8-羟基喹啉存在下水相(两相)中合成取代水杨酸二茂钛配合物

在8-羟基喹啉存在下,分别采用水相法和两相法简便合成了5种取代水杨酸二茂钛配合物,并用元素分析、IR及 1H NMR等手段对配合物进行了结构表征,发现配合物中均不含8-羟基喹啉配体,而是形成以取代水杨酸为双齿配体的六元杂环化合物.用电子吸收光谱分别对两相反应体系(H2O/CHCl3)的水相和有机相进行了动态监测,发现8-羟基喹啉首先通过两相界面与有机相中的二氯二茂钛形成水溶性的过渡性配合物,然后该过渡性配合物再与有机相中的取代水杨酸作用形成了目标配合物.     

硝基苯2位取代8-羟基喹啉锌配合物的合成及光学性质研究

近年来许多研究表明8-羟基喹啉是一个良好的发光性材料,在8-羟基喹啉环上引入不同的功能团可以调控其相应锌配合物的发光颜色。本文在2位上引入硝基苯基团,设计合成了2-(4-硝基苯-乙烯基)-8-羟基喹啉(1)和2-(3-硝基苯-乙烯基)-8-羟基喹啉(2)及其各自的锌配合物(3)、(4)四个新化合物;利用UV、荧光等分析其结构及研究其反应;紫外光谱显示化合物3和4的λmax分别是340nm和305nm。     

3-[2-(8-羟基喹啉基)-乙烯基]-N-芳基咔唑及其金属配合物的合成和光电性能研究

设计合成了3-[2-(8-羟基喹啉基)-乙烯基]-N-对甲苯基咔唑(8)和3-[2-(8-羟基喹啉基)-乙烯基]-N-对甲氧苯基咔唑(9)及其金属锌配合物(10和11), 用UV-Vis, FTIR, ESI-MS, FAB-MS, ¹H NMR和元素分析确认了化合物的结构. 热重分析实验结果表明, 金属锌配合物(10和11)有很好的热稳定性, 这对真空蒸镀制电致发光器件是有益的. 金属锌配合物组装成有机单层发光器件的结构为ITO/Organ layer(50 nm)/Al(100 nm), 其荧光发射峰分别位于592和583 nm, 为稳定的黄色光. 这两个发光器件的最大亮度分别为489和402 cd/m², 最大电流效率分别为0.41和1.81 cd/A. 电致发光研究表明, 通过化学修饰8-羟基喹啉的2-位取代基可以改变这两个金属锌配合物的电致发光性能.     

2-乙烯基硝基苯-8-羟基喹啉锌配合物的合成及紫外、荧光性质研究

设计合成了3种8-羟基喹啉衍生物配体:(E)-2-[2-(2-硝基苯基)乙烯基]-8-羟基喹啉(4a),(E)-2-[2-(3-硝基苯基)乙烯基]-8-羟基喹啉(4b),(E)-2-[2-(4-硝基苯基)乙烯基]-8-羟基喹啉(4c)及其相应的锌配合物5a～5c,产物经1H NMR,IR,MS和元素分析技术进行了结构表征.通过紫外滴定模拟了金属锌与配体的配位过程,分别测定了它们固态和溶液状态下的荧光性质:光谱显示化合物5a～5c固体荧光光谱的λmax分别是596,625,592 nm,在DMF溶液中的λmax分别是562,536,618 nm.荧光光谱显示硝基位置的改变可以调控8-羟基喹啉锌配合物的发光性质.     

偶氮苯磺酸镍配合物的合成、结构及荧光性质

以镍离子为中心离子,4-[(8-羟基-5-喹啉)偶氮]-苯磺酸(H2L)为配体,通过溶剂热合成反应成功合成配合物Ni2{4-[(8-羟基-5-喹啉)偶氮]-苯磺酸}2(乙二胺)4.通过红外光谱(IR)、元素分析、单晶X-射线衍射(XRD)、粉末X-射线衍射(PXRD)和热重分析(TGA)等方法对其结构进行表征.通过结构分析确定配合物是由2个H2L配体与2个镍离子分别配位形成的离散结构,并且离散结构之间通过多种N—H…O氢键连接形成二维超分子层状结构.荧光测试和理论计算表明,配合物的荧光性能主要来自于配体.     

含三氟苯基8-羟基喹啉锌配合物的合成及紫外、荧光性能对比研究

设计合成了两种含三氟苯基的新型8-羟基喹啉衍生物配体:(E)-2-[2-(2,4,6-三氟苯基)乙烯基]-8-羟基喹啉(B)、(E)-5-[2-(2,4,6-三氟苯基)亚胺基]-8-羟基喹啉(C)及其相应的锌配合物D与E,产物经NMR,IR,MS,元素分析等进行结构表征。通过核磁、紫外滴定跟踪了金属锌与配体的配位过程,并测定了两者溶液状态下的荧光性质:化合物D,E在甲醇溶液中的荧光发射峰位置分别在599 nm和572 nm处;相比于8-羟基喹啉,2位和5位取代8-羟基喹啉衍生物的荧光发生了明显红移。锌配合物固体荧光寿命的测定结果表明,配合物D表现出较长的荧光寿命。     

8-羟基喹啉衍生物铜（Ⅱ）配合物的合成及发光性能

设计合成了（E）-3-[2-（8-羟基喹啉基）-乙烯基]-N-对甲苯基咔唑8和（E）-3-[2-（8-羟基喹啉基）-乙烯基]-N．对甲氧苯基咔唑9及它们相应金属铜配合物10和11四个新的化合物,用UV—Vis,FT—IR,ESI—MS,FAB—MS,^1H NMR,^13C NMR和元素分析确认了化合物的结构．热重分析实验表明金属铜配合物10和11有很好的热稳定性,并把这两个金属铜配合物做成有机单层发光器件,都能发出稳定的蓝绿光．这两个发光器件的最大亮度分别是345cd／m^2,325cd／m^2,最大电流效率分别为0．68cd·A^-1,1．53cd·A^-1．     

含氟8-羟基喹啉锌配合物的合成与发光性能

设计合成了2种含三氟甲基的8-羟基喹啉衍生物配体:(E)-2-[2-(3-三氟甲基苯基)乙烯基]-8-羟基喹啉(3a)、(E)-2-[2-(4-三氟甲基苯基)乙烯基]-8-羟基喹啉(3b)及其相应的锌配合物(4a)、(4b),并由1H NMR、IR、MS、元素分析确认了其结构。通过紫外滴定观察了金属锌与配体的配合过程,测定了它们在DMF溶液中的荧光性质;荧光光谱显示化合物3a、3b在DMF溶液中的λmax分别是491nm和513nm,4a、4b的λmax分别是585nm和599nm,而且改变三氟甲基的位置可以调节配合物的发光性能。     

含8-羟基喹啉铝配合物的高分子聚合物的合成与表征

通过甲基丙烯酸甲酯(MMA)和含有8-羟基喹啉的单体共聚合成模板聚合物,再与二配体的8-羟基喹啉铝配合物(AlQ2)配位,实现了8-羟基喹啉铝配合物的高分子化,获得了一种高分子量金属配合物发光聚合物,并利用元素分析,FTIR,UV,PL光谱,GPC等方法对其结构和性能作了表征．     

8-羟基喹啉镍配合物[Ni2(HQ)3Q3]ClO4的晶体结构

8-羟基喹啉(HQ)是在化学分析中常用的试剂, 它与铝离子形成的配合物(AlQ3)也是目前有机电致发光领域最引人注目的明星分子. 在化学工业中, 8-羟基喹啉是有效的稀土及过渡金属的萃取剂, 它同中心离子的配合强度随条件改变亦有很大变化. 我们在钇和镍离子共同存在的条件下得到了标题化合物, 并测得其单晶结构.     

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。