新显色剂2－（5－硝基－2－吡啶偶氮）－5－二甲氨基苯胺与钯显色反应的研究及其应用

用新合成的偶氮试剂２－（５－硝基－２－吡啶偶氮）－５－二甲氨基苯胺（５－ＮＯ＿２－ＰＡＤＭＡ）研究了光度法测定他的反应条件。结果表明，在０．４５～１．２ｍｏｌ／Ｌ盐酸介质中，钯与试剂形成稳定的蓝色配合物，其最大吸收波长位于６２１ｎｍ处，表观摩尔吸收系数为９．４×１０￣４Ｌ·ｍｏｌ￣（－１）·ｃｍ￣（－１），配合成的组成为Ｐｄ：５－ＮＯ＿２－ＰＡＤＭＡ＝１：２，钯浓度在０～１０μｇ／１０ｍＬ范围内符合比尔定律。本方法是目前测定钯的高灵敏度和高选择性体系之一。用于含钯分子筛及二次合金管理样－８８中微量钯的测定，结果满意。     

SLS存在下meso 四(对三甲胺基苯基)卟啉测定微量铜

研究了表面活性剂十二烷基苯磺酸钠（ＳＬＳ） 存在时,ｍｅｓｏ 四（ 对三甲胺基苯基） 卟啉［Ｔ（４ ＴＭＡＰ）Ｐ］ 与铜的显色反应。在ｐＨ＝ ３ ．７ 的ＨＡｃ ＮａＡｃ 介质中,在ＳＬＳ存在下,铜与［Ｔ（４ ＴＭＡＰ）Ｐ］ 形成１∶２ 的稳定配合物,至少在４ ．５ｈ 内吸光度无变化。最大吸收波长位于４１０ｎｍ ,ε＝ ３ ．７９ ×１０５Ｌ·ｍｏｌ－ １·ｃｍ － １ 。铜在０ ～１ ．４０μｇ／２５ｍＬ内有良好线性关系。用于自来水及湖水中铜的测定,相对标准偏差小于３ ％ ,加标回收率在９８ ％ ～１０３％ 之间     

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。     

SLS存在下meso-四(对三甲胺基苯基)卟啉测定微量铜

研究了表面活性剂十二烷基苯磺酸钠存在时,ｍｅｓｏ－四（对三甲基苯基）卟啉「Ｔ（４－ＴＭＡＰ）Ｐ」与铜的显色反应。在ｐＨ＝３．７的ＨＡｃ－ＮＡａｃ介质中,在ＳＬＳ眄,铜与「Ｔ（４－ＴＭＡＰ）Ｐ」形成１：２的稳定配合物,至少在４．５ｈ内吸光度无变化。最大吸收波长位于４１０ｎｍ,ε＝３．７９×１０＾５Ｌ．ｍｏｌ＾０－１．ｃｍ＾－１。     

13，15－苯并－1，4，8，11－四硫杂环十六烷及其钯（Ⅱ）络合物的合成和结构测定

报导了硫冠醚１３，１５－苯并－１，４，８，１１－四硫杂环十六烷（ＴＴｍＸ）及其钯（Ⅱ）络合物（ＴＴｍＸ·２ＰｄＣ＿ｌ２）的合成，并通过Ｘ射线衍射分析测定了该配体及其络合物的晶体结构。ＴＴｍＸ属单斜晶系，Ｐ＿２＿１／ｎ空间群，晶胞参数：ａ＝９．５４５（３），ｂ＝９．０６５（１），ｃ＝１９．６４５（３）Ａ，β＝９５．３８（１）°，Ｖ＝１６９２．３（５）Ａ￣３，Ｚ＝４，μ＝５．２６ｃｍ￣（－１），Ｄｃ＝１．３０ｇ·ｃｍ￣（－３）。ＴＴｍＸ·２ＰｄＣｌ＿２属正文晶系，Ｐｂｃａ空间群，晶胞参数：ａ＝１１．３９２（２），ｂ＝１４．５８０（４），ｃ＝２７．１４６（９）Ａ，β＝９０．００（０）°，Ｖ＝４５０９（２）Ａ￣３，Ｚ＝８，μ＝２４．１２ｃｍ￣（－１），Ｄｃ＝２．０２ｇ·ｃｍ￣（－３）。     

镧系离子与5,7-二氯-8-羟基喹啉-藏红花三元离子缔合物的萃取-光度分析特性

以Ｓｍ３＋为例研究了Ｌｎ３＋５，７二氯８羟基喹啉（ＤＣＯ）藏红花（ＳＦＴ）形成三元离子缔合物的萃取光度特征。用平衡移动法测定了离子缔合物的摩尔比Ｌｎ３＋∶ＤＣＯ∶ＳＦＴ＝１∶４∶１。在ｐＨ６８０～７５０的范围内，萃取物的λｍａｘ＝５２４ｎｍ，εｍａｘ＝４７０×１０４Ｌ·ｍｏｌ－１·ｃｍ－１。Ｓｍ３＋在０２～１５μｇ·ｍｌ－１范围内符合比尔定律。研究表明镧系离子的相对吸光度（ＡＬｎ／ＡＬａ）随原子序数呈现奇偶变化规律。     

Fe（Ⅲ）－TEA－5－Br－PADAP－H_2O_2体系中催化波的研究及其应

在０．２ｍｏｌ·Ｌ￣（－１）ＮＨ＿４Ｃｌ－ＮＨ＿３·Ｈ＿２Ｏ底液中，（ｐＨ为９．２６），得到一个极为灵敏的Ｆｅ（Ⅲ）－ＴＥＡ－５－Ｂｒ－ＰＡＤＡＰ－Ｈ＿２Ｏ＿２配合吸附催化波，其峰电位为－０．７１Ｖ（ｖｓ．ＳＣＥ）。铁浓度在１．８×１０￣（－１０）～５．４×１０￣（－６）ｍｏｌ·Ｌ￣（－１）范围内与二阶导数波高呈线性关系。对该极谱波的性质进行了研究，证明是一种配合吸附催化波，并成功地应用于各类水样，钒催化剂中微量或痕量铁的测定。     

1,9-二(4-安替比林偶氮)嘌呤酮与钯的显色反应及其用于光度法测定钯

１引言 新合成的试剂１,９－二［４－安替比林偶氮］嘌呤酮（ＢＡＰＤ）,在ｐＨ＝４．５０．的ＨＡｃ－ＮａＡｃ缓冲溶液中与Ｐｄ（Ⅱ）生成稳定的红色络合物,其λｍａｘ＝ ５１０ ｎｍ,把含量在０． １２～２．４ ｍｇ／Ｌ范围内与吸光度呈线性关系。据此建立了测定Ｐｄ（Ⅱ）的分析方法,并应用于电镀液和镀层中钯含量的测定。２实验部分２．１仪器与试剂 ＤＵ－７ ＨＳ型分光光度计（美国 Ｂｅｃｋｍａｎ公司）;７６０ ＣＲＴ型紫外－可见光分光光度计（上海第三分析仪器厂）;ＨＭ－２０Ｅ型酸度计（日本ＴＯＡ公司）。钯标准溶液…     

新显色剂3,3′-二甲基联苯重氮氨基偶氮苯与钯显色反应的研究及其应用

研究了在表面活性剂Ｎ－氯代十六烷基吡啶（ＣＰＣ）存在下，新显色剂３，３′－二甲基联苯重氮氨基偶氮苯（ＤＭＤＰＤＡＡ）与钯（Ⅱ）显色反应的适宜条件。结果表明，在ｐＨ８．０～９．０范围内，钯（Ⅱ）与ＤＭＤＰＤＡＡ形成２∶２紫红色配合物，其最大吸收波长位于６００ｎｍ，配合物的表观摩尔吸光系数为８．４１×１０４Ｌ·ｍｏｌ－１·ｃｍ－１，钯浓度在０～１２μｇ／２５ｍＬ范围内遵守比尔定律，该方法灵敏度较高，选择性较好，用于含钯催化剂中微量钯的测定。     

Mo（Ⅵ）－PAN与Mo（Ⅵ）－PAR体系的极谱性质对比研究

本文比较了Ｍｏ（Ⅵ）－１－（２－吡啶基偶氮）－２－萘酚（ＰＡＮ）与Ｍｏ（Ⅵ）－４（２－吡啶基偶氮）间苯二酚（ＰＡＲ）的极谱性质，讨论它们在作为吸附波试剂时的优缺点，以求得在选择络合剂时的感性和理性认识．本文还报道了Ｍｏ（Ⅵ）－ＰＡＮ－ＫＢｒＯ３吸附催化波体系，最佳实验条件，０．１ｍｏｌ／ＬＨＡｃ－－ＮａＡｃ，ｐＨ＝４．６，０．０１ｍｏｌ／ＬＫＢｒＯ３，２．５×１０－５ｍｏｌ／ＬＰＡＮ．峰电位为－０．７１Ｖ（ｖｓ．ＳＣＥ），检出限１×１０－９ｍｏｌ／Ｌ，线性范围０～６×１０－７ｍｏｌ／Ｌ     

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。     

Acid hydrolysis of carboxymethylcellulose of low degree of substitution

Cotton cellulose was swollen in a sodium hydroxide solution and carboxymethylated by a two-bath method for different periods of time for each process. The kinetics of acid hydrolysis and the crystallinity of the swollen and carboxymethylated samples were measured. The proportion of broken bonds, rate constants for hydrolysis, and permeability of cellulose to hydrolyzing agents were calculated. The susceptibility of glycosidic linkages to acid hydrolysis was improved by carboxymethylation more than by swelling in alkali. The increased accessibility of carboxymethylcellulose to acid was regarded as a consequence of increased intra-and intercrystalline swelling and of the glycosidic bonds' weakness caused by the electron-attracting carboxymethyl group on the C-6 position.     

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^-。     

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.     

Estimation of Kinetic Parameters of Thermal Oxidation of Ilmenite

The aim of the presented work was the investigation of thermal oxidation of ilmenite in static air atmosphere. The investigations were carried out by use of a derivatograph (MOM, Hungary). The changes of crystallographic structure of investigated samples were identified by X-ray diffractometry on Philips PW-1710 diffractometer. In temperature above 500°C appears structure of hematite Fe₂O₃. On the basis of the thermogravimetric measurements, the contracting area and contracting volume models were found as the best fitting experimental data. This revised version was published online in August 2006 with corrections to the Cover Date.     

Mechanism of action of base-catalyzed oxygenation of phenol derivatives

Cyclopropyl derivative of 2,6-di-tert-butylphenol is synthesized as a probe to investigate the mechanism of base-catalyzed autooxidation of phenol derivatives. Our study indicates that one electron reduction of molecular oxygen from phenolate gives phenoxyl radical 3, a key intermediate of autooxidation. The coupling of phenoxyl radical and superoxide radical gives peroxylate anion 4 and produces the final epoxy alcohol adduct 6.     

化学计量中不确定度评定研究进展

测量不确定度是表征合理地赋予被测量之值的分散性的参数。本文针对化学计量不确定度评定基础模型仅适用于线性模型、概率分布为正态分布或缩放位移t分布等局限,介绍了近年来不确定度评定的研究热点:蒙特卡罗方法(Monte Carlo Method,MCM),不确定度评定的来源、评定概念、评估方法及其发展过程,扩大了测量不确定度评定与表示的适用范围。     

微量钙的测定方法研究进展

介绍了1995-2006年期间测定微量和痕量钙的方法,如电感耦合等离子体-原子发射光谱法、原子吸收光谱法以及离子色谱法等的工作原理和特点,并说明了其测定微量钙的应用领域。并对微量钙的测定技术进行了展望(引用文献55篇)。