双（十二烷基亚磺酰）乙烷溶剂萃取钯及其机理的研究

本文研究用双（十二烷基亚磺酰）乙烷萃取钯的性能，在ＫＩ存在下从７ｍｏｌ／Ｌ盐酸介质中用含有ＢＤＳＥ的氯仿能定量萃取钯，有机的钯可被硫脲或氨溶液反萃继之用ＴＭＫ－ＴｒｉｔｏｎＸ－１００光度法测定，研究了萃取的最佳条件及干扰情况，斜率法测得萃合物组成为Ｐｄ：Ｉ：ＢＤＳＥ＝１：２：１，红外光谱证实萃合物中ＢＤＳＥ的二个亚砜以硫原子与钯配位，萃合物为异位体络合物，提出了选择性萃取分离钯的新方法。     

Magnetic silica colloids for catalysis

Monodisperse magnetizable colloidal silica particles in a stable dispersion have been functionalized with a homogeneous catalyst: a PCP–pincer Pd-complex. In a proof-of-principle experiment we demonstrate the catalytic activity of the colloids in a C–C bond formation reaction. Advantages of the magnetic silica carriers are the large surface-to-volume ratio and the easy recovery by magnetic separation. After magnetic separation, the catalyst-loaded particles are readily redispersed for further use.     

铽－甲基吲哚乙酰丙酮三元配合物发光过程研究

测定和分析了ＲＥ．Ｌ１．Ｌ２（ＲＥ＝Ｔｂ（Ⅲ）、Ｇｄ（Ⅲ），Ｌ１＝３Ｍ（３甲基吲哚－１－乙酰基丙酮），Ｌ２＝ＴＰＰＯ、Ｐｈｅｎ、Ｄｉｐｙ）三元配合物的荧光光谱、磷光光谱、磷光寿命及变温荧光光谱等．讨论了Ｔｂ（Ⅲ）与配体之间的能级匹配和Ｌ１与Ｌ２的三重态之间传能的问题，说明了影响这些三元配合物荧光效率的主要因素及其发光过程．     

Syntheses,crystal structures and blue emission of three zinc(II) coordination polymers with a 4,4′‐dicarboxybiphenyl sulfone ligand

Three novel zinc complexes [Zn(dbsf)(H₂O)₂] ( 1 ), [Zn(dbsf)(2,2′‐bpy)(H₂O)]·(i‐C₃H₇OH) ( 2 ) and [Zn(dbsf)(DMF)] ( 3 ) (H₂dbsf = 4,4′‐dicarboxybiphenyl sulfone, 2,2′‐bpy = 2,2′‐bipyridine, i‐C₃H₇OH = iso‐propanol, DMF = N,N‐dimethylformamide) were first obtained and characterized by single crystal X‐ray crystallography. Although the results show that all the complexes 1–3 have one‐dimensional chains formed via coordination bonds, unique three‐dimensional supramolecular structures are formed due to different coordination modes and configuration of the dbsf^2? ligand, hydrogen bonds and π–π interactions. Iso‐propanol molecules are in open channels of 2 while larger empty channels are formed in 3 . As compared with emission band of the free H₂dbsf ligand, emission peaks of the complexes 1–3 are red‐shifted, and they show blue emission, which originates from enlarging conjugation upon coordination. Copyright © 2006 John Wiley & Sons, Ltd.     

二氯和邻菲罗啉二酮的镍(Ⅱ)、铜(Ⅱ)、锌(Ⅱ)配合物的合成与表征

以ＭＣｌ２和配体Ｌ（Ｌ＝１，１０－菲罗啉－５，６－二酮）为原料，合成了标题配合物ＭＬＣｌ２，Ｍ＝ＮｉⅡ，ＣｕⅡ，ＺｎⅡ，并经元素分析、热谱、ＩＲ和摩尔电导表征．三者均为四配位的电中性配合物，热稳定性高于５００Ｋ，易溶于ＤＭＦ、ＤＭＳＯ和吡啶，可溶于乙腈和水．它们在ＤＭＦ中于３５０ｎｍ和３１５ｎｍ附近显示出强的Ｍ－Ｌ荷移跃迁     

H andH NMR Relaxation in Hydrogen-Bonded Solids Due to a Complex Motion: Classical Jumps over a Barrier and Incoherent Tunneling

Equations for the temperature dependence of proton and deuteron spin–lattice relaxation rates and second moments due to a complex motion consisting of classical jumps over a potential barrier and quantum mechanical tunneling through the barrier have been derived. Asymmetric double and triple potential wells are considered. These equations have been employed to analyze proton spin–lattice relaxation data for solid naphthazarin in the laboratory and rotating frames as a function of temperature. It is shown that tunneling plays an important role in the proton transfer dynamics of this compound.     

Response to high acidity and basicity at a platinum electrode in chronopotentiometry

A simple and rapid method is developed to determine the high acidity and the basicity of solutions by chronopotentiometry with a platinum working electrode. The acidity range from 5.0 mol/l H⁺ to 1.0 mol/l OH⁻ can be measured by the adjustment of deposition potential and time. The response mechanism to acidity and basicity has been explored. The transition potential plateau in chronopotentiograms is caused from the oxidation of hydrogen adsorbed on electrode surface.     

Template atom transfer radical polymerization of a diaminopyrimidine‐derivatized monomer in the presence of a uracil‐containing polymer

Uracil‐derivatized monomer 6‐undecyl‐1‐(4‐vinylbenzyl)uracil and diaminopyrimidine‐derivatized monomer 2,6‐dioctanoylamido‐4‐methacryloyloxypyrimidine (DMP) were synthesized and polymerized by atom transfer radical polymerization (ATRP). A well‐defined, highly soluble, uracil‐containing polymer, poly[6‐undecyl‐1‐(4‐vinylbenzyl)uracil] (PUVU), was prepared in dioxane at 90 °C with CuBr/1,1,4,7,10,10‐hexamethyltriethylenetetramine as the catalyst and methyl α‐bromophenylacetate as the initiator. PUVU was further used as a template for the ATRP of DMP. The enhanced apparent rate constant of the DMP polymerization in the presence of PUVU indicated that the ATRP of DMP occurred along the PUVU template. The template polymerization produced a stable and insoluble macromolecular complex, PUVU/poly(2,6‐dioctanoylamido‐4‐methacryloyloxypyrimidine). An X‐ray diffraction study confirmed that the complex had strandlike domains. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 6607–6615, 2006