红外光谱中溶剂效应机理初探——配位机制的提出

本文就红外光谱中溶剂效应机理提出了溶质和溶剂分子间的瞬时配位作用机制，认为同－溶质在不同溶剂中的振动波数不同，是由于这种瞬时配位作用改变了溶质价电子运动状态所致。据此提出了溶剂效砂的定量关系式，测定了七种溶剂配位效应常数。用这一套经验参数处理了几种取代苯甲酸的羰基伸缩振动的溶剂效应，得较好的线性关系。还发现羰基的振动波数与取代基的Ｈａｍｍｅｔｔ常数σ之间，羰基伸缩振动对溶剂效应的敏感度与σ之间，Ｈ     

Ferrocene derivatives XXVIII. The metallation of phenylazoferrocene and the synthesis of phenylazocyclopentadienyl derivatives of other metals

Phenylazoferrocene undergoes nickelation and palladation exclusively on the phenyl group. Lithium phenylazocyclopentadienide has been converted into derivatives of Mo, Mn, Fe, Ru and Rh.     

Simulated cosmic strings in a “big bang” in superfluid3He at 100 μK

During studies of the impact of single neutrons on superfluid³He at around 100μK we have measured the thermal energy released in the superfluid following the nuclear reaction, n+³He→p+³H+764keV. However, we find that the measured energy deposited in the quasiparticle system shortly after this reaction is substantially less than what we expect. We believe that this energy deficit represents that energy which has gone into the creation of vortices, in analogy to the creation of cosmic strings in the early universe via the Kibble mechanism. Furthermore, from the magnitude of the deficit, we can infer the vortex density which compares favorably with that predicted in Zurek’s scenairo.     

Theoretical study of cyclization of 2′-hydroxychalcone

The isomerization mechanism of 2′(OH)chalcone (1) in flavanone (2) was studied. The calculations were performed with the semiempirical method AM1, using totally optimized molecular geometries. A 6-step mechanism including several equilibrium states was proposed. It was concluded that: (a) At the conformational equilibrium of 1 there could be 43.9% of s-cis conformer; (b) The acid dissociation of 1 trans-s-trans is considerable; (c) The E_E, ΔH_f and net charges show that the rotation of ring A of 1 and the formation of ring C of 2 occurs without greater impairments; (d) Although the keto structure is the most stable one, the enolate of 2 is present in the reaction medium; (e) The conversion of enol of 2 in the keto form would be the limiting step of the analyzed isomerization rate.     

Synthesis of a new class of uridine phosphorylase inhibitors

A new series of potent uridine phosphorylase inhibitors have been prepared from barbituric acid. Among them, 1-[(2-hydroxyethoxy)methyl]-5-)(m--benzyloxy)benzylbarbituric acid ( 37 , BBBA) is the most promising having a K_i value of 1.1 ± 0.2 nM with uridine phosphorylase from human liver. The new inhibitors are easily synthesized and are better inhibitors of human uridine phosphorylase than their uracil counterparts.     

Turbulence modelling of the shear layers in the trailing edge region of a modern rear-loaded airfoil at incidence

After carefull analysis in a turbulent zero-pressure gradient flow, various simple algebraic turbulence models were applied to the almost separated flow on the upperside of an airfoil at incidence. The Johnson-King and Horton non-equilibrium (or rate equation) models give clearly improved results.     

Electronic and electromagnetic devices for millimeter-wave beam control arrays

Device alternatives for millimeter-wave beam control arrays are examined. For the control function, a wide range of semiconductor device as well as bulk material alternatives are considered. In addition, alternatives to the traditional metal strip are considered for the passive electromagnetic array element. This work should provide a broader perspective regarding the choices available for the optimized design of new beam control arrays.     

萃取色谱法富集原子吸收法测定环境水中超痕量金属元素──两种萃取剂的比较

本文研究并比较了分别以８－羟基喹啉和巯基苯骈噻唑为萃取剂，以活性硅胶为载体的柱式萃取色谱法对环境水中Ｚｎ、Ｃｕ、Ｐｂ、Ｃｄ、Ｆｅ、Ｃｏ、Ｎｉ和Ｍｎ的最佳富集和洗脱条件。实验证明，后者明显优于前者。以巯基苯骈噻唑为萃取剂的色谱柱对金属元素的吸附具有快速、完全、寿命长和重现性好等特点。在ｐＨ＝７～８之间回收率可达９８％以上，富集倍数为２００倍。     

Separation of non UV-absorbing cations by capillary electrophoresis

Summary A new buffer system for the separation of cations with capillary electrophoresis using indirect UV-detection is described. p-Aminopyridine can be used in the wide pH-range between 3 and 10. High-speed separations of positively charged non-UV absorbing ions are possible. Separation of ions with similar mobilities can be achieved by the addition of complexation reagents. The separation of potassium and ammonium is possible either with the addition of crown ether or at high pH-values. Transition metals can be separated by adding 2-hydroxybutyric acid to the buffer.Dedicated to Professor Dr. Wilhelm Fresenius on the occasion of his 80th birthday     

Molecular electric field mapping of some anions and cations of 2- aminopurine and 6- thioguanine

Electric fields of the anions, cations and neutral forms of 2-aminopurine and 6-thioguanine have been mapped. Certain important features of the maps are similar to those found earlier in the neutral and ionic forms of adenine and guanine. The computed electric field patterns satisfactorily explain reactive sites and biological activity of the molecules.