Fused vs. spiro: Kinetic,not thermodynamic preference may direct the reaction of α-carbonyl oxonium ylides

Rh(II)-catalyzed decomposition of certain cyclic α-diazocarbonyl compounds in the presence of cyclic ethers has been shown to give bicyclic ring expansion products. These are thought to arise from a [1,4]-alkyl shift toward the carbonyl oxygen atom and are in contrast with the recently observed spirocyclic products of a Stevens-type [1,2]-alkyl shift within the postulated oxonium ylide intermediate. Quantum chemical calculations performed at the B3LYP/6-31G* level of theory showed that the former reaction pathway (toward fused bicycles) is kinetically preferred.     

Synthesis and conformational investigation of tetrapeptide analogues of the fragment B23-B26 of insulin

Tetrapeptides containing one of a set of four different α,α-dialkyl glycines at the C-terminus were synthesized by conventional methods in solution and their conformational behavior investigated by ¹H NMR spectroscopy in connection with molecular mechanics calculations. The results were consistent with conformations stabilized by a γ-turn in the case of compounds with alkyl groups larger than methyl, while the corresponding Aib derivative did not exhibit intramolecular hydrogen bonding.     

Synthesis of Dimethyl Carbonate from CO2 , Methanol, and Epoxides Using Re（CO） 5 Cl/K2 CO3 as Catalyst System

IntroductionOver the past few years, dimethyl carbonate(DMC) has been proven to be an efficientmethylating,methoxylating, and methoxycarbonylating agent inorganic syntheses, in which DMC is used to replace thetoxic methyl halides, dimethyl sulfate or carb     

The Transport Properties of the Cell Membrane Ion Channels in Electric Fields: Bethe Lattice Treatment

The interactive two-state model of cell membrane ion channels in an electric field is formulated on the Bethe lattice by means of the exact recursion relations. The probability of channel opening or maximum fractions of open potassium and sodium channels are obtained by solving a non-linear algebraic equation. Using known parameters for the conventional mean-field theory the model gives a good agreement with the experiment both at low and high trans-membrane potential values. For intermediate voltages, the numerical results imply that collective effects are introduced by trans-membrane voltage.     

First-principles study on the origin of optical transitions to be associated with F colour centers for PbWO4 crystals

The electronic structures of PbWO₄ crystals containing F type color centers with the lattice structure optimized are studied within the framework of the fully relativistic self-consistent Direc–Slater theory, using a numerically discrete variational (DV-Xα) method. The calculated results show that F and F⁺ centers have donor energy level in forbidden band. Their optical transition energy are 1.84 eV, 2.21 eV, respectively, which corresponds to the 680 nm, 550 nm absorption bands. It predicts that the 680 nm, 550 nm absorption bands originate form the F and F⁺ centers in PbWO₄ crystals.     

Generalized 3G theorem and application to relativistic stable process on non-smooth open sets

Let G(x,y) and GD(x,y) be the Green functions of rotationally invariant symmetric α-stable process in Rd and in an open set D, respectively, where 0<α<2. The inequality GD(x,y)GD(y,z)/GD(x,z)?c(G(x,y)+G(y,z)) is a very useful tool in studying (local) Schrödinger operators. When the above inequality is true with c=c(D)∈(0,∞), then we say that the 3G theorem holds in D. In this paper, we establish a generalized version of 3G theorem when D is a bounded κ-fat open set, which includes a bounded John domain. The 3G we consider is of the form GD(x,y)GD(z,w)/GD(x,w), where y may be different from z. When y=z, we recover the usual 3G. The 3G form GD(x,y)GD(z,w)/GD(x,w) appears in non-local Schrödinger operator theory. Using our generalized 3G theorem, we give a concrete class of functions belonging to the non-local Kato class, introduced by Chen and Song, on κ-fat open sets. As an application, we discuss relativistic α-stable processes (relativistic Hamiltonian when α=1) in κ-fat open sets. We identify the Martin boundary and the minimal Martin boundary with the Euclidean boundary for relativistic α-stable processes in κ-fat open sets. Furthermore, we show that relative Fatou type theorem is true for relativistic stable processes in κ-fat open sets. The main results of this paper hold for a large class of symmetric Markov processes, as are illustrated in the last section of this paper. We also discuss the generalized 3G theorem for a large class of symmetric stable Lévy processes.     

纳米晶复合Pr2Fe14B/α-Fe永磁材料磁性的研究

采用熔体快淬的方法制备Pr₂Fe₁₄B/α-Fe纳米晶复合永磁材料.使用振动样品磁强计(VSM)测量样品的室温磁性能.实验合金成分为(Pr_xFe_94.3-xB_5.7)_0.99Zr₁(其中x＝8.2，8.6，9.0，9.4，9.8，10.2，10.6，11.0，11.4(原子分数，%)).系统地研究了辊速及合金成分对快淬带磁性能的影响，当Pr原子分数由8. 关键词： 纳米复合永磁材料 熔体快淬 2Fe₁₄B/α-Fe')" href="#">Pr₂Fe₁₄B/α-Fe 磁性     

催化动力学光度法测定痕量钴(Ⅱ)

本法基于钴 (Ⅱ )对高碘酸钾氧化孔雀绿的催化作用 ,提出一种灵敏地测定痕量钴 (Ⅱ )的新方法。该方法线性范围在 0～ 0 8μg·2 5mL- 1 ,检测限为 2 1× 10 - 1 0 g·mL- 1 。测定出反应表现活化能Ea=37 94kJ·mol- 1 。此法用于茶叶、维生素B1 2 中钴的测定 ,结果满意     

Zur Synthese und Struktur von K3N

Synthesis and Structure of K₃N Two phases in the binary system K/N have been obtained via co‐deposition of potassium and nitrogen onto polished sapphire at 77 K and subsequent heating to room temperature. The powder diffraction pattern of one of these phases can be satisfactorily interpreted by assuming the composition K₃N, and the anti‐TiI₃ structure‐type, which is also adopted by Cs₃O. The resulting hexagonal lattice constants are: a = 779.8(2), c = 759.2(9) pm, Z = 2, P6₃/mcm. Comparison with possible structures of K₃N generated by computational methods and refined at Hartree‐Fock‐ and DFT level, reveals that the energetically most favoured structure has not formed (presumable Li₃P‐type), but instead one of those with very low density. In this respect, the findings for K₃N are analogous to the results on Na₃N. The thermal evolution of the deposited starting mixture has been investigated. Hexagonal K₃N transforms to another K/N phase at 233 K. Its XRD can be fully indexed resulting in an orthorhombic cell a = 1163, b = 596, c = 718 pm. Decomposition leaving elemental potassium as the only residue occurs at 263 K.