Isosteres of peptides: boron analogs as dipolar forms of α‐amino acids – a theoretical study

Modification of peptides to produce peptidomimetics is of great interest, with the aim of designing potent, selective, and metabolically stable analogs having certain conformational properties. Organoboranes have been reported in the literature with a wide range of therapeutic applications. One of the therapeutically important class of molecules is amine‐carboxyboranes derived from amino acids by replacement of the Cα atom of an amino acid/peptide by boron. The conformational preferences of these peptides, with respect to backbone ω, ?, and ψ torsion angles, have been investigated by theoretical calculations. The amide bond in these molecules has the same geometry in the ground and transition states as the natural peptides. However, the boron isosteres of glycine and alanine peptides are less structured than their natural derivatives, but are distinguished by structures with a positive value for the ? angle, which is normally disfavored for natural peptides. This property could be used to build peptides with a geometry not usually seen in natural peptides. Copyright © 2007 John Wiley & Sons, Ltd.     

将SVRT模型应用到单原子多原子反应F+CH2D2→CH2D/CHD2+DF/HF中

由于含时波包方法具有经典的直观又不乏量子力学的准确 ,选择含时波包方法来处理F +CH2 D2 →CH2 D/CHD2 +DF/HF反应 .把半刚性振转子 (SVRT)模型应用到该反应体系中 ,研究了两个通道中该反应从基态反应物开始在修正过的J1(MJ1)势能面上计算出来了反应几率、积分截面、速率常数 .反应几率随能量变化的图的数值结果给出了振荡结构 ,这些振荡结构是可以和动力学振荡联系起来的 .而这些振荡结构在积分截面随着能量变化的图中就被反应几率求和后的平均结果所掩盖了 .速率常数和实验结果的比较也得到了较好的结果 .     

Fe(110)面上CO化学吸附状态的吸附历史依赖关系

Fe(110)面上直接在室温时吸附的CO同先在170 K吸附然后升温到室温的CO吸附有所不同. 前者有解离而后者无解离; 另外, 前者的饱和吸附量比后者低. 这可以用前者发生了解离来解释. 根据以上结果, 提出了以下的设想, Fe(110)面上的CO解离除了需要足够的热能而外, 还需要在表面的吸附位上有邻近的其它未被覆盖Fe原子的存在, 即需要一定的表面结构.     

真空下X2 (X=Cl、Br)与AgOCN气-固反应机理

在真空条件下完成了X2 (X=Cl、Br)与AgOCN间的气-固异相反应，利用紫外光电子能谱（PES）仪，探测与确定反应产物是XNCO (X=Cl、Br)，并推断其可能为一过渡态反应，生成中间络合物，新键产生与旧键断裂同时进行.     

Pattern of separatrices and intrinsic reaction coordinates for degenerate thermal rearrangements

A structurally stable model of the standard adiabatic gradient field of the potential energy surface for certain pericyclic reactions is derived.These reactions are not subjected to the principles of orbital isomerism or to the Woodward-Hoffmann rules.Use is made of a principle established by Ariel Fernández and Oktay Sinanolu which precludes direct meta-IRC connections between transition states.It is shown that Jahn-Teller isomers of the singlet biradicals involved in the process are not interconvertible since the biradical configuration is not a transition state but a critical point with Hessian matrix with two negative eigenvalues.The topological features of the PES obtained by combinatorial methods are in full agreement with earlier results obtained from MINDO calculations.     

Fitting complex potential energy surfaces to simple model potentials: application of the simplex-annealing method

A stochastic method of optimization, which combines simulated annealing with simplex, is implemented to fit the parameters of a simple model potential. The main characteristic of the method is that it explores the whole space of the parameters of the model potential, and therefore it is very efficient in locating the global minimum of the cost function, in addition to being independent of the initial guess of the parameters. The method is employed to fit the complex intermolecular potential energy surface of the dimer of water, using as a reference the spectroscopic quality anisotropic site-site potential of Feller et al. The simple model potential chosen for its reparameterization is the MCY model potential of Clementi et al. The quality of the fit is assessed by comparing the geometry of the minimum, the harmonic frequencies, and the second virial coefficients of the parameterized potential with the reference one. Finally, to prove more rigorously the robustness of this method, it is compared with standard nonstochastic methods of optimization.     

几种热塑性特种工程塑料的热分析研究

聚芳醚和聚芳硫醚两类聚合物都为热塑性的耐高温特种高分子材料 ,由于它们的加工性好、加工成型效率高 ,受到了世界各国的高度重视。这两类聚合物在结构上有许多相似之处 ,如它们的主链都含苯环、酮基或砜基 ,而聚芳醚类聚合物的柔性基团为醚键 ,聚芳硫醚类聚合物的柔性基团为硫醚键 ,但由于氧和硫在元素周期表中属于同一族元素 ,原子结构仍然相似 ,因而在某些方面具有一定的可比性。研究它们的性能差异对于改进聚合物性能以及进行进一步的结构设计将有一定的帮助。在这两类聚合物中 ,国内已商品化生产的品种有ＰＥＥＫ、ＰＥＳ和ＰＰＳ ,有…     

Atomic radical—molecule reactions F + CH<Subscript>3</Subscript>C≡CH: mechanistic study

The reaction of atomic radical F with propyne has been studied theoretically using ab initio quantum chemistry methods and transition state theory. The potential energy surface was calculated at the CCSD(T)/aug-cc-pVDZ (single-point) level using the UMP2/6-311++G(d,p) optimized structures. Two reaction mechanisms including the addition–isomerization–elimination reaction mechanism and the directed hydrogen abstraction reaction mechanism are considered. For the hydrogen abstraction reactions, i.e., the most probable evolution pathway in the title reaction, the HF formation occurs via direct abstraction mechanism dominantly and the H atom picked up by the atomic radical F should come mostly from the methyl group of normal propyne. On the other hand, for the addition–isomerization–elimination mechanism, the most feasible pathway should be the atomic radical F attacking on the C≡C triple bond in propyne (CH₃C≡CH) to form a weakly-bound adduct A1 with no barrier, followed by F addition to the C≡C triple bond to form the low-lying intermediate isomer 5. Subsequently, isomer 5 directly dissociates to P3 H₂CCCHF + H via transition state TS₅/P3. The other reaction pathways on the doublet PES are less competitive due to thermodynamical or kinetic factors. Furthermore, based on the analysis of the kinetics of all channels through which the addition and abstraction reaction proceed, we expect that the competitive power of reaction channels may vary with experimental conditions for the title reaction. The present work will provide useful information for understanding the processes of atomic radical F reaction with other unsaturated hydrocarbons. This material is available from author via E-mail.     

Rg—HX(Rg=He,Ne;X=F,Cl,Br)分子间势的精确量子化学从头计算研究III.He—HBr

在用非迭代的三重激发项来校正CCSD的CCSD（T）理论水平下，采用aug-cc- pVQZ基函数对He—HBr的分子间势进行了系统的研究。结果表明：He—HBr以线型结 构存在。在极限基的情况下，复合物两种线型极小点结构He—H—Br和He—Br—H势 阱深分别为28.792 cm~(-1)和35.707 cm~(-1)，对应He原子到HBr分子质心的距离 R分别为0.407 nm和0.343 nm。讨论了不同的基函数和理论方法在研究此类弱束缚 态复合物的分子间势时的可靠性及其对结果的影响，同时也给出了热函数的解析形 式。     

Gaseous nitryl azide N4O2: A joint theoretical and experimental study

Gaseous nitryl azide N₄O₂ is generated by the heterogeneous reaction of gaseous ClNO₂ with freshly prepared AgN₃ at −50 °C. The geometric and electronic structure of the molecule in the gas phase has been characterized by in situ photoelectron spectroscopy (PES) and quantum chemical calculations. The experimental first vertical ionization energy of N₄O₂ is 11.39 eV, corresponding to the ionization of an electron on the highest occupied molecular orbital (HOMO) {4a″(π_{nb(N4–N5–N6)})}⁻¹. An apparent vibrational spacing of 1600 ± 60 cm⁻¹ (ν_asO1N2O3) on the second band at 12.52 eV (π_{nb(O1–N2–O3)}) further confirms the preference of energetically stable chain structure in the gas phase. To complement the experimental results, the potential-energy surface of this structurally novel transient molecule is discussed. Both calculations and spectroscopic results suggest that the molecule adopts a trans-planar chain structure, and a five-membered ring decomposition pathway is more favorable.