Y2O3:Eu纳米晶的硝基取代苯甲酸配合物固相热解制备和性能

以苯甲酸、邻硝基苯甲酸、间硝基苯甲酸、对硝基苯甲酸、3,5 二硝基苯甲酸等为配体制备了Y3+、Eu3+二元配合物,配合物中Y3+与Eu3+的摩尔比为9：1.利用这些配合物的爆炸式热分解特性通过固相热解反应制备了一系列Y2O3:Eu纳米晶.透射电镜观察,可以看出所得纳米晶呈球形,粒度介于40～60 nm,X射线衍射分析表明实验所得纳米晶属立方晶系,粒径与电镜观察所得结果基本一致；Eu3+的引入并不影响Y2O3的晶相组成；配体类型对纳米晶的结构没有显著影响,不过相对于硝基取代苯甲酸配合物,苯甲酸配合物热解所得Y2O3∶Eu纳米晶团聚严重；退火温度显著影响纳米晶粒度,退火温度高,纳米晶粒度大,反之亦然.荧光光谱测定表明所有Y2O3∶Eu纳米晶具有相似的发光行为,其中以苯甲酸配合物分解所得Y2O3:Eu纳米晶发光性能最为优越.     

Reaction of 3-Acetyl-4,6,6-trimethyl-5,6-dihydro-2-pyrone with Carboxylic Acid Hydrazides

The reaction of 3-acetyl-4,6,6-trimethyl-5,6-dihydro-2-pyrone with the hydrazides of a series of carboxylic acids led to the synthesis of 5-alkyl(cyanomethyl)carbonyl-3,5a,7,7-tetramethylpyrazolino-4,5-c]tetrahydro-2-pyrones, which are the products from cyclization of the intermediately formed alkyl(cyanomethyl)hydrazones of 3-acetyl-4,6,6-trimethyl-5,6-dihydro-2-pyran. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 998–1001, July, 2005.     

超支化聚氨酯固体电解质导电性能的光谱学研究

用超支化聚氨酯 +线性聚氨酯作为基体 ,LiClO4作为离子源制得聚合物固体电解质 .用Raman光谱 ,FTIR光谱等光谱学方法研究了聚合物电解质中盐离子和聚合物基团之间的相互作用 .研究表明超支化聚氨酯对盐有较好的溶解作用 .研究还表明超支化聚氨酯加入有利于提高体系的电导率     

Theoretical investigation of excited states of molecules. An application on the nitrogen molecule

Diverse existing lines for the calculation of excited states are exposed, with an emphasis on those methods that consider both types of correlation energy: the dynamic and the non-dynamic one. We analyze the possibility of to calculate the dynamic correlation energy using a correlation energy density functional applied to a multi-determinantal wavefunction, which would include the non-dynamic correlation energy, versus the use of mono-determinantal wavefunctions, which are not able to include the long-range correlation energy, and versus the use of variational or perturbative calculations from multi-determinantal wavefunctions, with their excessive computational cost. The results obtained with several methods are compared. Contribution to the Serafin Fraga Memorial Issue.     

Products of hydrolysis of C,N-chelated triorganotin(IV) chlorides and use of products as catalysts in transesterification reactions

Triorganotin(IV) chlorides containing one L^CN chelating ligand were hydrolyzed with an excess of sodium hydroxide. The composition of the products is strongly dependent on the nature of the organic groups bound to the tin atom. Di(n-butyl)tin, dimethyltin as well as the diphenyl derivative exhibits an equilibrium between hydroxide and stannoxane forms (oxide), whereas alkyltin species react spontaneously and reversibly with carbon dioxide present in the air to form carbonate species. On the other hand, diphenyl derivatives display virtually no reaction with CO₂ towards carbonates, while the di-t-butyl-substituted tin derivative is stable under the same experimental condition and remains as a tin hydroxide. In the case of the dimethyltin derivative, a methyl group migration was observed with displacement of one L^CN chelating ligand during the reaction on the air. The coordination geometry of the tin central atom(s) of all studied compounds can be described as trigonal bipyramidal with a dative bonded dimethylamino group occupying one coordination site. The catalytic activity of these compounds in transesterification reactions is generally lower compared to the systems reported in the literature, with the exception of the transesterification of ethyl acetate by cyclohexanol which displays a remarkable activity.     

Tl2O3/聚-N-乙烯基咔唑复合纳米线的研究

Stable monolayers of electropolymerized poly-N-vinylcarbazole (EPVK) and arachidic acid(AA) are obtained on a subphase of alkaline Tl2O3 colloidal solutions. As revealed by the atomic force microscope, there is phase separation in the mixed LB monolayers. Transmission electron microscopic observations reveal that ordered arrays of composite Tl2O3/Epvk nanowires are formed in the mixed monolayers. Formation of the composite nanowire arrays is attributed to the ordered adsorption of Tl2O3 colloidal particles along the polycationic EPVK chains. The composite nanowire array is 3.2nm wide with a spacing of 2.7nm.The composite nanowire arrays can also be formed when pure EPVK is used. Composite LB multilayers of Tl2O3/EPVK nanowire arrays are prepared. The bilayer spacing is 5.54nm.The present study is of importance to the fabrication of inorganic semiconductor/functional polymer composite nanowires.     

Structure and hydration of polycytidylic acid from the data of infrared spectroscopy, EHF dielectrometry and computer modeling

The aim of this paper is to summarize the original results concerned with the elucidation of the role of water environment in the formation of different structures of polyribocytidylic acid (poly(rC)), depending on the pH, temperature and ion content. To solve this problem, we studied the hydration of poly(rC)-K⁺ in films differing in water content, by methods of infrared spectroscopy and piezogravimetry, and in solution, using the dielectric measurements at a wavelength of 7.6 mm (extremely high frequencies — EHF). The experimental results were confirmed by a Monte Carlo simulation of the interaction between water molecules and single-strand and double-strand poly(rC) fragments in clusters of 800 water molecules. A model of hydration of double-strand complex of poly(rC)⁺-poly(rC) has been proposed based on our results and the known X-ray parameters of the complex. The obtained results and proposed structure of poly(rC)⁺-poly(rC) suggest that, the stabilization of this complex occurs due to intra- and inter-chain water bridges, together with the hydrogen bonds between neutral and protonated cytosines in pairs.     

Synthesis of ω- and (ω – 1)-acetylenic acids from five-, six-, or seven-membered cycloalkanones

A convenient method for the synthesis of - and ( – 1)-acetylenic acids involves free-radical oxidative scission of cycloalkanones containing five-, six, or seven-membered cycles to give the corresponding -olefinic acids followed by bromination of the latter and subsequent dehydrobromination under the action of alkalis.     

Thermal polymerization of acrylamide during the formation of the structures of acrylamide complexes with metal nitrates

The effects of the composition of Mn^II, Co^II or Ni^II nitrate hydrate — acrylamide (AAM) mixtures and of the duration of their aging at ambient temperature on the structurization of acrylamide complexes and on the character of their thermal polymerization have been studied by scanning and isothermic differential calorimetry. Structurization is a rather prolonged step in the synthesis of acrylamide complexes. The peculiarities and rate of this step are determined by the composition of the mixture and by the nature of the complexforming compound; it yields several structural modifications of the AAM complexes. The thermal polymerization of those structural forms of acrylamide complexes that polymerize at low temperatures may be formally described as polymerization in an acrylamide-nitrate-water mixture. The effective activation energy of the polymerization of acrylamide mixed with Mn^II nitrate hydrate is 45 kJ mol^–1.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 679–683, April, 1995.This work was carried out with financial support from the Russian Foundation for Basic Research, Project No. 93-03-4162.