显色剂N—间甲苯基—N‘—（氨基对苯磺酸钠）硫脲光度法测定向量铂（Ⅳ）

研究了新试剂－Ｎ间甲苯基－Ｎ’－（氨甘对苯磺酸钠）硫脲（ＭＭＰＴ）与铂（Ⅳ）的显色反应，结果表明，在ＰＨ３．７－４．４的ＨＡｃ－ＮａＡｃ缓冲体系中，Ｐｔ（Ⅳ）与ＭＭＰＴ形成１：３的绿色水溶性络合物，最大吸收波长位于７５４．４ｎｍ，表观摩尔吸光系数ε７５４．４＝８．５８＊１０＾４Ｌ．ｍｏｌ＾－．ｃｍ＾－１，铂含量在０－１．２８ｍｇ／Ｌ的范围内服从比尔定律。本法灵敏度高，选择好、操作简便，测定结果准确     

新试剂N-间甲苯基-N′-(氨基对苯磺酸钠)硫脲(MMPT)的合成及其在分析化学中的应用

本文合成新试剂Ｎ－间甲苯基－Ｎ′－（氨基对苯磺酸钠）硫脲（ＭＭＰＴ），经红外、紫外、核磁、元素分析等测试，确定其结构。研究测定了试剂与４０多种离子的反应及其配合物的表观摩尔吸光系数，它可作为Ｃｕ２＋（ｍ＝０．０１５μｇ，ｃ＝０．５μｇ／ｍＬ）、Ａｇ＋（ｍ＝０．１μｇ，ｃ＝３．３μｇ／ｍＬ）的新鉴定试剂和光度法测定Ｐｄ２＋（ε３０９．７＝６．３２×１０４Ｌ·ｍｏｌ－１·ｃｍ－１）、Ｐｔ（Ⅳ）（ε７５４．４＝８．５８×１０４Ｌ·ｍｏｌ－１·ｃｍ－１）等的显色剂，方法灵敏度高、选择性好，用于阳极泥、人发、矿石及催化剂中上述元素的鉴定或测定，均获满意结果。     

5-[2-(4-氯苯酚)偶氮]-若丹宁与铂(Ⅱ)的显色反应研究及应用

研究了新显色剂５－［２－（４－氯苯酚）偶氮］－若丹宁与铂（Ⅱ）的显色反应．在Ｈ２ＳＯ４－Ｈ３ＰＯ４介质中和ＣＴＭＡＢ存在下，试剂与Ｐｔ（Ⅱ）形成有色配合物，λｍａｘ位于４２６ｎｍ，摩尔吸光系数为３．２４×１０５Ｌ·ｍｏｌ－１·ｃｍ－１，Ｐｔ（Ⅱ）量在４．００～１０μｇ／２５ｍＬ符合比耳定律，方法用于铂催化剂中铂的测定，获得较好的结果．     

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（３，５－ｄｉＣｌ－ＰＡＤＭＡ）与铂（Ⅳ）的显色反应及铂配合物的质子化行为。结果表明，在０．０４～０．４８ｍｏｌ／Ｌ的Ｈ２ＳＯ４溶液中，于加热的条件下，试剂可与铂（Ⅳ）形成稳定的１∶２绿蓝色ＰｔＬ２Ｈ２＋２配合物，其最大吸收波长位于６３４ｎｍ，表观摩尔吸光系数为９．７３×１０４Ｌ·ｍｏｌ－１·ｃｍ－１，桑德尔灵敏度为０．００２μｇ·ｃｍ－２。铂配合物的三级质子化常数分别为：ｌｇＫａ１＝３．９１，ｌｇＫａ２＝－２．２１，ｌｇＫａ３＝－３．３７。较大量的常见金属离子及除钯、钌外的其它贵金属离子不干扰测定。利用Ｐｔ，Ｐｄ与试剂反应所需的温度差异，可以用差减法消除微量Ｐｄ的干扰．铂（Ⅳ）浓度在每１０ｍＬ０～７．５μｇ范围内符合比尔定律。所拟方法用于二次合金管理样－８８及催化剂中微量铂的测定，结果满意。     

2—（5—溴—2—吡啶偶氮）—5—二甲氨基苯胺与铂（Ⅳ）显色反应及其应用

１引言目前，已有多种杂环偶氮类试剂测定铂的报道，但其在显色灵敏度等方面大多还不理想。本文系统研究了２－（５－溴－２－吡啶偶氮）－５－二甲氨基苯胺（５－Ｂｒ－ＰＡＤＭＡ）与Ｐｔ（Ⅳ）的显色反应，结果表明，在ｐＨ４．０～６．０的酸度范围内，在加热条件下铂（Ⅳ）与试剂形成紫红色络合物。该络合物在１．６ｍｏｌ／Ｌ高氯酸溶液中转变为另一型体绿蓝色络合物，表观摩尔吸光系数ε＝８．３×１０４Ｌ·ｍｏｌ－１·ｃｍ－１，大多数常见金属离子及Ａｕ３＋、Ａｇ＋等贵金属离子在一定范围内对测定无干扰。在ＥＤＴＡ存在下，可…     

1-(4-磺酸基苯基)-3-[4-(苯基偶氮)苯基]-三氮烯与季铵盐型阳离子表面活性剂的显色反应及应用

合成了１－（４－磺酸基苯基）－３－［４－（苯基偶氮）苯基］－三氮烯（ＳＰＡＰＴ）,研究了该试剂在强碱性介质中与季铵盐型阳离子表面活性剂溴化十六烷基吡啶（ＣＰＢ）和溴化十六烷基三甲铵（ＣＴＭＡＢ）的显色反应体系,试剂与表面活性剂形成１∶３的紫红色离子缔合物,其表观摩尔吸光系数分别为１．６７×１０４和１．０６×１０４Ｌ·ｍｏｌ－１·ｃｍ－１。测定了显色体系中ＣＰＢ和ＣＴＭＡＢ的临界胶束浓度（ＣＭＣ）,证明在比尔定律范围内,ＣＰＢ和ＣＴＭＡＢ均以单分子缔合显色。确定了显色体系最佳实验条件     

新显色剂N－辛基－N＇－（氨基对苯磺酸钠）硫脲（OPT）与铜（Ⅱ）显色反应的研究和应用

Ｎ－辛基－Ｎ＇－（氨基对苯磺酸钠）硫脲是新合成的一种显色剂，该试剂极易溶于水而形成无色溶液。在ｐＨ３．６～５．２的ＨＡｃ－ＮａＡｃ缓冲体系中，试剂与铜（Ⅱ）形成一种稳定的蓝色水溶性配合物，其组成比为：Ｃｕ（Ⅱ）：ＯＰＴ＝１：３。配合物的最大吸收波长位于３０１．４ｎｍ，表观摩尔吸光系数ε＿（３０１．４）＝１．８２×１０￣５Ｌ·ｍｏｌ￣（－１）·ｃｍ￣（－１）。Ｃｕ（Ⅱ）在０～１０μｇ／２５ｍＬ服从比尔定律，相关系数ｒ＝０．９９９６，方法的检出限为３．８５×１０￣（－９）ｇ／ｍＬ。本法灵敏度高，选择性好、操作简单，可直接在水相中测定。将本法用于合金钢和生物制品中微量铜的测定，均获得满意结果。     

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     

Zn（ClO_4）_2－DAPTU（MAPTU）－H_2O三元体系30℃时的相平衡研究

测定了三元体系Ｚｎ（ＣｌＯ４）２－Ｌ－Ｈ２Ｏ（Ｌ＝ＤＡＰＴＵ，Ｎ，Ｎ′－二安替比林硫脲；Ｌ＝ＭＡＰＴＵ，Ｎ－甲基－Ｎ′－安替比林硫脲）在３０℃时的溶解度和饱和溶液的折光率，绘制了相应的溶度图和折光率－组成图．体系的溶度曲线和折光率曲线均由３支组成，分别与Ｌ（Ｌ＝ＤＡＰＴＵ，ＭＡＰＴＵ）、Ｚｎ（ＣｌＯ４）２·Ｌ２·ｎＨ２Ｏ（Ｌ＝ＡＰＴＵ．ｎ＝２；Ｌ＝ＭＡＰＴＵ，ｎ＝０）和Ｚｎ（ＣｌＯ４）２·６Ｈ２Ｏ相对应．从溶度图上发现两个未见报道的固液异组成溶解的化合物，经化学分析、元素分析、ＴＧ－ＤＴＡ、ＩＲ表征，结果表明，三元化合物Ｚｎ（ＤＡＰＴＵ）２（ＣｌＯ４）２．２Ｈ２Ｏ中ＤＡＰＴＵ是以两个羧基氧与Ｚｎ２＋离子配位，而在二元化合物Ｚｎ（ＭＡＰＴＵ）２（ＣｌＯ４）２中ＭＡＰＴＵ则以氧和硫原子与Ｚｎ（２＋）离子配位。     

4-(H酸偶氮)-1-苯基-3-甲基吡唑酮光度法测定铝

研究了新试剂４－（Ｈ酸偶氮）－１－苯基－３－甲基吡唑酮（ＨＡＰＭＰ）与铝的显色反应,在ｐＨ４．６的ＨＡｃ－ＮａＡｃ缓冲介质中,ＣＴＭＡＢ存在下,ＨＡＰＭＰ和Ａｌ（Ⅲ）反应生成２∶１红色络合物,λｍａｘ＝５５５ｎｍ,ε＝１．３４×１０５Ｌ·ｍｏｌ－１·ｃｍ－１,铝的含量在０～３．５μｇ／２５ｍＬ内符合比尔定律,方法已用于天然水样中铝的测定。     

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。