New reactivities of deltaline analogs: an efficient O-demethylation at C-1 and an unusual extrusion of the C-14 atom

O-Demethylation at C-1 in the C₁₉-diterpenoid alkaloids is very challenging. In this paper, it was firstly observed that 10-OH group in deltaline (1) is a determining factor for the O-demethylation reaction. After removal of this hydroxyl group, 1-O-methyl group in the corresponding deltaline analogs can be readily removed by treatment with HBr–HOAc. Meanwhile, the C-14 atom in bromides 18 or 20 can be extruded under basic condition probably via a sequence, including Grob fragmentation, aerobic oxidation, deformylation, and S_N2 nucleophilic substitution, to give enone 21 (70%) and oxetane 22 (14%). The structure of compound 22 was confirmed by X-ray crystallographic analysis of its derivative 21.     

Why calcium inhibits magnesium-dependent enzyme phosphoserine phosphatase? A theoretical study

Mechanisms for the formation of the Schiff base from acetaldehyde and butylamine, glycine and phosphatidylethanolamine based on Dmol3/DFT calculations were realized. For the case of phosphatidylethanolamine, calculations were done under periodic boundary conditions, in an amine-phospholipid monolayer model with two molecules of phosphatidylethanolamine by cell. All models contained explicit aqueous solvent. In the three cases, a neutral amino group is used to model the nucleophilic attack on the carbonyl group of acetaldehyde, and water molecules form hydrogen bond networks. These networks were involved in the reactions by performing as proton-transfer carriers, important in some steps of reactions, and stabilizing reaction intermediates. In all the studied reactions, they take place in two steps, namely: (1) formation of a carbinolamine and (2) its dehydration to the Schiff base, being the dehydration the rate-determining step of the process, consistent with available experimental evidence for similar reactions. The main difference between the studied reactions is found in the value for relative free energy for the intermediates and transition states in the second step; these values are lower in the cases of glycine and phosphatidylethanolamine in comparison with butylamine, due the influence of their molecular environments. Based on the results, the aminophospholipid surface environment and carboxylic group of glycine may boost Schiff base formation via a neighboring catalyst effect.     

Quantum mechanics in Dirac's front form

In 1949 Dirac published a paper in which he proposed various ways to combine special relativity with the Hamiltonian formulation of dynamics; these were referred toas forms and three differentforms, theinstant, thepoint, and thefront forms, were discussed. Dirac considered thefront form to be mathematically the most interesting. Despite this, thefront form appears to have been the least explored. This paper presents the results of a study of quantum mechanics in thefront form.     

铁电体爆-电换能的实验研究

使用掺铌PZT97.5/2.5铁电陶瓷样品在垂直工作模式下,进行了爆-电换能的实验研究。在电感-电容并联负载上获得了1360安的峰值电流;在电阻负载上获得了145×10³伏的峰值电压。实验结果与理论预计符合得比较好。 关键词：     

Ab initio方法研究~(40)Ca~(35)Cl分子的自旋轨道耦合效应和跃迁性质

本文研究了~(40)Ca~(35)Cl分子低态的自旋轨道耦合分裂以及获得更精确的光谱常数和更高的激发态.以从头算理论为基础,使用多参考组态相互作用方法获得了该分子的势能曲线和自旋轨道分裂,之后求解径向一维薛定谔方程获得光谱常数.得到了~(40)Ca~(35)Cl分子7个Λ-S低电子态的势能曲线和永久偶极矩,以及A~2Π→~2Σ~+,1~2Δ和C~2Π→~2Σ~+,1~2Δ跃迁的跃迁偶极矩,得到的光谱常数(不管是考虑了自旋轨道耦合(SOC)还是没有考虑SOC)与实验值非常符合,且要好于之前的理论计算结果 .值得注意的是,目前的计算还首次得到了C~2Π→~2Σ+,1~2Δ跃迁的跃迁性质,为之后实验观察~(40)Ca~(35)Cl分子的高激发态光谱和跃迁性质提供有益的理论参考.     

凸度量空间中单值和集值映象的公共不动点定理

§ 1.　Introduction　　Anecessaryandsufficientconditionandasufficientconditiontoensurethataset valuedmappingandasingle valuedmappinginacompletemetricspaceandacompleteconvexmetricspacehavingacommonfixedpointarerespectivelygivenin [1 ] .Meanwhilethemainresultsin[2 ]— [5]areimprovedandextendedin [1 ] .Inthispaper ,theexistenceatcommonfixedpointsoftwoset valuedmappingandasing valuedmappingwerestudied ,andthecorrespond ingresultsin [1 ]— [5]wereextendedandimproved .Let(X ,d)beanon emptymetricspa…     

Minimum embedding of P3‐designs into (K4—e)‐designs

A (K₄ ? e)‐design on v + w points embeds a P₃‐design on v points if there is a subset of v points on which the K₄ ? e blocks induce the blocks of a P₃‐design. It is shown that w ≥ ¾(v ? 1). When equality holds, the embedding design is easily constructed. In this paper, the next case, when w = ¾v, is settled with finitely many exceptions. © 2003 Wiley Periodicals, Inc. J Combin Designs 11: 352–366, 2003; Published online in Wiley InterScience ( www.interscience.wiley.com ). DOI 10.1002/jcd.10044