CuO／CeO2和CuO／Al2O3催化剂的催化性能

本文以ＣＯ氧化为模式反应考察了ＣｅＯ２和Ａｌ２Ｏ３负载氧化铜催化剂的氧化活性，运用ＸＲＤ和ＴＰＲ技术研究了催化剂的还原性能和物相结构，结果表明：载体性质对负载ＣｕＯ催化剂的ＣＯ氧化活性有很大影响，ＣｕＯ／ＣｅＯ２催化剂活性明显高于ＣｕＯ／Ａｌ２Ｏ３催化剂．催化剂的还原特性随载体不同而不同．同时发现，热处理对催化剂铜物种的存在形式，晶粒大小、还原特性及其催化活性有明显影响，ＣｕＯ／Ａｌ２Ｏ３催化剂活性下降的主要因素是生成了活性较低的ＣｕＡｌ２Ｏ４相，而ＣｕＯ／ＣｅＯ２催化剂活性下降是由于ＣｕＯ和ＣｅＯ２发生烧结，晶粒变大     

Thermodynamics of complexation of lanthanides and some of transition metal ions by 5,5-dimethyl-cyclohexane-2-(2-hydroxyphenyl)-hydrazono-1,3-dione (DCPHD) and its derivatives

Summary Equilibrium betweenDCPHD,DC-4-Cl-PHD, andDC-4-Me-PHD and protons, transition, and lanthanide ions have been investigated at 30 °C by means of potentiometric titration in 75% (v/v) methanol-water mixture containing 0.10M KNO₃ as a constant ionic medium. Thermodynamic parameters (G, H and S) referring to the formation of species HL ^–,L ^––,ML ^+n–2 andML ₂ ^+n–4 (L ^–– denotes the ligand anion) have been determined in solutions. The solvent effects on the thermodynamic parameters of the complex formation are discussed in terms of differences in the donor ability of methanol and water solvents. The plots of thermodynamic parameters versus ionic potential (Z ²/r) of the lanthanide elements is not linear as expected from ionic theory. The obtained curve can be resolved in an initial group (the lighter lanthanides), an intermediate group (Sm-Dy), and a final group (the heavier ones, Tb-Lu). This behavior was explained in terms of differences in the dehydration of lighter lanthanide(III) from that of heavier ones.

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Thermodynamik der Komplexierung von Lanthaniden und einigen Übergangsmetall-Ionen mit 5,5-Dimethylcyclohexyl-2-(2-hydroxyphenyl)-hydrazono-1,3-dion (DCPHD) und seinen Derivaten

Zusammenfassung Die Gleichgewichte zwischenDCPHD,DC-4-Cl-PHD undDC-4-Me-PHD mit Protonen, Übergangsmetall- und Lanthaniden-Ionen wurden bei 30 °C mittels potentiometrischer Titration in 75% (v/v) Methanol-Wasser mit einem Gehalt an 0.10M KNO₃ als konstantem ionischem Medium untersucht. Die thermodynamischen Parameter G, H und S zur Bildung der Spezies HL ^–,L ^––,ML ^+n–2 undML ₂ ^+n–4 (L ^–– steht für das Ligandenanion) wurden in Lösung bestimmt. Die Lösungsmitteleffekte auf diese Komplexbildungsparameter werden auf Basis der Differenz im Donorvermögen von Methanol und Wasser als Solventien diskutiert. Die Diagramme der thermodynamischen Parameter gegen die ionischen Potentiale (Z ²/r) der Lanthaniden sind, wie nach der Ionentheorie zu erwarten, nicht linear. Die erhaltene Kurve läßt eine Anfangsgruppe (die leichteren Lanthaniden), eine mittlere Gruppe (Sm-Dy) und eine Endgruppe (die schwereren Lanthaniden. Tb-Lu) erkennen. Dieses Verhalten kann aus dem Unterschied im Dehydratationsverhalten erklärt werden.

     

On the ternary B 2-phase in the Al-Co-Ga system

Summary Lattice parameter values were determined for the ternary B 2-phase in the Al-Co-Ga system, and it was found that a continuous solid solution exists between -AlCo and -CoGa. Phase boundaries of the ternary phase at 1 100 K were derived from the variation of the lattice parameter with composition.

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Über die ternäre B 2-Phase im System Al-Co-Ga

Zusammenfassung Im Bereich der ternären B 2-Phase im System Al-Co-Ga wurden die Werte des Gitterparameters bestimmt; es stellte sich heraus, daß eine durchgehende feste Lösung zwischen -AlCo und -CoGa besteht. Die Phasengrenzen der ternären Phase bei 1 100 K wurden aus der Änderung des Gitterparameters mit der Zusammensetzung abgeleitet.

     

A molecular modelling study of the interaction of noradrenaline with theβ 2-adrenergic receptor

Summary A model of the ₂-adrenergic receptor binding site is built from the primary structure of the receptor, experimental evidence for key binding residues and analogy with a homologous protein of partially determined structure. It is suggested that residues Trp-109, Thr-110 and Asp-113 are involved in ligand binding. Noradrenaline is successfully docked into this model, and the results of an INDO molecular orbital calculation on the complex indicate that a charge transfer interaction between Trp-109 and noradrenaline is possible.     

1H and 13C assignments of two new triterpenes from Cladocolea grahami

The structure elucidation and 1H and 13C assignments of the new triterpenes 3beta-palmitoxy-7beta-hydroxyolean-12-ene (1) and its hydrolysis product 3beta,7beta-dihydroxyolean-12-ene (2) and 3beta-sn-glyceroyl-(1'-palmitoxy)urs-12-ene (3), isolated from the aerial parts of Cladocolea grahami (Loranthaceae), are reported.     

Thermodynamic properties of aqueous organic mixtures near the critical demixing: Cases of 2,6-dimethylpyridine and of 2-isobutoxyethanol

Phase diagrams, volumes and heat capacities of aqueous mixtures of 2,6-dimethylpyridine (2,6-L) and 2-isobutoxyethanol (iBE) and activities of 2,6-L in aqueous mixtures were measured in the monophasic region near the lower critical solution temperature (LCST). With 2,6-L some measurement were also made just above the LCST. From the temperature dependence of these data, partial molar relative enthalpies (2,6-L), expansibilities and the temperature derivative of heat capacities were calculated and show that iBE undergoes a microphase transition at low concentration which is not related to the phase separation. On the other hand, the properties of 2,6-L in the water-rich region at temperatures well below the LCST indicates that this solute has only a slight tendency to associate. The heat capacities of 2,6-L show an important increase near the LCST. Such changes are not observed for iBE and other alkoxyethanols and amines since these systems already exist in the form of microphases; the partial molar properties of iBE near the LCST are nearly equal to the molar values of the pure liquid, and the changes in thermodynamic properties corresponding to the macroscopic phase transition, are therefore too small to be measured by the present techniques.     

团聚纳米SiO_2在苯乙烯乳液聚合过程中的再分散过程及机理

用二氧化硅 (SiO2 )存在下的乳液聚合法制备了聚苯乙烯 (PSt) 纳米SiO2 复合材料 ,研究了苯乙烯(St)乳液聚合过程中团聚纳米SiO2 的解离与再分散过程及分散的机理 .发现商品纳米SiO2 粒子以团聚体形式存在 ,团聚体大小远超出纳米级范围 .随聚合时间的延长 ,St的转化率逐渐增加 ,而PSt SiO2 复合微胶囊的粒径逐渐减小 ,反应 12 0min后 ,转化率和复合微胶囊粒子的粒径趋于稳定 .透射电镜 (TEM)也显示PSt SiO2 复合微胶囊粒子具有海岛结构 ,而SiO2 粒子的粒径在纳米范围内 ,表明在乳液聚合过程中SiO2 团聚体被逐渐解离 ,并重新分散到纳米尺度 .红外光谱研究发现 ,在乳液聚合过程中 ,除生成PSt均聚物外 ,还在纳米SiO2 表面生成了PSt接枝共聚物 ,改善了无机纳米粒子与聚合物之间的界面相容性 .聚合过程中的反应热和剪切搅拌是团聚体被解离和重新分散的主要原因 ,而生成的聚合物起到隔离作用     

Heterocyclic inflammation inhibitors

Non steroidal anti-inflammatory drugs are the most widely used medicines for relief of pain. These drugs have some side effects, particularly toxicity in the gastrointestinal tract and kidneys. Various approaches have been used for obtaining safer anti-inflammatory drugs. In this review we have summarized the recent developments in the following areas; (i) mode of action of NSAIDs (ii) Role of COX-1 & COX-2 in inflammation, (iii) Different approaches used to improve gastric tolerance i.e. chemical manipulation, formulation & co-administration, development of non specific (COX-1 & COX-2 inhibitors) and specific (COX-2 inhibitors) inflammation inhibitors, and development of inflammation inhibitors having a mode of action other than COX-1 & COX-2 inhibition. We have also focused on the safety of COX-2 inhibitors and the synthesis of heterocyclic compounds and their role as inflammation inhibitors.     

Synthesis of novel derivatives of 2-(azolylimino)thiazoline

Successive alkylation of 5-(3-phenylthioureido)-3H-imidazole-4-carboxamides with alkyl halides and chloroacetone gave (N-oxopropylimidazolyl)isothioureas, which were easily converted into derivatives of purine and imidazopyrazinone. In the case of ethyl 5-(3-phenylthioureido)-3H-imidazole-4-carboxylate, primary alkylation occurs at the N atom of the imidazole ring. Reactions of 5-(3-phenylthioureido)-3H-imidazole-4-carboxamides with haloketones afforded a number of 4-hydroxy-2-imidazolyliminothiazolidines and 2-imidazolylimino-Δ⁴-thiazolines.__________Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 2196–2204, October, 2004.