甲基苯基苄基膦的拆分

本文报道了用Ｒ－μ－二氯－二（Ｎ，Ｎ－二甲基－α－萘乙胺）合二钯（Ⅱ）为拆分试剂，拆分标题化合物的过程和结果。Ｓ－甲基苯基苄基膦的［α］２５Ｄ＝＋１１０．３°（Ｃ＝２．８２％，Ｃ６Ｈ５ＣＨ３），比文献报道值为高。并用３１ＰＮＭＲ信号对拆分纯度进行了讨论     

Mo（W）－Cu（Ag）－S原子簇化合物的研究现状

本文在研究Ｍｏ（Ｗ）－Ｃｕ（Ａｇ）－Ｓ原子簇化合物的低热固态合成化学基础上，详细地对该类簇合物进行了归纳，从中提出：１．（Ｍ＝Ｍｏ，Ｗ；ｎ＝２，３，４）作为配体中心．２．氧原子在簇合物中仅作为端基，不参与同其他金属成键．３．单个ＭＳ４（Ｍ＝Ｍｏ，Ｗ）基团最多只能键合六个Ｃｕ（Ａｇ）原子，即最大核数为七．４．迄今为止所有Ｍｏ（Ｗ）－Ｃｕ－Ｓ原子簇化合物中Ｃｕ均为＋１价．５．预计合低价态Ｍｏ（Ｗ）的这类簇合物将会有很大进展．     

3,3—二甲基—9—（5,5—二甲基—3—羟基—2—环己烯—1—酮—2—基）—1—氧代—2 …

标题化合物Ｃ２３Ｈ２６Ｏ４是水杨醛与５，６－二甲基－１，３－环己二酮在Ｎ，Ｎ－二甲基甲酰胺中反应而得。结果通过单晶Ｘ－射线衍射法确定，其晶体属于单斜晶系，空间群Ｐ２１／ｃ，ａ＝７．０５６，ｂ＝２０．２６３，ｃ＝１３．６６５Ａ，β＝９３．３２，Ｖ＝１９５０．７Ａ＾３，Ｍｒ＝３６６．４６，Ｄｃ＝１．２４８ｇ／ｃｍ＾３，Ｚ＝４，μ（ＭＯＫα）＝０．８４ｃｍ＾－１，Ｆ（０００）＝７８４。晶体结构用直接法解     

正电荷聚合物动态涂敷毛细管电泳柱对碱性蛋白的分离

以１，５－二甲基－二杂氮十一烷亚甲基聚Ｎ－甲溴化物（ＨＤＢ）为添加剂对毛细管柱进行动态修饰，对４种碱性蛋白质进行分离。实验结果表明：ＨＤＢ可使电渗流（ＥＯＦ）反转，很好地抑制了碱性蛋白质在石英毛细管壁上的吸附。ＨＤＢ浓度（Ｗ／Ｖ）为０．０１２％，ｐＨ４．０～８．０之间时平均柱效为１．０ ×１０~５～１．５×１０~５理论塔板数／ｍ。每次运行之间（ｎ＝６），天与天之间（ｎ＝６），迁移时间的相对标准偏差（ＲＳＤ）分别小于１％和４％，表明该动态涂敷方法具有良好的重现性和稳定性。     

端基为烯丙基修饰的树枝状聚醚的合成

以３，５－二烯丙氧基苄溴作起始物，以３，５－二羟基苯甲醇为文化单体，以三－（对羟基苯基）甲烷作核，通过收敛法合成了三代端基分别含六、十二、二十四个烯丙基的三代树枝状聚醚大分子，产物进行了１Ｈ－ＮＭＲ、１３Ｃ－ＮＭＲ、ＭＳ等表征．     

交联键合型聚丙烯酰胺毛细管电泳涂层柱的快速制备及评价

建立了一种简单快速制备交联键合聚丙烯酰胺涂层毛细管电泳柱的方法。在这一方法中,未经处理的毛细管柱直接用含有一定比例的丙烯酰胺、交联剂甲叉基双丙烯酰胺、硅烷化试剂乙烯基三乙氧基硅氧烷以及引发剂偶氮二异丁氰的丙酮溶液进行动态涂渍,再经热处理使单体的交联和聚合物在毛细管壁上的键合反应同时发生。所制柱能够有效地抑制电渗流和蛋白质在毛细管壁上的吸附。碱性蛋白在ｐＨ４．０的缓冲液中分离时,获得的平均分离柱效为     

Mo(W)-Cu(Ag)-S原子簇化合物的研究现状

本文在研究Ｍｏ（Ｗ）－Ｃｕ（Ａｇ）－Ｓ原子簇化合物的低热固态合成化学基础上，详细地对该类簇合物进行了归纳，从中提出；１，ＭＯ４－ｎＳｎ＾２＾－（Ｍ＝Ｍｏ，Ｗ；ｎ＝２，３，４）作为配体中心。２，氧原子在簇合物中仅作为端基，不参与同其他金属成键。３，单个ＭＳ４（Ｍ＝Ｍｏ，Ｗ）基团最多只能键合六个Ｃｕ（Ａｇ）原子，即最大核数为七。４，迄今为止所有Ｍｏ（Ｗ）－Ｃｕ－Ｓ原子簇化合物中Ｃｕ均为＋１价。５，预计     

三烷基膦—铂—氢配合物的合成及NMR研究

合成了配合物ｔｒａｎｓ－ＰｔＨＸＬ２（Ｌ＝ＰＢｕ３，ＰＰｒ３，ＰＥｔ３；Ｘ＝Ｃｌ＾－，Ｂｒ＾－，Ｉ＾－，ＮＯ＾－３，ＮＯ＾－２，ＳＣＮ＾－，ＣＮ＾－），并进行了ＨＮＭＲ研究。测得Ｐｔ－Ｈ键的Ｈ的高场的化学位移δ＝－８～－２４ｐｐｍ；Ｊ＝８００～１５００Ｈｚ和Ｊｐ－Ｈ＝１３．０～１７．０Ｈｚ，鉴定了配合物的顺反异构和键合异构。研究了阴离子配体（Ｘ）及中性配体（Ｌ）对Ｐｔ－Ｈ键的δ的关系，Ｐｔ－Ｈ化学     

meso－5，10，15，20－四（3，4，5－三甲氧基苯基）卟啉的晶体和分子结构

用Ｘ－射线测定了ｍｅｓｏ－５，１０，１５，２０－四（３，４，５－三甲氧基苯基）卟啉的溶剂（正庚烷）合物（ＴＴＯＭＰＰ·２Ｃ＿７Ｈ＿（１６））的晶体结构。实验表明，该化合物（Ｃ＿（７０）Ｈ＿（８６）Ｎ＿４Ｏ＿（１２））的晶体属三斜晶系，空间群Ｐ１，ａ＝８．７４９（６），ｂ＝１５．１２９（６），ｃ＝１６．４４９（３），ａ＝６０．０７（３），β＝７０．６４（４），γ＝８１．７０（５），Ｖ＝１７７９．６，Ｍ＿ｒ＝１１７５．４９，Ｚ＝１，Ｄ＿ｃ＝１．０９７ｇ／ｃｍ￣３，μ＝０．６９７ｃｍ￣（－１），Ｆ（０００）＝６３０。讨论了卟啉环上取代基的电子和立体效应及卟啉与铁（Ⅲ）离子配位后铁（Ⅲ）离于对卟啉结构参数的影响。     

meso－5，10，15，20－四（3，4，5－三甲氧基苯基）卟啉的晶体和分子结构

用Ｘ－射线测定了ｍｅｓｏ－５，１０，１５，２０－四（３，４，５－三甲氧基苯基）卟啉的溶剂（正庚烷）合物（ＴＴＯＭＰＰ·２Ｃ＿７Ｈ＿（１６））的晶体结构。实验表明，该化合物（Ｃ＿（７０）Ｈ＿（８６）Ｎ＿４Ｏ＿（１２））的晶体属三斜晶系，空间群Ｐ１，ａ＝８．７４９（６），ｂ＝１５．１２９（６），ｃ＝１６．４４９（３），ａ＝６０．０７（３），β＝７０．６４（４），γ＝８１．７０（５），Ｖ＝１７７９．６，Ｍ＿ｒ＝１１７５．４９，Ｚ＝１，Ｄ＿ｃ＝１．０９７ｇ／ｃｍ￣３，μ＝０．６９７ｃｍ￣（－１），Ｆ（０００）＝６３０。讨论了卟啉环上取代基的电子和立体效应及卟啉与铁（Ⅲ）离子配位后铁（Ⅲ）离于对卟啉结构参数的影响。     

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.     

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.     

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.     

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.

     

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)。     

Stages of thermal decomposition of sodium oxo-salts of sulphur

Thermal behaviour of sodium oxo-salts of sulphur: Na₂SO₄, Na₂S₂O₇, Na₂S₂O₆, Na₂SO₃, Na₂S₂O₅, Na₂S₂O₄, Na₂S₂O₃, Na₂S₃O₆ and of sulphides Na₂S and Na₂S₂ was studied on heating up to 1000°C. The experiments were performed with anhydrous compounds obtained from commercial products by recrystallisation and dehydration. The stage mechanisms of decomposition of anionic sub-lattices of the salts have been proposed basing on the Górski’s morphological classification of simple species. The thermal stability and the stage decomposition mechanisms were correlated with the structure and the potential chemical properties of the salt anions. The thermal decomposition processes were studied by means of thermal analysis, and the decomposition products were identified by means of X-ray phase analysis.     

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.