Prolinol-based nucleoside phosphonic acids: new isosteric conformationally flexible nucleotide analogues

trans-4-Hydroxy-l-proline has been used as a starting material for the synthesis of prolinol-based nucleotide analogues with an N-phosphonomethyl moiety attached to the prolinol ring nitrogen atom. The synthetic methodology based on the inversion of configuration at both 1- and 4-position led to all diastereoisomeric O-protected 4-mesyloxyprolinol-N-phosphonates. Alkylation of nucleobases using the synthons in the l-series afforded the nucleotide analogues corresponding to α-l- and β-l-nucleotide. The NMR-based conformational study of these compounds in aqueous solution performed at two different pH values, showing either N-fully protonated or deprotonated forms, revealed the occurrence of the same mostly populated conformer in both cases. All final l-prolinol-based nucleoside phosphonic acids were tested for cytotoxic and antiviral properties, but no significant activity was found.     

Influence of steric and intramolecular inductive effects on the variable trends in R-X (R=Alkyl) bond dissociation energy

The question “why are the variation trends of R-X bond dissociation energy different?” is answered. The R-X bond dissociation energy (BDE) may be influenced by three main factors: the C-X intrinsic bond energy, the 1,3 geminal repulsion, and the intramolecular charge-induced dipole. In the presence of atom X, the variation trend of BDE in R-X (R= Me, Et, i-Pr, t-Bu) is dominated by two factors, the 1,3 geminal repulsion and the intramolecular charge-induced dipole. The former decreases the R-X BDE, and the latter either increases or decreases the R-X BDE. For the series of R-X with the R-C bond (such as R-Me, R-CH == CH², R-C≡CH, and R-CN), the 1,3 geminal repulsion decreases the R-X BDE, and the variation trends of R-C BDE decrease from Me to t-Bu. As regards the series of R-X (such as R-H, R-BH², and R-SiH²) in which the electronegativity of atom X is smaller than that of the carbon atom, the above two factors decrease the R-X BDE, and the variation trends of the R-X BDE decrease from Me to t-Bu. As to the series of R-X (such as R-F, R-OH, R-Cl, R-Br, R-I, and R-NH²) in which the electronegativity of atom X is larger than that of the carbon atom, the 1,3 geminal repulsion decreases the R-X BDE, while the intramolecular charge-induced dipole increases the R-X BDE. In this case, the variation trends of R-X BDE depend on the competition of the two factors. As a result, some of them (e. g., R-F, R-OH) increase from Me to t-Bu, some (e. g., R-I) decrease from Me to t-Bu, and some (e. g., R-Br) change very little.     

(np)~3电子组态的波函数

根据泡利不相容原理、费米子所满足的反对称波函数和升降算符的对称性,应用二次量子化的方法,讨论(np)3电子组态在L-S耦合情况下的波函数.     

Mechanisms and Möbius strips: understanding dynamic processes in annulenes

Exploratory computational studies on annulenes with planar, Möbius, and two‐twist topologies have resulted in new mechanisms to explain facile thermal configuration change (cis‐trans isomerization) for medium‐sized annulenes ([12]‐ to [16]annulene). Möbius π‐bond shifting through both aromatic and antiaromatic transition states, two‐twist π‐bond shifting, and planar nondegenerate π‐bond shifting can all be invoked to explain experimental results. Moreover, a simple bond‐shift rule, which is based on the change in number of trans C?C double bonds (Δtrans), was developed that predicts the topology of the transition state(s) necessary to effect the desired cis‐trans isomerization. The bond‐shift rule was also applied to configuration change in dehydro[12]annulene. Finally, extensive investigation of the [14]annulene hypersurface revealed that numerous Möbius minima exist within 10 kcal/mol of the global minimum. Copyright © 2012 John Wiley & Sons, Ltd.     

Minimal configuration trees

A graph is singular of nullity η if zero is an eigenvalue of its adjacency matrix with multiplicity η. If η(G)=1, then the core of G is the subgraph induced by the vertices associated with the non-zero entries of the zero-eigenvector. A connected subgraph of G with the least number of vertices and edges, that has nullity one and the same core as G, is called a minimal configuration. A subdivision of a graph G is obtained by inserting a vertex on every edge of G. We review various properties of minimal configurations. In particular, we show that a minimal configuration is a tree if and only if it is a subdivision of some other tree.     

Structural and stereochemical aspects of the enantioselective halogenation of 1,3-dicarbonyl compounds catalyzed by Ti(TADDOLato) complexes

Complexes of the type [Ti(1-Np-TADDOLato)(carbonylenolato)₂] (3a-d), derived from β-keto esters, have been prepared and structurally characterized by NMR and X-ray crystallography. In solution, two main diastereoisomeric forms were identified. In the major C₂-symmetric isomer, the face-on naphthyl group of the (S,S)-TADDOL shields the Si-side of the coordinated enolate. Therefore, electrophilic attack of the halogenating agent can only occur at the Re-side of the substrate. α-Acyl-γ-lactams (4) were fluorinated with NFSI in the presence of the Ti(TADDOLato) catalyst in up to 87% ee. The absolute configuration of one of the products was determined by X-ray crystallography after derivatization. The observed absolute configuration at the fluorinated stereogenic center matches the one inferred from the structural analysis of the Ti(TADDOLato) complexes.     

Fragment molecular orbital study of the electronic excitations in the photosynthetic reaction center of Blastochloris viridis

All electron calculations were performed on the photosynthetic reaction center of Blastochloris viridis, using the fragment molecular orbital (FMO) method. The protein complex of 20,581 atoms and 77,754 electrons was divided into 1398 fragments, and the two‐body expansion of FMO/6‐31G* was applied to calculate the ground state. The excited electronic states of the embedded electron transfer system were separately calculated by the configuration interaction singles approach with the multilayer FMO method. Despite the structural symmetry of the system, asymmetric excitation energies were observed, especially on the bacteriopheophytin molecules. The asymmetry was attributed to electrostatic interaction with the surrounding proteins, in which the cytoplasmic side plays a major role. © 2009 Wiley Periodicals, Inc. J Comput Chem 2010     

O-Alkylation of Menthone Oxime: Synthesis and 13C NMR Studies of a Series of Novel Oxime Ethers

A series of novel menthone oxime ethers were synthesized in three steps starting from (–)-menthol. Analysis of the ¹³C NMR chemical shift differences between α carbons of oxime derivatives (O-alkyl oximes) provides a convenient and reliable means of assigning oxime stereochemistry. It has been found that carbons syn to the oxime are shifted more upfield than carbons anti to the oxime moiety. Significant E products were obtained.     

叶轮机械中叶顶间隙形态对气动性能影响的数值研究

本文针对几种不同形态的叶栅顶部间隙,在环壁转动与静止的不同情况下,研究间隙内的泄漏流动对三维粘性流场的影响。结果表明,至少对本文算例而言,在相同的工作条件下,具有适当小间隙的叶栅往往可以获得比无间隙叶栅更高的效率;而在相同的切向泄漏面积下,沿流向渐扩型间隙的叶栅可以获得更高的效率．本文的结果可以从定性和定量的角度为改进设计并合理利用叶栅间隙的泄漏流动提供参考．