丁基罗丹明B-铜钨杂多酸光度法测定微量铜

在聚乙烯醇（ＰＶＡ）存在下，丁基罗丹明Ｂ（ＢＲＢ）与铜钨杂多酸形成离子缔合物。缔合物的形成条件为ｃＨ２ＳＯ４＝１．２ｍｏｌ／Ｌ，ｃＷＯ２－４＝６．１×１０－５ｍｏｌ／Ｌ，ｃＢＲＢ＝３．８×１０－５ｍｏｌ／Ｌ和ＰＶＡ０．０８％。缔合物的最大吸收波长位于５７０ｎｍ，摩尔吸光系数ε＝１．６６×１０６Ｌ·ｍｏｌ－１·ｃｍ－１，铜量在每２５ｍＬ０～０．５μｇ范围内服从比耳定律，检测限为每ｍＬ０．６５ｎｇ（ｎ＝１２），对每ｍＬ１８ｎｇＣｕ测定的ＲＳＤ为０．８５％（ｎ＝１０）。缔合物至少稳定１５０ｈ，其摩尔比为Ｃｕ∶Ｗ∶ＢＲＢ＝１∶１２∶５，红外图谱表明铜钨杂多酸具有Ｋｅｇｇｉｎ结构。考察了４０多种共存离子的影响，大多数常见元素不干扰。本法已用于天然水、自来水、降水、人发、中药和蔬菜中铜的测定，结果满意。     

丁基罗丹明B—钼酸盐光度法连续测定铈和钪

在聚乙烯醇（ＰＶＡ）存在下，丁基罗丹明Ｂ（ＢＲＢ）分别与铈钼、钪钼杂多酸络阴离子形成离子缔合物，其最大吸收均位于５７０ｎｍ，表面摩尔吸光度分别为εＣｅ＝３．９６×１０＾６Ｌ．ｍｏｌ＾－１．ｃｍ＾－１，εＳｃ＝４．７１×１０＾５Ｌ．ｍｏｌ＾－１．ｃｍ＾－１，服从比耳定律范围分别为０－２４μｇ／Ｌ Ｃｅ和０－６０μｇ／ＬＳｃ，测定极限为Ｃｅ１．０μｇ／Ｌ（ｎ＝１２）和Ｓｃ１．９μｇ／Ｌ（ｎ＝１０），对     

用钼酸盐和罗丹明B连续光度法测定铈和钪

聚乙烯醇存在下，铈或钪钼杂多酸与罗丹明Ｂ（ＲＢ）形成离子缔合物，最大吸收均位于５７０ｎｍ，摩尔吸光系数分别为１．１６×１０＾６和５．６２×１０＾５Ｌ．ｍｏｌ＾－１．ｃｍ＾－１，ｃｍ＾－１，０－１．２μｇ／２５ｍＬＣｅ和０－２．０μｇ／ｍＬＳｃ服从比耳定律，检测限１．５ｎｇ／ｍＬＣｅ（ｎ＝１０）和１．１ｎｇ／ｍＬＳｃ（ｎ＝９）。缔合物的摩尔比为Ｃｅ：ｍＯ：ＲＢ＝１：６：３和 Ｓｃ：Ｍｏ：ＲＢ＝１：１     

铑（Ⅲ）—钼酸盐—罗丹明B显色体系的研究和应用

在聚乙烯醇（ＰＶＡ）存在下，铑（Ⅲ）与钼酸盐和罗丹明Ｂ（ＲＢ）形成离子缔合物，缔合物的最大吸收位于５８０ｎｍ，摩尔吸光系数ε值１．６８×１０＾５Ｌ·ｍｏｌ＾－１·ｃｍ＾－１，服从比耳定律范围０￣１０μｇ Ｒｈ／２５ｍＬ，方法用于催化剂和冶金产品中铑的测定，结果满意。     

钍钼杂多酸-丁基罗丹明B测定岩矿中痕量钍

本文报道了一个灵敏度高、选择性好的测定痕量钍的新光度分析法。在聚乙烯醇（ＰＶＡ）存在下，钍钼杂多酸和丁基罗丹明Ｂ（ＢＲＢ）形成离子缔合物，其适宜条件为ｃＨＣｌＯ４＝１．３ｍｏｌ／Ｌ，ｃＭｏＯ４２－＝６．８×１０－４ｍｏｌ／Ｌ，ｃＢＲＢ＝２．７×１０－５ｍｏｌ／Ｌ，ＰＶＡ０．０８％。络合物的最大吸收波长为５７０ｎｍ，服从比耳定律范围０～０．８ｍｇ／２５ＬＴｈ，表观摩尔吸光度ε为３．６３×１０６Ｌ·ｍｏｌ－１·ｃｍ－１，测定极限１．８μｇ／Ｌ（ｎ＝１２），对０．０２ｍｇ／ＬＴｈ分析１１次的相对标准偏差为２．９％，络合物的摩尔组成Ｔｈ∶Ｍｏ∶ＢＲＢ＝１∶１２∶７。大多数常见元素、１００倍Ｃｅ（Ⅲ）、４０倍Ｕ（Ⅵ）和２０倍Ｐ（Ⅴ）不干扰钍的测定。本法已用于地质标样中钍的测定，结果满意。     

聚乙烯醇存在下钼酸盐和罗丹明B光度法测定钪

在聚乙烯醇存在下，钪相杂多酸和罗丹明Ｂ（ＲＢ）形成离子缔合物，其最大吸收位于５７０ｎｍ，表观摩尔吸光系数ε值为５．６２×１０＾５Ｌ．ｍｏｌ＾－１．ｃｍ＾－１，服从比耳定律范围０－１．０μｇＳｃ／２５ｍＬ，检出限１．１ｎｇ／ｍＬ（ｎ＝９），考察了５０多种外来离子影响，缔合物的摩尔组成为Ｓｃ：Ｍｏ：ＲＢ＝１：１２：６，方法用于地质样品中钪的分析，结果满意。     

锡钨杂多酸-耐尔蓝光度法测定纳克量锡

本文报道一个光度法测定纳克量锡的新方法。在聚乙烯醇（ＰＶＡ）存在下锡（Ⅳ）与钨酸盐和耐尔蓝（ＮＢ）反应形成离子缔合物,离子缔合物的最大吸收位于５８０ｎｍ,表观摩尔吸光系数ε值２．９５×１０７Ｌ·ｍｏ１－１·ｃｍ－１,服从比耳定律范围０～２．０μｇ／Ｌ,检出限（３σ）０．０８３μｇ／Ｌ（ｎ＝１０）,对２．０μｇ／Ｌ锡测定的ＲＳＤ为１．４２％（ｎ＝１１）,离子缔合物至少稳定７２ｈ。考察了４０多种共存离子的影响,大多数常见元素不干扰。测定锡的适宜条件［Ｈ２ＳＯ４］＝１．２０ｍｏ１／Ｌ,［ＷＯ２－４］＝６．０５×１０－５ｍｏ１／Ｌ,［ＮＢ］＝５．５×１０－５ｍｏ１／Ｌ和ＰＶＡ０．０８％。本法已用于某些合金钢和锌合金中纳克量锡的测定,结果与推荐值吻合,回收率满意。     

用金钨杂多酸和耐尔蓝光度法测定纳克量金

在阿拉伯胶存在下，金与钨酸钠和耐尔蓝（ＮＢ）形成离子缔合物，它的最大吸收位于５８０ｎｍ，表观摩尔吸光系数ε值为２．３８×１０＾７Ｌ·ｍｏｌ＾－１·ｃｍ＾－１，体系至少稳定２４ｈ。金量在０￣４．４μｇ／Ｌ范围内服从比尔定律，检测限（３σ）为０．０６９μｇ／Ｌ（ｎ＝１２），对４．０μｇ／Ｌ Ａｕ（Ⅲ）测定的相对标准偏差为１．９％（ｎ＝１１），离子缔合物的摩尔比为Ａｕ（Ⅲ）：ＮＢ＝１：３。考察了４０多种     

金钨杂多酸-丁基罗丹明B光度法测定痕量金

研究了金钨杂多酸（ＡｕＷ）－丁基罗丹明Ｂ（ＢＲＢ）－聚乙烯醇（ＰＶＡ）体系的显色反应．离子缔合物的最大吸收位于５６５ｎｍ，表现摩尔吸光系数ε值为２．９６×１０７ｄｍ３·ｍｏｌ－１·ｃｍ－１，金量在０～２．８μｇ／Ｌ范围内服从比耳定律，检出限为０．１２μｇ／Ｌ（ｎ＝１２），对２．４μｇＡｕ（Ⅲ）／Ｌ测定的相对标准偏差为１．９％（ｎ＝１１）．离子缔合物至少稳定２４０ｈ．研究了离子缔合物的红外光谱，考察了４０多种共存离子的影响，大多数常见离子不干扰，允许２００倍量Ｐｔ（ＩＶ）、４００倍量Ｐｄ（Ⅱ）存在．本法用于某些矿物和炭粉中金的测定，结果与ＡＡＳ法吻合     

2－（3，5－二氯－2－吡啶偶氮）－5－二甲氨基苯胺与铂（Ⅳ）显色反应的研究

研究了２－（３，５－二氯－２－吡啶偶氮）－５－二甲氨基苯胺与铂（Ⅳ）的显色反应，在ｐＨ３．５～６．０醋酸－醋酸钠介质中，沸水浴加热２５ｍｉｎ，试剂与铂（Ⅳ）形成１：４的紫色配合物，再提高酸度至２．９～４．０ｍｏｌ／Ｌ盐酸溶液，其最大吸收峰红移至６３０ｎｍ，灵敏度显著提高，表现摩尔吸光系数ε＿（６００）＝７．０×１０￣４Ｌ·ｍｏｌ￣（－１）·ｃｍ￣（－１），铂含量在０～３２μｇ／２５ｍＬ范围内符合比耳定律。大多数常见金属离子不干扰测定，所拟方法操作简便，用于催化剂中微量铂的测定，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。