Potentiometric studies on the complexation equilibria between some trivalent lanthanide metal ions and biologically active 2-hydroxy-1-naphthaldehyde thiosemicarbazone (HNATS)

Summary The chelation behaviour of some trivalent lanthanide and yttrium metal ion with biologically active 2-hydroxy-1-naphthaldehyde thiosemicarbazone (HNATS) has been investigated by potentiomotric measurements at 20±0.5°C in 75% (v/v) dioxane-water medium at various ionic strengths of sodium perchlorate. The method of Bjerrum and Calvin, as modified by Irving and Rossotti has been used to find out the values of (average number of ligand bound per metal ion) andpL (free ligand exponent). The formation constants of metal chelates have been computed on a PC-XT computer, using a program patterned after that of Sullivan et al. to give _n values using weighted least squares method. TheS _min values (S _min =²) have been calculated. The order of formation constants of chelates was found to be: La³⁺3+3+3+3+3+3+3+3+3+. The formation constants of the chelates formed have been correlated to size and ionization potentials of the metal ions.

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Potentiometrische Untersuchungen der Komplexierungsgleichgewichte zwischen einigen trivalenten Metallionen und biologisch aktivem 2-Hydroxy-1-naphthaldehyd-thiosemicarbazon (HNATS)

Zusammenfassung Es wurde das Chelierungsverhalten einiger trivalenter Lanthanidenionen mit biologisch aktivem 2-Hydroxy-1-naphthaldehyd-thiosemicarbazon (HNATS) mittels potentiometrischer Messungen bei 20±0.5°C in 75% (v/v) Dioxan-Wasser bei verschiedener Ionenstärke an Natriumperchlorat untersucht. Die Methode nach Bjerrum und Calvin in der Modifikation nach Irving und Rossotti wurde zur Ermittlung der Werte (mittlere Anzahl an Liganden pro Metallion) undpL (Exponent an freiem Liganden) verwendet. Die Komplexbildungskonstanten wurden in Anlehnung an Sullivan et al. an einem PC-XT Computer errechnet. DieS _min-Werte (S _min=²) wurden ebenfalls bestimmt. Die Reihung der Chelatbildungskonstanten war: La³⁺3+3+3+3+3+3+3+3+3+. Die Bildungskonstanten sind mit der Größe und dem Ionisierungspotential der Metallionen zu korrelieren.

     

The elimination of fast variables in complex chemical reactions. III. Mesoscopic level (irreducible case)

The master equation for a complex chemical reaction cannot always be reduced to a simpler master equation, even if there are fast and slow individual reaction steps. Nevertheless the elimination of intermediates can be carried out with the help of the-expansion. This is illustrated with a well-known complex reaction: the dissociation of N₂O₅. It is shown that the intrinsic fluctuations in the N₂O₅ decay are larger than those implied by the master equation suggested by the macroscopic rate law.     

在线氧含量分析中的自动反吹

为解决在线氧含量分析测试仪表常被聚合物堵塞的问题，提出了自动反吹的时序分配和实施控制方案，从而为安全生产提供了保障。     

Formation of Amorphous AgI Aggregates Dominating Fast Ion Conductivity in AgI-based Glasses

Precise calorimetry was performed for (AgI)_x(AgPO₃)_1–x and (AgI)_x(Ag₂PO_3.5)_1–x glasses with very high AgI compositions (x0.75). The glasses showed -glass transitions due to the freezing-in of the rearrangement of conductive Ag⁺ ions. Magnitude of the associated heat-capacity jump increased with increasing the AgI composition in the respective glass systems, and was larger in the former system than in the latter when compared at the same AgI composition. All the results were well explained by the amorphous AgI aggregate model for the AgI-based fast ion conducting glasses, indicating the appropriateness of the model for the structure of the glasses with high AgI compositions. The formation of the hypothetical bulk amorphous AgI was also indicated in the glasses at the highest limit of AgI composition.This revised version was published online in November 2005 with corrections to the Cover Date.     

新的酰胺型开链冠醚的合成与性质

Simon在70年代开发了一类酰胺型开链冠醚,能选择性配位碱土金属离子并可作为中性载体制备离子选择性电极.由于酰胺型开链冠醚易于制备,因此受到人们广泛地重视.Vgtle等提出的“末端基”概念为开链冠醚的合成、设计起了重要的指导作用.前文报道2-甲氧基-1-氨甲基萘与三甘醇二碘化物在无水碳酸钠存在下于乙腈中反应得到双手臂的套索冠醚与碘化钠的配合物.X射线衍射晶体结构分析表明萘环上的甲氧基中的氧原子参加了与钠离子的配位,生成了扭曲的六边形双锥结构配合物.因此2-甲氧基-1-氨基萘可以作为开链冠醚的“末端基”.开链冠醚的合成路线是:     

Asymmetric Baeyer—Villiger oxidation: control of stereoelectronic demand

The recent development of asymmetric Baeyer—Villiger oxidation of prochiral and racemic ketones is briefly summarized, focusing on the regio- and stereocontrol of the oxidation attained by regulating the stereoelectronic demand in the step of rearrangement of the Criegee intermediate.Based on the report presented at the International Conference Modern Trends in Organoelement and Polymer Chemistry dedicated to the 50th anniversary of the A. N. Nesmeyanov Institute of Organoelement Compounds of the Russian Academy of Sciences (Moscow, May 30–June 4, 2004).Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1784–1794, September, 2004.     

Li+粘贴CHnCl3-nO2和CFnCl3-nO2( n = 1~3 )自由基：Li+–CHnCl3-nO2和 Li+–CFnCl3-nO2的结构与性质的研究

The structures and stabilities of these still experimentally unknown CH_nCl_(3-n)O_(2-)Li~ and CF_nCl_(3-n)O_(2-)Li~ ionshave been theoretically investigated by ab initio molecular orbital theory and density functional theory(DFT)inconjunction with the 6-311G(d,p),6-311 G(d,p),6-311 G(2d,p)and 6-311 G(2df,2p)basis sets.The optimizedgeometries,chemical bonding and NBO analysis indicate that these complexes of CH_nCl_(3-n)O_(2-)Li~ and CF_nCl_(3-n)O_(2-)Li~ exist as ion-dipole molecules.The calculated affinity energies of these species exceed 41.9 kJ/mol,which arelarge enough to suggest the possibility that these title complexes could be detected as stable species in gas phase byLi~ ion attachment mass spectrometry.     

新型稀土芳香羧酸类配合物的合成及其光致和电致发光性质

合成了新型可溶性稀土芳香羧酸类配合物，测定了有机配体的三重态能级，并考察了其光致发光相对强度、荧光寿命，发现该系列稀土配合物具有很高的光致发光效率。利用其优良的溶解性，采用高聚物掺杂、旋涂技术将其制成薄膜应用于电致发光研究中，成功地制备出具有高色纯度的稀土有机电致发光器件。对于ITO／PVK／PVK：Tb(AS)3Phen：PBD／PBD／Al电致发光器件，其最大亮度为32cd．m^-2。     

[2+2]-Photocycloaddition von Cyclohexen an 2-Acetyl-5,5-dimethyl-1,3-cyclohexandion und 3-Acetyl-1,5,5-trimethyl-2,4-pyrrolidindion

Summary Irradiation of solutions of excess cyclohexene and 2-acetyl-5,5-dimethyl-1,3-cyclohexanedione (1), and 3-acetyl-1,5,5-trimethyl-2,4-pyrrolidinedione (4) results mainly in the formation of 1,5-diones2 and5. These originate from intermediate cycloadducts of cyclohexene and theexo-enols of the cyclic 1,3-diketones. The yields decrease with increasing polarity of the solvent. In solution2 and5 are in equilibrium with the cyclic hemiacetales3 and6.