生物分子的毛细管电泳-化学发光检测法研究

根据某些氨基酸和蛋白质在碱性条件下具有能显著增强鲁米诺-铁氰化钾体系化学发光信号的特性,对毛细管电泳-化学发光法直接分离测定生物分子的可行性进行了研究.电泳所用缓冲溶液为2.5 mmol/L、含2.0 mmol/L鲁米诺的硼砂缓冲溶液;氧化试剂为2.0×10-4 mol/L铁氰化钾.在优化条件下,L-精氨酸和胃蛋白酶可直接实现分离,其检出限(S/N=3)分别为1.3×10-4 mol/L和7.1×10-7 mol/L.通过对市售的3种L-精氨酸标准样品进行分离分析研究,证明该方法可应用于L-精氨酸标准样品的纯度分析.     

毛细管电泳-间接化学发光法检测染发剂中苯二酚异构体和苯酚

根据某些酚类化合物在碱性条件下具有能猝灭鲁米诺-铁氰化钾体系化学发光信号的特性,建立了毛细管电泳-间接化学发光分离检测苯二酚异构体和苯酚的新方法.电泳缓冲溶液选用7.5 mmol/L Na2B4O7-2.5 mmol/L Na2HPO4.在优化的化学发光和电泳条件下,对苯二酚、间苯二酚、邻苯二酚和苯酚在10 min内可直接实现分离,其检出限(S/N=3)分别为2.9×10-8 mol/L、3.7×10-7 mol/L、8.4×10-8 mol/L和4.4×10-6 mol/L;相对标准偏差(RSD)为2.5%～4.8%(n=5).通过对不同染发剂实际样品进行分离分析研究,证明该方法可以用于实际染发剂样品的分析测定,结果令人满意.     

一种基于微芯片电泳平台的级联化学发光信号放大策略用于HIV-DNA的高灵敏检测

该文基于微芯片电泳-化学发光检测（MCE-CL）平台,以辣根过氧化酶标记的DNA(HRP-DNA)作为信号探针,利用HRP 催化鲁米诺和双氧水化学发光反应及目标分子与DNA的杂交反应,结合T7Exo酶辅助信号放大,建立了一种MCE分离辅助双循环化学发光信号放大的新方法。结果显示：优化实验条件下,在1.0×10-14~5.0×10-9 mol/L范围内,HIV-DNA的浓度对数值与HIV-DNA的化学发光强度呈良好的线性关系,检出限（S/N=3）为1.6×10-15 mol/L,在0.10、0.25、1.0、10（×10-12 mol/L）4个加标水平下的回收率为93.0%～103%,相对标准偏差（RSD）为0.50%～3.7%,方法具有较好的准确度,可应用于人血清中HIV-DNA的高灵敏检测。     

双酚A的流动注射化学发光法测定

基于双酚A对鲁米诺 铁氰化钾化学发光反应体系的化学发光的抑制作用,建立了一种测定环境雌激素双酚A的流动注射化学发光分析新方法。双酚A的浓度在8.0×10-7～1.0×10-5mol/L范围内与ΔI成良好的线性关系,检出限为3.05×10-7mol/L,已用于聚碳酸酯塑料水溶出液中双酚A的测定。     

铜-鲁米诺化学发光法测定抗坏血酸

本文采用鲁米诺-铜-抗坏血酸体系,建立了一种化学发光测定抗坏血酸的方法,方法具有操作简单,灵敏度高,重复性好等优点,用该方法测定抗坏血酸的线性范围为2.0×10~(-6)～6.0×10~(-5)mol/L,对4.0×10~(-6)mol/L抗坏血酸连续11次测定的相对标准偏差(RSD)为1.1％,用建立的方法对市售饮料、复合维生素及维生素片剂中的抗坏血酸进行了测定,结果满意.     

铊(Ⅲ)直接氧化鲁米诺化学发光测定岩矿样品中的痕量铊

液相化学发光主要是利用离子的催化作用进行测定。有几种高价金属离子能直接氧化鲁米诺化学发光。U.Fritsch等研究了铊(Ⅲ)在磷酸盐介质中直接氧化鲁米诺化学发光测定微量铊的方法,检测限为0.1ppm。本文在研究介质对铊(Ⅲ)-鲁米诺体系化学发光反应影响的基础上,选择H_3 BO_3-KOH介质测定铊,提高了灵敏度,检测限达到1ng/mL。铊浓度在4×10~(-9)—1×10~(-5)g/mL范围内有良好线性关系。用泡沫塑料从岩矿试液中分离铊。     

铁氰化镍化学修饰电极对亚硫酸根离子的电催化氧化及其应用

本文采用电化学方法在玻碳(GC)基体上制备出性能稳定的铁氰化镍(NiHCF)修饰膜电极,表征了NiHCF膜的电化学行为,研究了其对SO_3~(2-)离子的电催化氧化作用。结果表明,SO_3~(2-)离子在NiHCF/GC上氧化是受NiHCF媒介作用的,属EC平行催化反应。催化峰电流与SO_3~(2-)离子浓度在1.0×10~(-6)～2.0×10~(-2)mol/L范围内呈线性关系,检测限可达5.0×10~(-7)mol/L。用于测定空气中SO_2含量,结果良好。     

十六烷基三甲基溴化铵逆胶束介质中邻氯代苯亚甲基丙二腈的化学发光测定

以十六烷基三甲基溴化烷 (CTMAB)在氯仿 环己烷为主体溶剂相中所形成的逆胶束介质 ,基于鲁米诺 H2 O2 化学发光体系对邻氯代苯亚甲基丙二腈 (CS)进行定量分析 ,详细研究了氯仿与环己烷的不同配比、R值 ([H2 O] [表面活性剂 ])、CTMAB浓度、pH值、鲁米诺浓度及H2 O2 浓度对化学发光强度的影响。CS的检测线性范围为 1× 10 - 5～ 5 .5× 10 - 3mol L ,检出限达 4× 10 - 6 mol L(S N =3) ,对水样及土样的回收率均在 90 %以上。     

沙林在CTAB逆胶束介质中的化学发光分析

以 CTAB在氯仿 /环已烷为主体溶剂相中所形成的逆胶束介质 ,基于鲁米诺 - H2 O2 化学发光体系对沙林进行定量分析 ;研究了氯仿与环已烷的不同配比、R值、CTAB浓度、p H、鲁米诺浓度及 H2 O2 浓度对化学发光强度的影响。沙林的检测线性范围为 1× 1 0 -6～ 1× 1 0 -2 mol/L,检出限为 1 .5× 1 0 -7mol/L ,对水样及土样测定的回收率均在 90 %以上     

基于纳米CeO_2增敏鲁米诺化学发光法测定对乙酰氨基酚的研究

基于碱性条件下,CeO_2纳米粒子能够有效增敏鲁米诺-KMnO_4体系的化学发光,并结合流动注射技术建立了一种对乙酰氨基酚测定的新方法。实验研究了影响化学发光检测信号的多种因素,并初步探讨了可能的化学发光机理。在最佳实验条件下,对乙酰氨基酚浓度在1.0×10-7~5.0×10-5mol/L范围内与相对化学发光强度的抑制值呈良好的线性相关,相关系数(r2)为0.996 4,检出限(3σ)为3.3×10-8mol/L。对5.0×10-6mol/L的对乙酰氨基酚溶液平行测定11次,计算得相对标准偏差(RSD)为0.3%。该法用于银翘片中对乙酰氨基酚含量的测定,回收率为98.0%;对尿液的加标回收率为97.9%~98.7%,结果满意。     

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。