高效阴离子交换色谱-脉冲安培法测定支链淀粉糖链长分布

采用高效阴离子交换色谱-脉冲安培法,建立了不同作物中支链淀粉糖链长分布的分析方法.通过异淀粉酶水解支链淀粉糖分枝点的α-1,6糖苷键,形成不同长度的葡萄糖链.比较了不同色谱柱和不同色谱条件对支链淀粉糖链长分布测定结果的影响,优化了测定方法.以水、0.1 mol/L NaOH和1 mol/L NaAc+0.1 mol/L NaOH溶液为淋洗液进行梯度淋洗,通过CarboPac PA 20阴离子交换柱分离,实现了对聚合度(DP)大于80的支链淀粉糖葡萄糖链的测定.分别选取玉米、木薯、马铃薯与水稻的淀粉进行支链淀粉糖链长分布的研究,并用于其分子构型的判断.实验结果表明该方法简便、检测范围广、重现性良好,连续5次进样,在聚合度小于65时,各峰面积的相对标准偏差小于5％,可为进一步的淀粉糖理化特性研究和品种改良提供有效的实验依据.     

山茱萸酸性多糖FCP5-A的分离纯化与结构表征

从山茱萸中提取出水溶性粗多糖, 经柱色谱分离纯化得到一种酸性多糖组分FCP5-A. 采用高效凝胶渗透色谱法(HPGPC)测定其为均一性多糖, 平均分子量为8.7×104. 经IR、GC、部分酸水解、13C NMR及甲基化分析等方法对该多糖的化学结构进行了表征. 结果表明, 该多糖由鼠李糖、阿拉伯糖、半乳糖及半乳糖醛酸组成, 其摩尔比为1∶5.7∶0.6∶1.2. FCP5-A为多分支结构, 由-2)Rha(1-及-4)GalA(1-构成主链, 在鼠李糖的4位存在分支; 支链主要由高度分支的阿拉伯糖构成, 此外还存在-3)Gal(1-; 末端残基为Ara(1-及Gal(1-. 结果提示, FCP5-A为一种新的山茱萸酸性分支多糖.     

巴戟天中一种多糖的分离与结构表征

以巴戟天的根为原料, 经热水浸提、Sevag法除蛋白、乙醇沉淀和DEAE-Sepharose CL-6B离子交换柱层析, 得到一种水溶性的巴戟天多糖(MOPI-3). 通过UV、IR、NMR、GC-MS、高碘酸氧化、Smith降解和甲基化等物理化学方法对MOPI-3的纯度、理化性质和组成结构进行表征. 结果表明, MOPI-3分子量为36061, 是一种由阿拉伯糖、半乳糖和葡萄糖组成的杂多糖, 以α-1,3-吡喃葡萄糖和α-1,4-吡喃半乳糖为主链, 平均每5个葡萄糖连接一个半乳糖, 每个重复单元具有一个支链, 支链由3个呋喃阿拉伯糖以α-1,3-键型组成, 连接在主链葡萄糖的6位碳上, MOPI-3含有乙酰基, 连接在主链半乳糖的2位碳原子上.     

灵芝多糖的结构特征分析

采用沸水回流法从灵芝子实体中提取多糖,经Sevage法除蛋白,乙醇沉淀,离心、透析、膜分离,浓缩、冻干后得灵芝多糖。经HIO4氧化、Smith降解及甲基化反应,并利用多糖及刚果红混合液在碱性溶液中的波长的红移变化,通过UV-VIS,IR,GC,GC-MS,NMR对灵芝水提多糖的结构特征及三螺旋体结构进行分析研究。结果表明:灵芝多糖含有三螺旋体构型,GC-MS分析灵芝多糖的主要单糖组分为葡萄糖,还有少量的半乳糖、甘露糖、木糖和艾杜糖,IR及1HNMR分析多糖为β-构型,HIO4氧化、Smith降解和甲基化分析表明:多糖主要为(1→3)糖苷键连接构型,并伴有少量的1→6位支链键连接的结构,灵芝多糖是由D-葡萄糖单元通过β-(1→3)糖苷键连接葡聚多糖,其主要构型特征为(1→3)β-D-线性连接的骨架结构。     

中酯化度果胶离子络合复合物凝胶对葡萄糖迁移的影响

通过控制中酯化度果胶多糖溶液pH、多价离子浓度以及对凝胶-溶胶温度曲线的测定,研究其凝胶敏感特性和可逆性能.利用中酯化度果胶多糖的凝胶特性,以体外模拟实验研究不同凝聚态多糖体系中葡萄糖的生成和迁移行为.结果表明:中酯化度果胶多糖具有酸敏感、多价离子敏感等凝胶特性,且其凝胶具有温度可逆性.在降低葡萄糖迁移速率和降低淀粉生成葡萄糖速率两方面,中酯化度果胶钙凝胶体系效果较其他体系明显,并且使生成葡萄糖呈均化释放.     

离子液体对淀粉酶催化反应的影响

用分光光度法研究了二烷基咪唑氯类和二烷基咪唑磷酸酯类离子液体对淀粉酶催化反应的影响,通过吸光度的变化来测定淀粉水解的程度。 结果表明,这两类离子液体对淀粉酶催化反应均有明显的抑制作用,其中1-己基-3-甲基咪唑氯[HMIM]Cl的抑制作用最大。 而且,对于相同的阴离子,随着阳离子咪唑环烷基取代基链长的增加,抑制作用也增加。     

沙蒿籽水溶性胶多糖ASPI-A的结构与免疫活性的初步研究

从沙蒿籽中提取出水溶性胶多糖,经柱色谱分离纯化得到一种中性多糖组分ASPI-A.采用高效凝胶渗透色谱法(HPGPC)测定其为均一性多糖,平均分子量为5.42×104Da.经IR,GC部分酸水解、甲基化分析等方法对该多糖的化学结构进行了表征.结果表明,该多糖由阿拉伯糖、甘露糖、葡萄糖及半乳糖组成,其物质的量的比为1∶2.8∶4.9∶1.9.ASPI-A为多分支结构,以(1→4)-β-Glc构成主链,部分葡萄糖C6存在分支,由甘露糖以-4)Man(1-连接在葡萄糖C6位,Glc(1-和Gal(1-连接在甘露糖C4位构成.免疫活性实验结果表明,ASPI-A在10～50μg·mL-1浓度范围内对ConA诱导的小鼠T淋巴细胞增殖反应具有促进作用.     

半乳糖基葡聚糖的制备与结构表征

本文提出了一种在固态条件下,通过磷酸(5 mol%)催化半乳糖与葡聚糖共聚合成了半乳糖基葡聚糖的方法。采用1H NMR确定了不同条件下产物的摩尔取代度,发现当投料比为2:1,反应时间为9h,反应温度为110℃时,MS最大为0.43。还通过凝胶渗透色谱考察了不同反应时间条件下产物分子量,发现随反应时间延长,分子量逐步减小。最后使用甲基化分析法确定了MS=0.27的半乳糖基葡聚糖糖单元连接结构,发现半乳糖基葡聚糖的主链仍然由(1→6)-连接的葡萄糖组成,支化度为11.5%,其中位于主链糖单元C3的支链比例最大。支链半乳糖均为线型连接,并且其中(1→6)-连接比例最大,平均链长约为3个糖单元。     

接枝型阳离子淀粉絮凝剂对石材废水的絮凝降浊性能与机理研究

混凝/絮凝工艺是去除废水中悬浮胶体颗粒、降低浊度的有效手段.本研究以一种常见的天然高分子材料——淀粉为原材,以丙烯酰胺和甲基丙烯酰氧乙基三甲基氯化铵为共聚单体,采用接枝共聚技术,开发了一系列接枝链分布相同、但电荷密度及平均接枝链链长不同的接枝型阳离子淀粉改性絮凝剂:淀粉接枝共聚丙烯酰胺-聚甲基丙烯酰氧乙基三甲基氯化铵(St-G).并以一种具有高浊度特征的行业废水——石材废水为研究对象,详细讨论了St-G的结构因素(电荷密度与平均接枝链链长)及环境因素(絮凝剂投加量和pH等)对其絮凝性能的影响,结合絮凝后上清液Zeta电位、絮体结构的动态监测结果以及扩展DLVO(Derjguin-Landau-Verwey-Overbeek)胶体稳定理论等,详细探究了其絮凝机理.研究结果表明, St-G对石材废水的絮凝性能明显优于传统无机混凝剂聚合氯化铝, St-G对石材废水的除浊作用主要是电荷碎片机制为主导,且与黏结架桥作用协同作用的结果.随着St-G电荷密度的增加,其浊度去除率增加而对应最佳絮凝剂用量减少,且絮体破碎后恢复因子增加;而絮体尺寸、絮体生长速度及其破碎因子均与St-G平均接枝链链长呈正相...     

氨基酸功能化的果胶/姜黄素胶体粒子的合成与性质

通过酯化反应合成了新型的氨基酸功能化的果胶衍生物, 通过红外光谱(FTIR)和元素分析确认了果胶衍生物的化学组成及结构, 用动态光散射(DLS)和透射电子显微镜(TEM)表征了果胶衍生物胶体的形貌和尺寸. 结果表明, 果胶衍生物胶体呈现不规则的球状结构, 粒度分布较均一, 平均粒径200 nm. 用紫外-可见(UV-Vis)光谱测试了果胶衍生物胶体对姜黄素的包裹和控制释放, 结果表明, 姜黄素能够有效被果胶衍生物胶束包裹. 体外细胞毒理实验结果表明, 果胶衍生物胶体载体能显著提高姜黄素对HepG2细胞生长的抑制作用.     

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。