层状嵌接式卟啉钴的合成,表征及其对H2O2催化降解研究

采用有机溶剂在层状锑磷酸中在位分步分成了层状嵌接卟啉然材料；用红外光谱、紫外可见光 、Ｘ射线衍射和顺磁共振技术对其进行了表征。该合成材料对Ｈ２Ｏ２降解反应体系的进一步研究表明，卟啉钴嵌接于锑磷层状环境中对Ｈ２Ｏ２具有良好的催化降解活性和抗失活稳定性。     

层状嵌接式酞菁材料对烷烃的非均相氧化催化作用

层状嵌接式酞菁材料对烷烃的非均相氧化催化作用胡希明皮宗新古国榜黄仲涛＋（华南理工大学应用化学系化学工程系＋广州５１０６４１）关键词嵌接式酞菁层状锑磷酸Ｈ２Ｏ２氧化催化酞菁是一种金属离子被吡咯环包围的“镶木工艺品式”平面网络状配位化合物。在结构上它与叶...     

金属酶模拟活性材料的微波诱导合成及性能研究

金属酶模拟活性材料的微波诱导合成及性能研究１）胡希明黄剑刘海洋（华南理工大学应用化学系广州５１０６４１）黄仲涛（华南理工大学化学工程系广州５１０６４１）赖声礼（华南理工大学电子通讯工程系广州５１０６４１）关键词金属卟啉层状锑磷酸微波诱导嵌接合成分类号...     

细胞色素P－450单加氧酶的模拟──轴向配体在锰卟啉／亚碘酰苯催化环己烷加氧反应中的作用

细胞色素Ｐ－４５０单加氧酶的模拟──轴向配体在锰卟啉／亚碘酰苯催化环己烷加氧反应中的作用江淑萍，叶兴凯，吴越（中国科学院长春应用化学研究所，长春１３００２２）关键词环己烷，锰卟啉，轴向配体，氧化，单加氧酶目前，细胞色素Ｐ－４５０单加氧酶的模拟有两个途...     

氧络锰(Ⅳ)卟啉与烯烃反应的研究

单加氧酶细胞色素P-450在生物体中温和条件下活化分子氧,选择性地催化氧化碳氢化合物,其活性中间体可能是氧络铁原卟啉Ix的配合物。锰卟啉配合物也在温和条件下活化分子氧,选择性地催化氧化碳氢化合物,其活性中间体也可能是氧络锰卟啉配合物,是细胞色素P-450的很好的模型体系。目前人们已用一系列的氧化剂,诸如氧化碘苯(PhIO)、NaOCl、KHSO_5、RCOOOH、HCIO_4和HIO_4将三价的锰卟啉氧化为氧络锰卟啉。本实验     

氧化碘苯对甲苯酚锰(Ⅳ)四苯基卟啉络合物的合成

锰卟啉络合物在温和条件下活化分子氧,选择性地催化氧化碳氢化合物,是单加氧酶细胞色素p-450的很好的模型体系。由于已合成的高价锰卟啉络合物很少,所以严重地阻碍其反应机理和活性中间体的研究。Hill等人合成了二种类型的双核的锰(IV)四     

层状嵌接式钴酞菁／NaCIO体系环氧化催化研究

层状嵌接式钴酞菁／ＮａＣＩＯ体系环氧化催化研究胡希明皮宗新谷云骊黄仲涛＊（华南理工大学应用化学系＊化学工程系广州５１０６４１）生物体系的叶绿素和血红蛋白将配位活性中心包覆于蛋白质肽链所构成的空间立体环境中，近年来利用无机材料的刚性，将金属酞菁固载于分...     

金属卟啉催化下环己烷羟基化反应的Hammett关系

合成了４０个卟啉环上具有不同取代基的单铁、锰卟啉和μ－氧桥连双铁、锰卟啉、研究了这些金属卟啉模拟细胞色素Ｐ－４５０单充氧酶在温和条件下催化环己烷羟基化的反应。首次用线性自由能关系对金属卟啉仿生催化反应和金属卟啉自氧人反应进行相关分析，获得一 些新的结果和规律。在此基础上，对金属卟啉仿生催化反应的可能机理进行了探讨。     

金属卟啉催化下环己烷羟基化反应中的Hammett关系

合成了40个卟啉环上具有不同取代基的单铁、锰卟啉和u-氧桥连双铁、锰卟啉,研究了这些金属卟啉模拟细胞色素P－450单充氧酶在温和条件下催化环己烷羟基化的反应.首次用线性自由能关系对金属卟啉仿生催化反应和金属卟啉自氧化反应进行相关分析,获得一些新的结果和规律.在此基础上,对金属卟啉仿生催化反应的可能机理进行了探讨.     

Mn（TMPP）Cl／NaOCl体系对苯乙烯催化环氧化反应的研究

为了实现温和条件下的烯烃环氧化,近年来对模拟单加氧酶细胞色素P—450的催化氧化研究十分活跃。Tabushi,I.,Meunier,B.等人用卤素取代的四苯基卟啉锰/次氯酸钠作为烯烃催化环氧化的模拟体系实现了环辛烯和1一十二碳烯的环氧化,并讨论了轴向配体、配体—卟啉比及溶液PH对催化活性和选择性的影响,但有关这方面的研究报道不多。已有的研究表明:多卤代和多甲基取代的金属卟啉催化效果较为理想,卟啉环上取     

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.     

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.     

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。     

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.     

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.

     

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。     

Investigation of Kinetics of Solid-Phase Synthesis of Lithium Orthosilicate

The kinetics of the interaction between lithium carbonate and silica with various degrees of dispersion was investigated by TG and DTA methods. It was found that the utilization of pyrogenic silica with a specific surface area of about 300 m²g^-1 instead of aerosil with one of 175 m²g^-1 leads to an increase of the reaction rate between lithium carbonate and silica, which depends on the formation and growth of lithium orthosilicate crystals in the first stage, and is conditioned by the diffusion of lithium and oxygen ions through the lithium orthosilicate layer formed at temperatures above 800 K. This supposition is supported by the kinetic analysis results obtained with the use of the different models. The optimal regime of heating is recommended. This revised version was published online in July 2006 with corrections to the Cover Date.     

小环化合物中饱和碳质子化学位移的计算

小环化合物由于其张力、构型、构象和各向异性效应等原因,环碳上质子化学位移缺乏规律性,难以预测,对此作者曾提出一种近似算法。本文根据303种小环化合物中饱和碳质子的化学位移实验数据,将适于计算这类质子化学位移的公式表述为:     

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。