壳聚糖超声可控降解及降解动力学研究

通过正交实验法考察了壳聚糖溶液浓度、反应温度、超声强度以及醋酸溶液浓度对超声降解反应的影响,确定了最佳反应条件,制备了一系列不同分子量的壳聚糖.研究了壳聚糖溶液浓度、反应温度以及壳聚糖原料分子参数与降解速率常数的关系.通过红外光谱、X-射线衍射和凝胶渗透色谱对降解产物进行了表征.结果表明,超声降解壳聚糖的最佳条件为10℃,壳聚糖溶液浓度2.5g/L.降解速率常数随壳聚糖溶液浓度和反应温度的降低而增大.高分子量和低脱乙酰度的壳聚糖原料有较高的降解速率和降解速率常数,壳聚糖原料的分子量对降解速率和降解速率常数的影响大于脱乙酰度对其的影响.超声波导致了壳聚糖分子量的降低和产物晶体结构的破坏,但没有改变产物的脱乙酰度和糖残基结构.     

溶菌酶降解壳聚糖条件的研究

研究了溶茵酶对壳聚糖的降解条件,结果表明：脱乙酰度约70％的壳聚糖较易被溶菌酶水解;水解反应的最适温度为55℃、pH值为4．0,低速摇床振荡对水解有利;在壳聚糖水解初期,溶液中还原糖浓度迅速增加,0．5h后水解速率逐渐减慢,至8h后还原糖浓度的增加已很缓慢;酶解液中还原糖的生成量瞳壳聚糖及溶茵酶浓度的增加而增大,当壳聚糖溶液浓度为20mg／mL、溶茵酶浓度为2．48mg／mL时,水解6h后,还原糖的含量可达6．758mmol／L。水解6h后酶解液中还原糖浓度与壳聚糖的浓度呈线性关系。     

碱量法测定壳聚糖脱乙酰度的研究

碱量法(包括酸碱滴定法和电位滴定法)是目前测定壳聚糖脱乙酰度较为常用的方法,其原理是用过量的稀酸与一定量的待测壳聚糖反应,然后用标准NaOH溶液滴定过量的酸来测量壳聚糖中自由氨基的量,从而计算壳聚糖的脱乙酰度(DD值)。计算脱乙酰度的公式多用:DD=(-NH2)%/0.094×100%(公式一)。而另外一个碱量法中未用过的脱乙酰度计算公式为:DD=[203n/(G 42n)]×100%(公式二),本文用计算公式一和公式二分别计算在酸碱滴定法和双突跃电位滴定法中壳聚糖的脱乙酰度,结果表明:在酸碱滴定法中,用公式一的计算的结果准确度更高,而在双突跃电位滴定法中用公式二计算的结果准确度更高。     

羟丙基三甲基氯化铵壳聚糖制备的可控性研究

用壳聚糖与缩水甘油三甲基氯化铵反应制备羟丙基三甲基氯化铵壳聚糖,所得产物的结构受壳聚糖分子量和脱乙酰度、反应温度、反应时间、壳聚糖与缩水甘油三甲基氯化铵投料比的影响。实验结果表明：随着反应温度升高,羟丙基三甲基氯化铵壳聚糖的取代度增加,在70～80℃达最大;反应时间增加,取代度增加,产物分子量降低。缩水甘油三甲基氯化铵与壳聚糖比例达3：1前取代度随比例升高而增加。脱乙酰度和分子量越大的壳聚糖其季铵盐取代度越高。控制反应温度在30～90℃,反应时间3～10h,投抖比为1：1～4：1,可以得到取代度15％～909／6,分子量1万到100万的羟丙基三甲基氯化铵壳聚糖。     

中性蛋白酶对壳聚糖的降解

用粘度测定法和还原糖测定法,研究了中性蛋白酶非专一性降解壳聚过程中温度,ｐＨ值,反应时间,酶浓度,底物浓度,金属离子及壳聚糖的脱乙酰度对中性蛋白酶降解壳聚糖反应速度的影响,确定了以壳聚糖为底物的中性蛋白酶的一些催化特性：最适温度为５０℃;最适ｐＨ值为６．０;米氏常数Ｋｍ值为１．１×１０＾－２ｇ／ｍＬ;一定浓度的Ｃｕ６２＋,Ｂａ＾２＋,Ｍｎ＾２＋抑制该酶的活性;     

壳聚糖的基质辅助激光解吸电离飞行时间质谱分析

利用基质辅助激光解吸电离飞行时间质谱(MALDI-TOF-MS)分析甲壳素脱乙酰化降解产物——壳聚糖,对基质、制样方法等影响MALDI-TOF-MS测定结果的因素进行了研究。实验发现,以2,5-二羟基苯甲酸(DHB)为基质,二次结晶法制样分析壳聚糖,既获得了壳聚糖的分子量信息,又可以推断壳聚糖的脱乙酰度,对壳聚糖的制备及其质量与性能控制有着十分重要的指导意义。     

海洋烟曲霉菌产脱乙酰酶发酵条件优化

几丁质酶是一类复合酶,包括脱乙酰酶、几丁质酶、壳聚糖酶、几丁寡糖酶、几丁二糖酶等,将脱乙酰酶应用于壳聚糖的制备中,不仅可以有效地从甲壳素(几丁质)分子中脱除乙酰基,而且不会把甲壳素的长链降解为小分子,可以制备出高脱乙酰度且性能独特的壳聚糖,同时不存在排放废碱液而对环境造成严重污染.     

臭氧降解法制备壳低聚糖及其结构表征

以85％脱乙酰度、相对分子质量为25×10^4的壳聚糖为原料,在20℃、pH为3、氧气流量0．7m^3／h的条件下降解6h,降解液用氨水调至pH为9,无沉淀,分别用截留相对分子质量为2k、3k、5k、10k的中空纤维膜超滤,获得所需聚合度的壳低聚糖。降解产物的结构用红外光谱、核磁共振碳谱表征,结果说明降解前后的结构基本没有变化。降解产物的聚合度用飞行时间质谱表征,其中经过2k中空纤维膜超滤后的壳低聚糖聚合度主要为4～10。     

凝胶渗透色谱法研究壳聚糖生物材料酶降解过程的均匀性

壳聚糖是一种重要的生物医用材料,脱乙酰度是影响其生物降解性能的重要因素。运用凝胶渗透色谱研究了脱乙酰 度及相对分子质量分布相似、而聚合单元N-乙酰氨基-D-葡萄糖和D-氨基葡萄糖分布不同的两种壳聚糖材料在溶菌酶作用 下的降解过程,分析检测了壳聚糖材料在降解过程中的重均相对分子质量、相对分子质量多分散性和相对分子质量分布 的变化。发现聚合单元为随机分布的壳聚糖样品,其降解是均匀的;而聚合单元为段状分布的壳聚糖样品,其降解是非 均匀的;表明其聚合单元的分布方式决定壳聚糖材料酶降解过程的均匀性。     

锑电极-电位滴定法测定壳聚糖的脱乙酰度

<正>壳聚糖又名脱乙酰甲壳素,是甲壳素经浓碱脱乙酰基后得到的衍生物,具有良好的生物相容性和生物可降解性,广泛应用于医药、食品、化妆品、轻工、印染、环保和生物工程等领域~[1-3]。而壳聚糖的脱乙酰度(DD)则是指壳聚糖多糖分子氨基上脱去乙酰基的百分比,其高低直接影响壳聚糖的溶解度、絮凝能力、螯合金属离子能力和N-选择性酰化能力等物化特性,是鉴定壳聚糖产品质量的一个重要指标。因此,如何快速准确地测定壳聚糖的脱乙酰度     

Dichroism of absorption and polarization of phosphorescence of molecules of the closed form of nitrobenzospirothiopyran

The spectral-polarization characteristics of absorption and phosphorescence of molecules of the initial form of nitro-substituted indolinospirobenzothiopyran were studied in oriented polyethylene films and in solutions with different polarity. An oscillator model of the electron transitions responsible for the formation of absorption and luminescence spectra was suggested. It was established that the principal differences in the spectral and photophysical properties of the compound studied and its oxygen-containing analog are associated with the fact that the electronegativity of the S atom is lower than that of the O atom. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1143–1146, June, 1997.     

非那雄胺合成工艺改进

非那雄胺能抑制5α-还原酶的活性,明显降低二氢睾酮水平,是一种治疗良性前列腺增生的有效药品。该合成工艺以甾烯酮酸为原料,将其与氯化亚砜反应,无须分离即与叔丁胺反应得17β-酰胺化合物,再氧化开环,环合,氢化,脱氢合成了非那雄胺。经元素分析、IR、1HNMR、13CNMR、MS分析表征了其结构。该法无须使用昂贵的2,2-二吡啶二硫化物和剧毒药品苯亚硒酸酐,且以乙酸铵代替氨气,降低了对设备的要求和腐蚀,更适用于工业生产。     

Determination of heats of detonation and influence of components of composite explosives on heats of detonation of high explosives

The heats of detonation of 20 simple high explosives and explosive mixtures were determined by means of an adiabatic detonation calorimeter designed by the authors. The results indicated that the performance of the instrument was reliable and the experimental data were very accurate. For explosive mixtures, there was a linear accumulative relationship between the heats of detonation of the explosive mixture and its components. Accordingly, the heats of detonation of explosive mixtures could be calculated directly from the heats of detonation of simple explosives and the characteristic heats of other components. The experiments showed that the gold or brass shell of the cylindrical charge could be substituted by a thick-walled porcelain shell, which had the advantage of cheapness.

     

Synthesis of phenolic components of Grains of Paradise

Two vanilloids, (5E)-8-(4-hydroxy-3-methoxyphenyl)oct-5-en-4-one (1) and 4-[3-hydroxydecyl]-2-methoxyphenol (2), isolated from the dried seeds of Grains of Paradise (Aframomum melegueta), were synthesized; the latter compound was made as the S-enantiomer and the material derived from the seeds was found to be a 1:1.7 mixture of the R and S isomers. The synthetic route used should allow the preparation of analogs having extended alkyl chains and consequently different lipophilicity, and 3, a homolog of 2, was also prepared.     

Summary of development of the theory of stability of colloids and thin films

In this review, the research of the author in the field of colloidal systems is summarized. The factors influencing colloidal stability are systematized and analyzed. Examples are presented to illustrate the practical utilization of the theory of stability of colloids and thin films.This review was prepared on the basis of the works of the author, which were awarded the State Premium for 1991 in the field of science and technology, chemistry section.Institute of Physical Chemistry, Russian Academy of Sciences, 117915 Moscow. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 8, pp. 1708–1717, August, 1992.     

Study of hydration of two cements of different strengths

Main hydration products of two cement pastes, i.e. CSH-gel, portlandite (P) (and specific surface S) were studied by static heating, and by SEM, TEM and XRD, as a function of cement strength (C-33 and C-43) hydration time (th) and subsequent hydration in water vapour.Total change in mass on hydration and air drying, M_o, increased with strength of cement paste and with hydration time. Content of water escaping at 110 to 220°C, defined as water bound with low energy, mainly interlayer and hydrate water, was independent on cement strength but its content increased with (th). Content of chemically bound (zeolitic) water in CSH-gel, escaping at 220-400°C, was slightly dependent on strength and increased with (th). It was possibly derived from the dehydroxylation of CSH-gel and AFm phase. Portlandite water, escaping at 400-500°C, was independent on cement strength and was higher on longer hydration. Large P crystals were formed in the weaker cement paste C-33. Smaller crystals were formed in C-43 but they increased with (th). Carbonate formated on contact with air (calcite, vaterite and aragonite), decomposed in cement at 600-700^oC. It was high in pastes C-33(1 month) and C-43(1 month), i.e. 5.7 and 3.3%, respectively; it was less than 1% after 6 hydration months (low sensitivity to carbonation) in agreement with the XRD study showing carbonates in the air dry paste (1month), and its absence on prolonged hydration (6 months) and on acetone treatment. Water vapour treatment of (6 months) pastes or wetting-drying increased this sensitivity.Nanosized P-crystals, detected by TEM, could contribute to the cement strength; carbonate was observed on the rims of gel clusters.This revised version was published online in November 2005 with corrections to the Cover Date.     

氯氧化镁生成热的研究

用氧化镁氯化镁水溶液制备了8水合氯氧化镁[nMg(OH)2·MgCl2·8H2O], 并测定了其在盐酸中的溶解热, 实验结果表明, 氯氧化镁溶解热与n值呈线性关系, 根据溶解热求出5Mg(OH)2·MgCl2·8H2O和3Mg(OH)2·MgCl2·8H2O的生成热分别为-7727.1和5888.1kJ·mol^1^-。     

Thermodynamics of the formation of oxosulfides of rare-earth elements

The enthalpies of solution of several oxosulfides of rare-earth elements and the high-temperature enthalpies of oxosulfides and oxosulfates of lanthanum and yttrium were measured using solution calorimetry and high-temperature microcalorimetry techniques. Standard enthalpies of formation and some thermodynamic properties of oxosulfides and oxosulfates were calculated. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2 pp. 294–297, February, 1997.     

探究“铁的锈蚀条件”实验创新设计

设计了铁的锈蚀实验,说明了铁钉的处理方法,增加了温度、酸、碱的影响条件,实现了铁跟蒸馏水及空气中氧气快速反应而生锈,使实验在5 min左右就能够得到准确的结果。