苯酚氧化羰化合成碳酸二苯酯的新型PdCl2-Co(Pyca)2催化体系

研究了新型的Ｐｄ－Ｃｏ催化体系催化氧化碳化苯酚合成碳酸二苯酯。当ｎ（ＰｄＣｌ２）：ｎ「Ｃｏ（Ⅱ）」：ｎ（四丁基化铵）：ｎ（苯醌）＝１：１：１０：２５,Ｔ＝１２０,Ｐ＝２．５ＭＰａ（Ｐｃｏ／Ｐｏ２＝４：１）,反应时间８ｈ,ＰｄＣｌ２－Ｃｏ（Ｐｙｃａ）２比ＰｄＣｌ２－Ｃｏ（ＯＡｃ）２的催化活性高。当使用ＰｄＣｌ２－Ｃｏ（Ｐｙｃａ）２催化剂时,ＤＰＣ的产率为６．０３％。最佳的反应温度是１２０℃,ＤＰＣ的产率随着体系的总压增加而增大,当压力升到３．５ＭＰａ时,ＤＰＣ产率为８．５３％。     

催化－萃取光度法研究Ⅱ．H_2O_2－Co（Ⅱ）－phen－DPC／CHCl_3体系测定钴

催化－萃取光度法研究Ⅱ．Ｈ_２Ｏ_２－Ｃｏ（Ⅱ）－ｐｈｅｎ－ＤＰＣ／ＣＨＣｌ_３体系测定钴孙登明，吴峰（淮北煤炭师范学院化学系，２３５０００）动力学分析法测定钴已有报道［１～３］。但把动力学指示反应和显色反应相结合，建立催化－萃取光度法测定钴还未见报道?..     

联氨在d—过渡金属配合物的MTP（о—NO2）TBP修饰石墨电…

研究了Ｎ２Ｈ４在间－四（邻－硝基苯基）四苯并卟啉铁（Ⅲ）、钴（Ⅱ）、锌（Ⅱ）和镍（Ⅱ）配合物［ＭＴＰ（о－ＮＯ２）ＴＢＰ，简称ＭＴＢＰ］修饰石墨电极上的催化电氧化反应，测得该系列金属四苯并卟啉的催化活性的顺序为Ｃｏ（Ⅱ）ＴＢＰ＞ＣｌＦｅ（Ⅲ）ＴＢＰ＞Ｎｉ（Ⅱ）ＴＢＰ＞Ｚｎ（Ⅱ）ＴＢＰ≈石墨，考察了Ｃｏ（Ⅱ）ＴＢＰ和ＣｌＦｅ（Ⅲ）ＴＢＰ催化联氨电氧化反应的动力学过程。结果表明，ＯＨ＾－和Ｎ２Ｈ４在Ｃ     

催化动力学光度法测定痕量钴的研究

本文提出了钴（Ⅱ）催化Ｈ２Ｏ２氧化茜素红Ｓ褪色反应体系的新催化光度法。本方法灵敏度高，选择性好，精密度高（测２μｇＣｏ（Ⅱ）６次，ＲＳＤ＝１．４３％）适用于水样中痕量钴（Ⅱ）的测定。     

邻联甲苯胺-过氧化氢催化光度法测定钴

１引言 在碱性介质中,痕量Ｃｏ（Ⅱ）见对Ｈ２Ｑ２氧化邻联甲苯胺（ｏ－Ｔｏｌｉｄｉｎｅ）的显色反应具有强烈的催化作用,探讨了利用该反应进行痕量Ｃｏ（Ⅱ）测定的影响因素,建立了测定痕量Ｃｏ（Ⅱ）的催化动力学光度法,该方法的灵敏度为１．７８ × １０－６ｇ／Ｌ,测定的线性范围为０．８～３．６ μｇ／Ｌ Ｃｏ２＋,应用于维生素Ｂ１２中痕量Ｃｏ（Ⅱ）的测定,结果满意。２实验部分２．１仪器与试剂 ７２１－１００型分光光度计;电热恒温水浴槽;Ｎｉｃｏｌｅｔ ＦＴ－ＩＲ ５ＤＸ红外光谱仪。钴（Ⅱ）标准溶液：１ｍｇ／Ｌ;…     

钴铬复合氧化物超细微粒的制备,结构及其催化性能

钴铬复合氧化物超细微粒的制备、结构及其催化性能刘常坤，申永存，奚强（武汉化工学院精细化工系武汉４３００７３）关键词钴铬复合氧化物，超细微粒，催化剂，制备，结构，催化氧化，三甲苯酚，三甲苯醌２，３，６－三甲苯酚（ＴＭＰ）的氧化产物之一２，３，６－三甲苯...     

四苯基卟啉钴催化有机化合物与二氧化碳的电羧化反应Ⅱ.

研究了α、β、γ、δ－四苯基卟啉钴（ＣｏＴＰＰ）存在下苄基氯、苯乙酮、二苯甲酮和萘等与ＣＯ＿２的电羧化反应，与无催化剂体系相比，ＣｏＴＰＰ可使这些有机化合物与ＣＯ＿２电羧化反应的过电位降低约８００～１０００ｍＶ，对反应有较高的催化活性．用ＵＶ，ＩＲ和ＧＣ－ＭＳ确认了电羧化产物，并探讨了ＣｏＴＰＰ催化反应机理．     

o／o型单核铁（Ⅲ）卟啉二聚体模拟细胞色素P450酶催化环已烷羟化？…

合成和表征了一系列以柔韧烷氧链相连的ｏ／ｏ型单核铁卟啉二聚体,利用Ｘ－光电子能谱（ＸＰＳ）研究了卟啉二聚体中由自由卟啉环向铁卟啉环发生的分子内电子转移,考察３了在以分子氧为氧源还原剂存在的温和条件下,该类配合物模拟细胞色素Ｐ４５０酶对环已烷羟化反应的催化性能。结果表明,该系列ｏ／ｏ莳的卟啉二聚体的催化性能明显优于相应的铁卟啉单体ＦｅＴＰＰＣｌ。随着烷氧链的增长,催化活性次序为：Ｃ２〉Ｃ４〉Ｃ６〉Ｃ     

四—[邻（叔丁氧羰甘氨酸）氨基苯基]卟啉锌配合物的合成 …

合成并表征了四－「邻（叔丁氨酸）氨基苯基」卟啉Ｈ２Ｔ（ｏ－ＢｏｃＧｌｙ）ＡＰＰ（１）及其锌（Ⅱ）配合物ＺｎＴ（ｏ－ＢｏｃＧｌｙ）ＡＰＰ（２）,用紫外－可光谱测定滴定法测定了配合物２与６种咪唑配体轴向配位反应的平衡常数,研究了它作为主体分子对咪唑类小分子的识别,研究结果表明,各配体的缔合常数按Ｋ（Ｉｍ）〉Ｋ（２－ＣＨ３Ｉｍ）〉Ｋ（ＫＭＩｍ）〉Ｋ（Ｎ－ＣＨ３Ｉｍ）〉Ｋ（２－ＨＯＣＨ２Ｉｍ）〉Ｋ（ＧＭＡ     

杂多酸固载催化剂催化氧化合成2,3,5—三甲基苯醌

探索了固载磷－钼－钒杂多酸Ｈ３＋ｎＰＭｏ１２－ｎＯ４ｏ（ＨＰＡ－ｎ，ｎ＝１～３）催化氧化２，３，６－三甲基苯酚合成２，３，５－三甲基苯醌的工艺过程，考察了杂多酸、载体以及搅拌速度对催化氧化反应的影响。     

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.     

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.     

恶臭嗅辨实验室建设探讨

针对恶臭测试的环境影响问题,提出了解决的实例方案,并对方案的要点及优缺点进行讨论,此方案在实际操作中具有较好的效果。     

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^-。     

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.     

解决能源问题的新途径——光解水制氢的研究

面对日益枯竭的能源危机,氢能是一种洁净、最有前景的替代能源。目前在各种制氢的方法中光催化分解水制氢的研究最多,光解水过程中催化剂最关键,本文对利用太阳能光解水的途径、提高光催化反应效率以及光催化剂的开发研究进行了综述。