黑木耳酸性杂多糖构效关系的研究

研究了不同分子量的黑木耳酸性杂多糖６个分级和未分级试样的生物活性，小鼠腹腔注射试验结果表明该多糖具有促进白细胞增加、抗凝血和降低血小板的作用，其活性随着多糖分子量和糖醛酸含量降低而增大，即生物活性依赖于多糖在水中的溶解度，用酸碱返滴定法测定多糖中糖醛酸含量。实验结果与文献值一致。     

野生和人工栽培漆树液多糖的分子结构与生物活性

从湖北毛坝野生(大木)和人工栽培(小木)漆树液中分离纯化出酸性杂多糖D-LP和X-LP,化学降解和光谱分析表明两种多糖均含有D-Gal、D-GlcA、L-Ara和L-Rha,其摩尔比分别为77:18.3:3.7:1和63.7:13.3:3.9:1.两种漆多糖都是以β(1→3)D-Gal为主链的高度支化酸性杂多糖.D-LP支化度较高,分支点在Gal的C₆和C₄位;而X-LP仅有部分主链D-Gal的C₆位发生支化.小鼠腹腔注射试验表明,两种漆多糖均具有明显的免疫抑制作用,同时由野生漆树液提取的D-LP显示出比X-LP更高的免疫抑制功能和升白细胞活性功能.     

黑木耳酸性杂多糖溶液性质研究

从黑木耳子实体提取出的酸性杂多糖,通过重沉淀分成8个级分,用小角激光光散射和膜渗透压法测得试样在0.5mol/L NaCl/10％镉乙二胺饱和液(C)中的M_w(5.88×10~5)、M_n(1.43×10~5)和A_2值.研究了各个分级试样在3种水溶液中30℃的粘度行为,确立了Mark-Houwink方程为:(A)0.5mol/L NaCl,[η]=0.235 M_w~(0.48);(B)0.2mol Na_2SO_4/0.01 mol/L 磷酸盐缓冲液,[η]=7.61×10~(-2)M_w~(0.57);(C)[η]=6.44×10~(-2) M_w~(0.59).无扰尺寸(S~2)_0/M及K_8为12.9×10~(-18)cm~2·mol/g及0.175cm~3/g.确证该多糖分子在溶液中呈稍刚硬的柔性无规线团状态.     

桑叶多糖SJB的结构分析和蛋白酪氨酸磷酸酯酶PTP1B抑制活性

通过DEAE-纤维素和凝胶过滤柱色谱对桑叶碱提粗多糖进行分级分离, 获得均一多糖SJB, 进行结构鉴定. 采用蛋白酪氨酸磷酸酯酶PTP1B体外模型对SJB进行降血糖活性测定. 结果表明: SJB的相对分子质量为5.4×104, 由鼠李糖、阿拉伯糖、葡萄糖、半乳糖、半乳糖醛酸组成的酸性杂多糖; 主链由1,2-、1,2,4-连接的鼠李糖和1,4-、1,3,4-连接的半乳糖醛酸组成; 侧链包括末端、1,5-、1,3,5-连接的阿拉伯糖; 末端、1,4-连接的葡萄糖以及末端、1,3-、1,4-、1,6-连接的半乳糖, 主要通过鼠李糖的O4位和半乳糖醛酸的O3位与主链相连. 该多糖为首次从桑叶中获得的酸性杂多糖. 20 μg/mL SJB对PTP1B的抑制率为31.7%.     

灵芝子实体水溶性多糖的分离和分子量测定

用磷酸盐缓冲液、热水、碱和热碱水分别从灵芝子实体分离出五种水溶性杂多糖ＧＬ１、ＧＬ２、ＧＬ３、ＧＬ４和ＧＬ５．紫外光谱、红外光谱、气相色谱及硫酸咔唑分析结果表明，它们主要由葡聚糖、木糖、甘露糖、半乳糖组成，ＧＬ３、ＧＬ４和ＧＬ５含葡萄糖醛酸．由粘度、光散射和膜渗透压法测定了特性粘度［η］、重均分子量Ｍｗ及数均分子量Ｍｎ，ＧＬ２、ＧＬ３和ＧＬ５多糖的Ｍｗ值分别为１２４×１０４、１２８×１０４和５８×１０４．实验结果表明这些杂多糖含水溶性Ｄ 葡聚糖，并且初步推断，用磷酸盐缓冲液提取出的杂多糖ＧＬ２中包含刚性链β Ｄ 葡聚糖     

百合多糖的超声波提取工艺研究

以百合多糖的得率为指标,对超声波提取与沸水回流提取进行了比较。采用单因素试验和正交试验对超声波提取百合多糖工艺进行优选。实验表明,超声波提取百合多糖的最佳工艺条件为:提取温度90℃,料液比1∶6,提取3次,提取时间40 min,百合多糖的得率为1.37%。     

防风多糖化学成分的研究

从中药防风Saposhnikovia divaricata（Turcz．）Schichk中分离得到两种酸性杂多糖SPSa和SPSb,经凝胶渗透色谱证实为均一组分．UV-Vis光谱证实两种多糖中不含蛋白质．采用薄层色谱和毛细管电泳色谱确定了SPSa和SPSb中单糖的组成及摩尔比,SPSa：半乳糖：阿拉伯糖：鼠李糖：半乳糖醛酸=1：2．3：0．15：4．8;SPSb：半乳糖：阿拉伯糖：鼠李糖：木糖：半乳糖醛酸=1：1．5：0．8：0．2：10．2．采用IR光谱对多糖进行了初步结构研究．与现有的防风多糖的组成相比较,确定出SPSa和SPSb为新的防风多糖．     

黑海参多糖组成的研究

通过酶降解、酒精沉淀、DEAE柱纯化和脱色精制四步，从黑海参体壁中制得黑海参多糖的纯品。经电泳法及凝胶拉法鉴定，所得样品为均一组分，是一种典型的动物酸性杂多糖，内含硫酸酯基。样品经水解后用HPLC检测，得葡萄糖（36．7％）、岩藻糖（16．4％）、葡萄糖醛酸（34．2％）、木糖（7．22％）及一些未知成分（5．47％）。经Smith降解及一些波谱特征表明，单糖之间苷键是α-型，主要为1-2和1-3连结。凝胶往法测定其平均分子量约是96×104。     

多糖酸水解预处理方法的研究进展

多糖是构成生命的基本物质之一,单糖组成的测定是多糖质控的主要指标。近年来对多糖酸水解的预处理方法的研究受到人们的重视。目前多糖酸水解的预处理方法有直接酸水解、微波预处理、超声波预处理和离子液预处理等,多糖酸水解研究和开发具有广阔的前景。     

硫酸化高山红景天多糖(RSASL)的制备及鉴定

从高山红景天中分离出一种酸性杂多糖（ＲＳＡ）．该多糖由阿拉伯糖（Ａｒａ）、鼠李糖（Ｒｈａ）、半乳糖（Ｇａｌ）、木糖（Ｘｙｌ）、葡萄糖（Ｇｌｃ） 与半乳糖醛酸（ＧａｌＡ）组成,其单糖摩尔比为１．００∶３ ．２３∶０ ．２６∶０ ．３４∶０ ．８４∶１０．２４．用氯磺酸－吡啶法制备硫酸化高山红景天多糖（ＲＳＡＳＬ）．用离子色谱法测定ＲＳＡＳＬ 中Ｓ的质量分数为１１．０１％ ,其硫酸基取代度为０．８５．用红外光谱,紫外光谱,Ｓｅｐｈａｒｏｓｅ ＣＬ－４Ｂ柱层析,激光解吸电离飞行时间质谱等方法鉴定,ＲＳＡＳＬ均显示了多糖硫酸酯的特征     

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.     

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.     

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。     

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.     

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.

     

Investigation of Kinetics of Solid-Phase Synthesis of Lithium Orthosilicate

The kinetics of the interaction between lithium carbonate and silica with various degrees of dispersion was investigated by TG and DTA methods. It was found that the utilization of pyrogenic silica with a specific surface area of about 300 m²g^-1 instead of aerosil with one of 175 m²g^-1 leads to an increase of the reaction rate between lithium carbonate and silica, which depends on the formation and growth of lithium orthosilicate crystals in the first stage, and is conditioned by the diffusion of lithium and oxygen ions through the lithium orthosilicate layer formed at temperatures above 800 K. This supposition is supported by the kinetic analysis results obtained with the use of the different models. The optimal regime of heating is recommended. This revised version was published online in July 2006 with corrections to the Cover Date.     

小环化合物中饱和碳质子化学位移的计算

小环化合物由于其张力、构型、构象和各向异性效应等原因,环碳上质子化学位移缺乏规律性,难以预测,对此作者曾提出一种近似算法。本文根据303种小环化合物中饱和碳质子的化学位移实验数据,将适于计算这类质子化学位移的公式表述为:     

恶臭嗅辨实验室建设探讨

针对恶臭测试的环境影响问题,提出了解决的实例方案,并对方案的要点及优缺点进行讨论,此方案在实际操作中具有较好的效果。     

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.