室温下钯催化生成联苯的合成方法

在催化量级的二价钯和氧化剂的作用下,苯直接经碳氢键活化在酸性体系中室温下氧化偶联生成联苯。通过对各种催化剂、氧化剂、酸等因素对联苯产物生成的影响的考察,醋酸钯/过硫酸钾/三氟乙酸体系确定为最有效的反应体系,联苯收率在24 h内可达24%,转化数TON值为6.0。     

取代1-氯蒽醌中分子内卤键的电子密度拓扑分析

运用量子化学密度泛函B3LYP方法,在6-311＋＋G（d,p）基组水平上对邻位和间位取代1-氯葸醌的分子内卤键进行了研究．用电子定域函数和“分子中的原子,,理论对分子内卤键的性质进行了电子密度拓扑分析．通过对计算得到的密度矩阵进行σ-π兀分离,得到了π-键的键径和分子图,并讨论了。电荷密度和兀电荷密度对卤键的影响．结果表明,键鞍点和环鞍点处的电子密度拓扑性质均可作为衡量分子内卤键强度的量度．键鞍点和环鞍点处的电荷密度P越大,键鞍点与环鞍点的距离越大,卤键强度越大．除σ电荷密度外,π电荷密度对分子内卤键的性质也有明显影响．     

Charge‐Induced Unzipping of Isolated Proteins to a Defined Secondary Structure

Here we present a combined experimental and theoretical study on the secondary structure of isolated proteins as a function of charge state. In infrared spectra of the proteins ubiquitin and cytochrome c, amide I (C=O stretch) and amide II (N–H bend) bands can be found at positions that are typical for condensed‐phase proteins. For high charge states a new band appears, substantially red‐shifted from the amide II band observed at lower charge states. The observations are interpreted in terms of Coulomb‐driven transitions in secondary structures from mostly helical to extended C₅‐type hydrogen‐bonded structures. Support for this interpretation comes from simple energy considerations as well as from quantum chemical calculations on model peptides. This transition in secondary structure is most likely universal for isolated proteins that occur in mass spectrometric experiments.     

Thermally Induced Carbohydroxylation of Styrenes with Aryldiazonium Salts

The radical carbohydroxylation of styrenes with aryldiazonium salts has been achieved under mild thermal conditions. A broad range of aryldiazonium salts was tolerated, and the reaction principle based on a radical–polar crossover mechanism could be extended to carboetherification as well as to a two‐step, metal‐free variant of the Meerwein arylation leading to stilbenes.     

宽板塑性弯曲成形过程中的板厚变化规律

根据宽板弯曲过程中的变形与应力分布特征，提出了一种计算弯曲过程中板料厚度随弯曲程度变化的新的近似解答方法．该方法基于塑性增量理论，应用塑性成形过程的体积不变假设和弯曲过程的平面假设．作为算例，得到了理想刚塑性材料的板料厚度、变薄系数以及应变中性层内移系数随板料弯曲内表面曲率半径变化的规律，并与实验数据进行了比较，两吻合良好．     

Synthesis of Benzo[4,5]thiazolo[2,3-c][1,2,4]triazole Derivatives via C-H Bond Functionalization of Disulfide Intermediates

Many nitrogen- and sulfur-containing heterocyclic compounds exhibit biological activity. Among these heterocycles are benzo[4,5]thiazolo[2,3-c][1,2,4]triazoles for which two main synthetic approaches exist. Here we report a new synthetic protocol that allows the preparation of these tricyclic compounds via the oxidation of a mercaptophenyl moiety to its corresponding disulfide. Subsequent C-H bond functionalization is thought to enable an intramolecular ring closure, thus forming the desired benzo[4,5]thiazolo[2,3-c][1,2,4]triazole. This method combines a high functional group tolerance with short reaction times and good to excellent yields.     

The Phosphorus Bond,or the Phosphorus-Centered Pnictogen Bond: The Covalently Bound Phosphorus Atom in Molecular Entities and Crystals as a Pnictogen Bond Donor

The phosphorus bond in chemical systems, which is an inter- or intramolecular noncovalent interaction, occurs when there is evidence of a net attractive interaction between an electrophilic region associated with a covalently or coordinately bonded phosphorus atom in a molecular entity and a nucleophile in another, or the same, molecular entity. It is the second member of the family of pnictogen bonds, formed by the second member of the pnictogen family of the periodic table. In this overview, we provide the reader with a snapshot of the nature, and possible occurrences, of phosphorus-centered pnictogen bonding in illustrative chemical crystal systems drawn from the ICSD (Inorganic Crystal Structure Database) and CSD (Cambridge Structural Database) databases, some of which date back to the latter part of the last century. The illustrative systems discussed are expected to assist as a guide to researchers in rationalizing phosphorus-centered pnictogen bonding in the rational design of molecular complexes, crystals, and materials and their subsequent characterization.     

Laser polarization effects on K-shell Compton scattering

We study Compton scattering on the ground state of the hydrogen atom in the presence of an intense low-frequency electric field (the laser) of arbitrary polarization, for incident and scattered photons of energies around 15 keV. The adopted formalism is the nonrelativistic one developed by Voitkiv et al. [J. Phys. B: At. Mol. Opt. Phys. 36, 1907 (2003)] and applied by them for a circularly polarized laser. We explore the spectrum and the electron energy distribution in their dependence on the incident photon energy or electric field intensity, for different polarizations.     

Research on Flood Loss Distribution and Catastrophe Bond Pricing Based on Bayesian Inference

Taking flood catastrophe risk in China as the research background, aiming at the characteristics of flood loss ``low frequency and high loss', Bayesian inference method is used to fit the loss distribution, and Bayesian inference is used to obtain the loss frequency distribution and loss quota distribution of flood in China. On this basis, Monte Carlo simulation method is used to calculate the probability distribution of annual flood loss in China under different trigger conditions, and then CAPM is used to study the pricing of flood catastrophe bonds in China. It is concluded that under different trigger conditions, as the trigger value increases gradually, the corresponding trigger is triggered. Comparing the three types of bonds, it can be found that the price of bonds decreases with the decrease of principal guarantee ratio and the increase of principal loss ratio, that is, the investment risk is directly proportional to the return, which provides reference for issuing flood catastrophe bonds in China.