用燐光寿命变化分析血中游离色氨酸

全血用三氯醋酸(TCA)去蛋白的上清液中加入不同量色氨酸(x),测燐光寿命(τ).以加入色氨酸与燐光寿命变化回归方程与应用推导的公式。x_0=τ_i-bx_i)/b,计算血中游离色氨酸(x。)为 11.1μg/mL.与文献报道的一致.     

用磷光寿命变化测定碘离子与磷光体反应动力学参数

利用Ｉ＾－促进系间窜越，加快发现过程，缩短磷光寿命的特点，研究Ｉ＾－量改变与色氨酸，色胺磷光寿命关系，分别为：τ＝３．９８ｅ＾－０．０６５８ｘ，与τ＝３．５ｅ＾－０．０８９９ｘ，应用静态分析，推导Ｓｔｅｒｎ－Ｖｏｌｍｅｒ式，计算平衡常数Ｋｓ与ｋｉ，分别为：０．１０９与０．２００ｍｍｏｌ；０．０２７与０．０５１ｓｍｍｏｌ＾－１。利用本法分析了酷氨酸，苯丙氨酸，Ｌ－色氨酸，牛血清白蛋白，葡糖苷酸酶。     

用Lin光寿命变化分析血中游离色氨酸

全血用三氯醋酸去蛋白的上清液中加入不同量色氨酸，测Ｌｉｎ光寿命，以加入色氨酸与Ｌｉｎ光寿命变化回归方程与应用推导的公式ｘ０＝（τｉ－ｂｘｉ）／ｂ，计算血中游离色氨酸为１１．１μｇ／ｍＬ。与文献报道的一致。     

西维因无保护流体室温燐光的重原子效应和有机溶剂的影响

在无任何保护性介质存在的水溶液中 ,仅以KI为重原子微扰剂 ,亚硫酸钠为除氧剂 ,西维因 (CBL)能发射强而稳定的室温光 (RTP)信号 ,峰波长λex λem =2 85 4 95 ,5 2 3nm ,光强度与CBL浓度在 10～ 16 0μg L 范围内呈良好线性关系 ,检出限 0 .90 μg L。详细研究了重原子微扰剂浓度对光寿命的影响 ,发现I- 浓度 (x ,mol L)与RTP寿命 (τ ,ms)间的关系能表示为τ =0 .5 2 0e- 0 .4 2 5x,T1 →S0 的光发射速率常数kp 和KI重原子效应常数a分别为 1.92ms- 1 和 1.0 4ms- 1 ·mol·L- 1 。研究还发现 ,少量有机溶剂 (约 3% ,V V)的存在 ,因能增加CBL的溶解度 ,可获得最高的RTP强度 ,使检出限比无有机溶剂时的类似方法降低了约 1个数量级 ,重原子微扰剂的适宜浓度降低了 2 3。所拟定的测定CBL的室温光分析法 ,用于强化的环境土壤及水样中CBL的测定 ,回收率为 95 .2 %～ 10 4 .5 % ,相对标准偏差为 2 .2 6 %～ 3.76 % (n =3)。     

核黄素的燐光分析

核黄素无磷光,加碱在沸水中作用３０ｍｉｎ后产生强的磷光，λｅｘ３９０，λｅｍ５２ ０ｎｍ寿命０．７３ｓ。研究了１６个化合物对核黄素磷光的影响，结果表明，只有硫胺、叶酸、色氨酸、Ｂa＾２＋、Ｉ＾－在浓度比核黄素大１０～１００倍以上才有影响。建立了核黄素的磷光分析法，用于制剂分析及血浆中核黄素的测定，方法简单快速。     

色氨酸荧光猝灭法测定人发稀土总量

研究了稀土元素对色氨酸的荧光猝灭效应，结果发现，在pH=11的HAc-H3BO3-H3PO4-NaOH缓冲溶液中，。各种稀土元素对色氨酸的荧光有猝灭效应，在此基础上建立了色氨酸荧光猝灭法测定稀土总量的分析新方法。稀土总量在0－50ug/25mL范围内，色氨酸荧光强度的差值与稀土总量呈现良好的线性关系，方法检出限为0．23ug/L；相对标准偏差为1．1％－2．9％；样品加标回收率为98．9％－101．2％，方法简便，灵敏度高，已用于人发样品中稀土总量测定。     

非离子表面活性剂Tween-20胶束体系流体室温燐光法测定色氨酸

提出了一种以非离子表面活性剂Tween 2 0为胶束介质、I-作重原子微扰剂、Na2 SO3 为除氧剂的胶束增稳室温光测定色氨酸的方法。详细研究了各种实验条件的影响。线性范围 8.0× 1 0 -8～ 8.0× 1 0 -6mol L ,检出限达 1 .4×1 0 -9mol L。直接用于大米、花生、大豆及竹笋中色氨酸的测定 ,相对标准偏差2 4%～ 3.3% ,与荧光法比较 ,相对误差 - 3.1 %～ 4.2 %。     

苯胲电解液的高效液相色谱分析

利用高效液相色谱，采用以苯甲酸为内标，分析了苯胲电解液中的对氨基苯酚、苯胺、苯胲及硝基苯的含量。紫外检测器检测波长为254nm，色谱柱为μ-Bondapak C18柱，采用0．05mol/L磷酸二氢钾缓冲液(pH3．5) 甲醇(70 30)为流动相，其流速为1．0mL/min，柱温为室温，对样品进行分析。求出待测组分对氨基苯酚，苯胺，苯胲及硝基苯的回归方程分别为，y=12．75x 0．60，y=2．84x-1．38,y=10．14x 4．33，y=37．46x 3．71，其相应的相关系数依次为0．9995，0．9992，0．9980，0．9981。上述待测组分对内标的相对校正因子分别为2．416，2．176，0．5453，0．1624。     

单次碰撞条件下Ar(3P0.2)与SO2,SOCl2的传能反应

利用化学发光方法研究了Ar（3P0,2）与SO2，SOCl2在单次碰撞条件下SO（A）的形成动力学，通过对实验光谱进行曲线拟会，得到了SO（A，υ＇）的初生态布居．分别是N0：N1：N2：N3：N4：N5：N6＝1．00：0．67：0．57：0．55：0．50：0．35：0．30和1．00：0．69：0．61：0．53：0．40：0．34：0．26．利用参考反应法求算了SO（A）的形成速率，分别为：4．55×10－12cm3•molecule－1•s－1和2．87×10－12cm3•molecule－1•s－1，与总猝灭速率相比较，发现解离激发为反应的次要出口通道．通过惊奇度分析，对激发解离机理进行了讨论．     

硫胺的燐光研究

硫胺无燐光，在碱中氧化后才产生燐光。 λ激发＝３００ｎｍ，λ发射＝４１０ ｎｍ，燐光寿命为１．３ｓ．硫胺燐光受溶剂极性影响甚小，１５种金属离子中只有铜离子可增强流胺燐光，寿命变短为 ０． ９４ ｓ，但不影响燐光光谱。在开始３０ｍｉｎ内有ＣｕＳＯ４的作用较快，以后逐渐变慢，到 ４ｈ后达平衡与不用ＣｕＳＯ４的燐光相近，启示ＣｕＳＯ４具有催化硫胺的氧化作用，建立了硫胺的燐光分析方法，用于两种维生素Ｂ１片的分析，分别为９８．５％与９８％。     

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。