Nickel/Photoredox-Catalyzed Asymmetric Reductive Cross-Coupling of Racemic α-Chloro Esters with Aryl Iodides

A unique nickel/organic photoredox co-catalyzed asymmetric reductive cross-coupling between α-chloro esters and aryl iodides is developed. This cross-electrophile coupling reaction employs an organic reductant (Hantzsch ester), whereas most reductive cross-coupling reactions use stoichiometric metals. A diverse array of valuable α-aryl esters is formed under these conditions with high enantioselectivities (up to 94 %) and good yields (up to 88 %). α-Aryl esters represent an important family of nonsteroidal anti-inflammatory drugs. This novel synergistic strategy expands the scope of Ni-catalyzed reductive asymmetric cross-coupling reactions.     

Various exact analytical solutions of a variable-coefficient Kadomtsev–Petviashvili equation

Nonlinear Dynamics - Under investigation is a generalized (3 + 1)-dimensional variable- coefficient Kadomtsev– Petviashvili equation in fluid mechanics. Various exact analytical solutions are...     

Syntheses,Characterization, and Luminescence Properties of Three Coordination Complexes with Sulfonate-Phenol Anions and Trivalent Metal Ions

Russian Journal of General Chemistry - A dinuclear Tb complex, Tb2(H2L)3(phen)2 (1), and two similar N-donor coordination complexes, Fe(phen)3·HL (2), Fe(bipy)3·HL·5H2O (3) (Na2H2L =...     

蛋白质-多糖复合体系在活性物质传递中的应用

蛋白质-多糖复合体系作为生物活性物质传递系统的壁材,有着人工合成聚合物或无机物等其他材料不可比拟的多重优势。本文就蛋白质和多糖之间的连接方式及蛋白质-多糖复合体系形成传递系统的多种形式进行了综述,以及对此领域的发展趋势进行了展望。结合蛋白质和多糖的结构特点,二者之间的链接方式分为非共价结合的物理共聚,和共价结合的美拉德偶联、化学交联、酶催化交联等方式,文中分别对各种连接方式的原理和机理,以及其影响因素做了深入阐述。以蛋白质-多糖复合体系为壁材对活性物质的传递形式大体上分成乳化系统、胶束、纳米凝胶、分子复合物以及壳核结构等系统。不同的活性物质的特征和传递需求,可针对性地选择合适结构的蛋白质和多糖种类以及二者的连接方式和传递系统的形式。并且,随着研究的逐步发展和推进,此领域的发展趋势朝着智能化和靶向性的方向进行。目前活性物质的蛋白质-多糖复合体系的传递系统,还依然面临着系统设计、评价和应用等多方面的挑战,这就要求我们在更全面更深入了解认识其对活性物质影响和功效的基础上,安全合理地设计和深入细致地评价活性成分的传递系统。     

A novel LC–MS/MS method for the determination of ziritaxestat in rat plasma and its pharmacokinetic study

Ziritaxestat is a first-in-class autotoxin inhibitor. The purpose of this study was to develop a liquid chromatography/electrospray ionization tandem mass spectrometric (LC–MS/MS) method for the determination of ziritaxestat in rat plasma. The plasma sample was deproteinated using acetonitrile and then separated on an Acquity BEH C₁₈ column with water containing 0.1% formic acid and acetonitrile as mobile phase, which was delivered at 0.4 ml/min. Ziritaxestat and the internal standard (crizotinib) were quantitatively monitored with precursor-to-product transitions of m/z 589.3 > 262.2 and m/z 450.1 > 260.2, respectively. The total running time was 2.5 min. The method showed excellent linearity over the concentration range 0.5–2000 ng/ml, with correlation coefficient >0.9987. The extraction recovery was >82.09% and the matrix effect was not significant. Inter- and intra-day precisions (RSD) were <11.20% and accuracies were in the range of −8.50–7.45%. Ziritaxestat was demonstrated to be stable in rat plasma under the tested conditions. The validated LC–MS/MS method was successfully applied to study the pharmacokinetic profiles of ziritaxestat in rat plasma after intravenous and oral administration. Pharmacokinetic results demonstrated that ziritaxestat displayed a short half-life (~3 h) and low bioavailability (20.52%).     

General Formation of Macro-/Mesoporous Nanoshells from Interfacial Assembly of Irregular Mesostructured Nanounits

Mesoporous core–shell nanostructures with controllable ultra-large open channels in their nanoshells are of great interest. However, soft template-directed cooperative assembly to mesoporous nanoshells with highly accessible pores larger than 30 nm, or even above 50 nm into macroporous range, remains a significant challenge. Herein we report a general approach for precisely tailored coating of hierarchically macro-/mesoporous polymer and carbon shells, possessing highly accessible radial channels with extremely wide pore size distribution from ca. 10 nm to ca. 200 nm, on diverse functional materials. This strategy creates opportunities to tailor the interfacial assembly of irregular mesostructured nanounits on core materials and generate various core–shell nanomaterials with controllable pore architectures. The obtained Fe,N-doped macro-/mesoporous carbon nanoshells show enhanced electrochemical performance for the oxygen reduction reaction in alkaline condition.     

A comparative study of the structure and crystallization of bulk metallic amorphous rod Pr60Ni30Al10 and melt-spun metallic amorphous ribbon Al87Ni10Pr3

Pr-based bulk metallic amorphous （BMA） rods （Pr60Ni30Al10） and Al-based amorphous ribbons （Al87Ni10Pr3） have been prepared by using copper mould casting and single roller melt-spun techniques, respectively. Thermal parameters deduced from differential scanning calorimeter （DSC） indicate that the glass-forming ability （GFA） of Pr60Ni30Al10 BMA rod is far higher than that of Al87Ni10Pr3 ribbon. A comparative study about the differences in structure between the two kinds of glass-forming alloys, superheated viscosity and crystallization are also made. Compared with the amorphous alloy Al87Ni10Pr3, the BMA alloy Pr60Ni30Al10 shows high thermal stability and large viscosity, small diffusivity at the same superheated temperatures. The results of x-Ray diffraction （XRD） and transmission electron microscope （TEM） show the pronounced difference in structure between the two amorphous alloys. Together with crystallization results, the main structure compositions of the amorphous samples are confirmed. It seems that the higher the GFA, the more topological type clusters in the Pr-Ni-Al amorphous alloys, the GFAs of the present glass-forming alloys are closely related to their structures.     

约束层对激光驱动冲击波压力影响机理的理论研究

针对刚性约束层、柔性约束层以及液体约束层，从激光诱导冲击波阵面状态、汽化物(包括气体和等离子体)扩散以及冲击波的反射进行分析，发现对于脉宽小于冲击波通过汽化物层的时间间隔的短脉冲激光，约束层并不能直接提高冲击波的冲量，而对于脉宽大于冲击波通过汽化层时间间隔的激光，其增强冲击效果是通过约束汽化物的扩散，提高压力幅值和由于冲击波在约束层与工件表面的多次反射而延长对工件的作用时间来实现的.刚性约束层能最大地增加冲击冲量，而柔性约束层和液体约束层的主要优点是其形状可与非平面形工件表面符合. 关键词： 激光 约束层 扩散 反射波