Vibronic intensities in centrosymmetric coordination compounds of the rare earths Part II. A vibronic crystal field-closure-ligand polarisation model and applications to the PrCl6 and UBr6 complex ions in octahedral symmetry

A symmetry adapted formalism to evaluate the vibronic intensities induced by the ungerade vibrational modes in centrosymmetric coordination compounds of the rare earths is put forward and applied to several selected electronic transitions of the PrCl³⁻₆ and UCl²⁻₆ complex ions in octahedral symmetry. This current model is based upon a modified symmetry adapted version of the combined vibronic crystal field-closure-ligand polarisation approach. This model differs from that developed in Part I of this series, in that for the vibronic crystal field contribution to the total transition dipole moment, the closure procedure is employed rather than the utilisation of a truncated basis set for the central metal intermediate electronic states. A criterion is introduced to choose an appropriate set of phases for both the electronic and the vibrational coordinates so that to ensure the right sign for the interference term (which couples together both the vibronic crystal field and the vibronic ligand polarisation contributions to the total transition dipole moment). We have focused our attention on the modulation of the intermolecular force field and a version of a modified general valence force field has been adopted. The reasons for using this formalism rather than the superposition model (SM) are fully discussed in the text. Finally, it is shown that the agreement with experiment is satisfactory for most of the components of the transitions studied, despite the apparent simplicity of our model calculation. General master equations applicable to any f^N electronic configurations are derived to show the utility and flexibility of this current formalism.     

一类新的红色荧光粉MY2S4:Er3+(M=Sr2+,Ba2+)的合成与表征

Eu2 激活的CaS: Eu[1],Eu3 激活的硫氧化物[2]，Pr3 激活的Ca0.8Zn0.2TiO3[3]以及Eu2 和Mn2 掺杂的SrY2S4[4]都是重要的红色发光材料.     

Chemical modification of silica surface by immobilization of functional groups for extractive concentration of metal ions

Increased utilization of mechanically stable synthetic matrices particularly silica gel as a solid support and its surface modification either by impregnation of organic ligands directly or covalent grafting through spacer unit for extractive concentration of trace elements are highlighted in the present article. Experimental evidences for existence of surface silanol and its chemical nature have explored the idea of silica surface modification. Recent methods of development in functionalized silica synthesis by attachment of various ligands or organic reagents to the silica surface and techniques of characterization of the modified surface have been reported. Analytical applications of various modified silica surfaces, in particular, adsorption of trace elements taking separation and preconcentration into account from complex synthetic mixture as well as natural water is presented.     

金属离子掺杂对TiO2光催化性能的影响

TiO₂光催化反应过程涉及光生电荷、电荷迁移、电荷在TiO₂表面的反应和溶液体相反应4个顺序相接并相互影响的步骤.在TiO₂中掺杂金属离子对以上4个步骤均有重要影响,合理的掺杂可有效地提高其光催化性能.本文综合了国内外此方面的最新研究成果,从提高TiO₂光催化性能和优化光催化反应的角度出发,在材料吸光能力、电荷扩散、表面反应、粒径和晶型等方面,全面地分析总结了金属离子掺杂的影响效果和规律性认识,并对TiO₂基光催化材料的金属离子掺杂改性研究的未来发展方向提出了建议.文中还简要介绍了相关的掺杂方法和材料表征手段.     

Structure of the blue forms of bisphthalocyanines of rare-earth elements

Using electron spectroscopy, X-ray photoelectron spectroscopy, and ESR spectroscopy, the blue forms of bisphthalocyanines of rare-earth elements were found to have structures of sandwich-type complexes with isoelectronic phthalocyanine ligands linked with tetravalent metal ions, [Pc^2–Ln⁴⁺Pc^2–]⁰. A comparative spectral and electrochemical study of the blue and green forms oftert-butyl-substituted bisphthalocyanines was carried out for almost the whole series of rare-earth metals. Lutetium octa(perfluoro-tert-butyl)- and perchlorobisphthalocyanines were synthesized for the first time.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 425–430, March, 1995.This study was financially supported by the Russian Foundation for Basic Research (grant No. 94-03-08903).     

Clustering of nucleosides in the presence of alkali metals: Biologically relevant quartets of guanosine,deoxyguanosine and uridine observed by ESI-MS/MS

Electrospray ionization (ESI) mass spectra of nucleosides, recorded in the presence of alkali metals, display alkali metal ion-bound quartets and other clusters that may have implications for understanding non-covalent interactions in DNA and RNA. The tetramers of guanosine and deoxyguanosine and also their metaclusters (clusters of clusters), cationized by alkali metals, were observed as unusually abundant magic number clusters. The observation of these species in the gas phase parallels previous condensed-phase studies, which show that guanine derivatives can form quartets and metaclusters of quartets in solution in the presence of metal cations. This parallel behavior and also internal evidence suggest that bonding in the guanosine tetramers involves the bases rather than the sugar units. The nucleobases thymine and uracil are known to form magic number pentameric adducts with K+, Cs+ and NH4+ in the gas phase. In sharp contrast, we now show that the nucleosides uridine and deoxythymidine do not form the pentameric clusters characteristic of the corresponding bases. More subtle effects of the sugars are evident in the fact that adenosine and cytidine form numerous higher order clusters with alkali metals, whereas deoxyadenosine and deoxycytidine show no clustering. It is suggested that hydrogen bonding between the bases in the tetramers of dG and rG are the dominant interactions in the clusters, hence changing the ribose group to deoxyribose (and vice versa) generally has little effect. However, the additional hydroxyl group of RNA nucleosides enhances the non-selective formation of higher-order aggregates for adenosine and cytidine and results in the lack of highly stable magic number clusters. Some clusters are the result of aggregation in the course of ionization (ESI) whereas others appear to be intrinsic to the solution being examined.     

Mass spectrometry of metastable ions from lagochiline-type diterpenoids

Low-and high-resolution mass spectra and spectra of metastable ions were studied using direct analysis of daughter ions (DADI) and metastable defocusing (MD) of lagochiline-type diterpenoids. Patterns in their fragmentation were found. __________ Translated from Khimiya Prirodnykh Soedinenii, No. 1, pp. 56–60, January–February, 2007.     

2-巯基苯并咪唑保护的铜纳米团簇的制备及银离子检测

以2-巯基苯并咪唑为保护剂,聚乙烯吡咯烷酮为稳定剂,水合肼为还原剂,“一锅法”合成2-巯基苯并咪唑保护的,高稳定性、强荧光、大斯托克斯位移的铜纳米团簇(Cu NCs),并用于检测水样中的银离子含量。采用透射电子显微镜(TEM)和X射线光电子能谱(XPS)对铜纳米团簇的结构进行表征,通过荧光光谱和紫外可见光谱对其光学性能进行研究。研究表明:该铜纳米团簇的最大激发和发射波长分别为340和558 nm,在日光灯和紫外灯下分别为无色和橙色。Cu NCs具有较高的分散性,尺寸大小为2~3 nm。在最佳反应条件下,铜纳米团簇可以选择性地被银离子猝灭,且灵敏度高,线性范围为1~40μmol/L,检测限为0.5μmol/L。该方法用于检测实际水样(自来水、湖水)中银离子的浓度,结果令人满意,表明在环境监测中有非常高的应用价值。     

二价金属离子萃取速率常数与软硬酸碱规则

用上升液滴法测定了２－乙基己基膦酸单（２－乙基己基）酯－正辛烷从硝酸介质中萃取镁、钙、锌、镍、铜和铅等二价金属离子的正向初始速率，建立了速率方程，计算出正向萃取反应的速率常数、活化能及活化熵，首次将软硬酸碱规则与金属溶萃取速率常数关联。结果表明，在萃取机理相同时，萃取速率常数的大小与金属离子的软硬酸碱标度一致，即萃取过程中，作为酸的被萃取金属离子，其硬度越大，萃取速率常数亦越大，萃取反应的活化能…     

Cu离子A位掺杂对LaSrCoO4复合氧化物氧化性能的影响

采用聚丙烯酰胺法制备了La1-xCuxSrCoO4(x=0.2-0.8)复合氧化物,考察了Cu离子掺杂量(x)对CO及C3H8氧化反应活性的影响,并运用XRD、IR、TPR和TPD等多种手段对复合氧化物催化剂进行了表征。结果表明,催化剂活性随x的变化而变化,Cu部分取代A位La能提高LaSrCoO4催化剂的CO及C3H8氧化反应活性,当x=0.4时La1-xCuxSrCoO4催化剂的晶格氧和Co3 含量较多,晶格氧的活动性较高,催化活性最佳。