血红蛋白过氧化物模拟酶胶束催化显色体系

在胶束Tween80介质中，研究了以血红蛋白（hemoglobin,Hb)作为过氧化物模拟酶、隐性亮绿（recessive brilliant green,RGB)为氢供体底物、溶解氧为受氢体的酶催化反应特性。在pH5.64(NH4)2HPO4-KH2PO4缓冲溶液中，利用模拟酶对溶解氧作为受氢体催化RBG氧化生成亮绿（brilliant green,BG)而拟定了测定Hb含量的新方法。讨论了胶束介质对酶体系催化反应的影响及酶催化反应的可能机理。     

基于酶催化反应的核酸定量新方法

近年来 ,将染料自缔合或诱导缔合用于核酸定量测定备受关注 [1～ 3 ] .但是将酶与染料的缔合用于核酸定量测定尚未见报道 .氯化血红素 (hemin)可作为辣根过氧化物酶 (HRP)的模拟酶 ,能催化 H2 O2氧化对 -羟基苯乙酸 (p- HPA)生成荧光产物——联二对 -羟基苯乙酸的反应 [4 ,5] .由于 hemin在碱性介质中是阴离子化合物 ,能与阳离子化合物如阿尔新蓝 (Alcian Blue 8GX)发生缔合作用 ,从而使自身的催化性质被抑制 .当加入带负电荷的脱氧核糖核酸 (DNA)时 ,由于阿尔新蓝与 DNA的强烈作用使hemin与阿尔新蓝的缔合物被破坏 ,hemin的催化活…     

血红蛋白的过氧化物酶催化特性研究

探讨了用血红蛋白（Hb)作为辣根过氧化物酶（HRP）的替代物，用于率H2O2氧 化对甲基酚的反应体系，研究了血红蛋白的过氧化物酶特征及其酶催化动力学特性 。稳态速率法测定了米氏常数（Km)、米氏速率（Vm)及反应级数等动力学参数。讨 论了对甲基酚作为血红蛋白的氢供体底物的酶催化反应机理，确立了反应速率方程 。实验比较发现血红蛋白作为过氧化物酶（HRP）的替代物，其催化活性比氯化血 红素（Hemin)，β-环糊精－氯化血红素（β－CD－Hemin)等过氧化物模拟酶要高。     

氯化血红素作为过氧化物模拟酶与HRP的比较研究

用荧光光谱和紫外－可见吸收光谱研究了氯化血红素（hemin)催化过氧化氢与对羧基苯丙酸反应的动力学和反应产物,表明hemin同时具有模拟过氧化物酶、过氧化氢酶的活性,在反应过程中hemin自身被氧化分解。hemin催化反应的产物除与天然的辣根过氧化物酶（HRP）催化的产物相同（λex/λem=310nm/406nm）外,还有激发峰在258nm和300nm,发射峰在360nm的荧光物质。通过对产物光谱特性的比较,研究了hemin和HRP的特异性差异。该研究结果对进一步筛选和研究高特异性过氧化物模拟酶具有重要的指导意义。     

直链醇对反胶束体系中木素过氧化物酶催化活性的影响

根据研究发现, 在有醇作助表面活性剂的CTAB反胶束中木素过氧化物酶(LiP)不能表现活力, 而在水介质中CTAB对LiP的催化活性影响又不是很大. 为了揭示其中醇的影响, 本工作就不同碳链长度的醇对LiP酶催化性能的影响进行了研究. 由于CTAB反胶束体系中醇浓度较高, 且碳原子数大于4的直链醇在水中的溶解度又很小, 为此采用了LiP可在其中显示催化活性的CTAB正胶束、AOT反胶束和Brij30反胶束作介质, 通过研究这些介质中不同链长的醇对LiP催化活力的影响, 来探讨CTAB反胶束中木素过氧化物酶(LiP)不能表现活力的原因. 结果表明, 不管表面活性剂聚集体的结构、电性质及反胶束大小如何, 只要醇的浓度超过500 mmol•L^－1 (丁醇≥1200 mmol•L^－1), LiP在上述原本可显示活力的介质中均无催化活性. 据此推测CTAB反胶束中木素过氧化物酶(LiP)不能表现活力的原因主要是由助表面活性剂醇造成的.     

β-环糊精修饰氯化血红素的合成、表征及人工酶性质

血红素是含有铁卟啉的天然化合物。以天然的或人工的金属卟啉模拟过氧化物酶是近年来研究的活跃领域^[1]。本研究认为,β-环糊糈(βCD)在结合某些酶底物或药物有更合适的空腔尺寸,将氯化髙铁血红素(Hemin)共价结合上去在仿生化学中有广泛的应用。本文用DCC缩合法合成了βCD-Hemin,作为过氧化物酶的底物的共受体,并将其均相催化动力学性质与天然酶(HRP)、氯化血红素辅基模型进行比较,应用光谱法通过监测在弱酸性介质中H₂O₂氧化隐色孔雀绿(MGL)生成孔雀绿(MG)染料的变化过程,来研究其仿生催化反应机理。     

β-环糊精修饰氯化血红素在弱碱介质中的仿酶性质研究

将β-环糊精共价结合的氯化血红素(βCD-Hemin)作为过氧化物酶底物的共受体, 将其均相催化动力学性质与天然酶HRP或锰卟啉等辅基模型物进行比较,应用光谱法通过测量H₂O₂、苯酚和4-氨基安替比林(AAP)作用生成醌式染料的反应来研究其仿生催化机理。     

轴向配基对HRP模拟酶Hemin催化荧光及化学发光反应影响的研究

以氯化血红素作为辣根过氧化物酶（ＨＲＰ）的模拟物,对二十种氨基酸和其他含氮有机配体的轴向配位效应进行了研究。发现在氯化血红素催化的荧光和化学发光体系中,组氨酸和咪唑均使ｈｅｍｉｎ的催化活性显著提高,而酪氨酸,色氨酸,Ｌ－半胱氨酸及卤代烷基吡啶等具有淬灭效应。     

咪唑衍生物金属胶束模拟过氧化物酶研究

咪唑衍生物铜配合物Cu(biap)·Cl2及其与胶束形成的金属胶束模拟过氧化物酶成功地用于催化H2O2氧化苯酚反应,反应遵循酶催化的动力学规律.过氧化氢/催化剂物质的量比和酸度对反应的影响符合生物催化剂条件影响的一般规律.讨论了不同类型表面活性剂胶束对该氧化反应的影响.     

Schiff碱铜配合物模拟过氧化物酶的研究

两种Schiff碱铜配合物首次作为过氧化物酶的模拟物用于催化过氧化氢氧化苯酚的反应;分析了配合物的特征光谱;研究了Schiff碱铜配合物的催化氧化机理,建立了催化氧化反应动力学数学模型;讨论了过氧化氢／催化剂摩尔比、体系温度、体系pH和胶束微环境对催化反应速率的影响．结果表明：这两种Schiff碱铜配合物在不同的反应条件下均表现出过氧化物酶催化的特征．     

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.     

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。