carboxylate contents (>1.1 mmol/g) in oxidation of wood cellulose, comparable to TEMPO. Correspondingly, these TEMPO derivatives as well as TEMPO gave high nanofibril yields >56%. On the other hand, the use of 4-hydroxy-TEMPO and 4-oxo-TEMPO resulted in the lowest efficiency in oxidation: oxidation times >24 h, carboxylate contents <0.3 mmol/g, and individualized and surface-oxidized nanofibril yields <2%.