Online resource for theoretical study of hydration of biopolymers

An online resource has been developed for the theoretical study of hydration of biopolymers by the RISM (Reference Interaction Site Model) method, deriving from the integral equation theory of liquids. The online resource is based upon original software developed by the authors and includes all steps in studying a biopolymer with a given spatial structure and force field. It prepares the input data and carries out the RISM calculation yielding the atom-atom correlation functions of the biopolymer with water as solvent. From these functions the algorithm finds atomic partial contributions to the hydration free energy using various free energy expressions from integral equation theory. The calculated results are automatically recorded in a database, and become available on the website as tables of partial thermodynamic quantities. In addition, the website displays an interactive 3D model of a given molecule, the atoms of which can be painted in different colors in accordance with their partial contributions to the thermodynamic quantity chosen by the user. The user can interactively choose atoms on this molecule and their correlation functions will be displayed. The aim of our work was to develop and present a publicly-accessible resource on the basis of original software which could be used for scientific and educational purposes.     

Synthesis of CuCorePtShell Nanoparticles as Model Structures for Core–Shell Electrocatalysts by Direct Platinum Electrodeposition on Copper

The synthesis of Cu(core)Pt(shell) model catalysts by the direct electrochemical deposition of Pt on Cu particles is presented. Cu particles with an average diameter of 200 nm have been deposited on glassy‐carbon electrodes by double pulse electrodeposition from a copper sulfate solution. Subsequent deposition from a platinum nitrate solution under potential control allows for a high selectivity of the Pt deposition towards Cu. Using a combination of cyclic voltammetry, XPS and sputtering, the structure of the generated particles has been analyzed and their core–shell configuration proven. It is shown that the electrocatalytic activity for the oxygen reduction is similar to that of other PtCu catalyst systems. The synthesized structures could allow for the analysis of structure–activity relations of core–shell catalysts on the way to the simple and controlled synthesis of supported Cu(core)Pt(shell) nanoparticles as oxygen reduction catalysts.     

Cr2O3和CrO3/Cr2O3催化剂的2-氯-1,1,1-三氟乙烷气相氟化反应的活性物种和失活

采用沉淀法和浸渍法制备了2种铬基（Cr₂O₃和CrO₃/Cr₂O₃）催化剂,用于气相氟化2-氯-1,1,1-三氟乙烷合成1,1,1,2-四氟乙烷。研究发现含有低价铬（Cr³⁺）物种的Cr₂O₃催化剂上2-氯-1,1,1-三氟乙烷的稳态转化率为18.5%,而含有高价铬（Cr⁶⁺）物种和低价铬（Cr³⁺）物种的CrO₃/Cr₂O₃催化剂初始转化率达到30.6%,然而存在明显的失活。含有Cr⁶⁺物种的CrO₃/Cr₂O₃催化剂的2-氯-1,1,1-三氟乙烷氟化反应初始TOF值为1.71×10^-4 mol_HCFC-133a·mol_Cr（Ⅵ）^-1·s^-1,高于含有Cr³⁺物种的Cr₂O₃催化剂（4.16×10^-5 mol_HCFC-133a·mol_Cr（Ⅲ）^-1·s^-1）。Cr₂O₃催化剂在氟化反应前后催化剂的物相结构保持不变;而含有高价铬物种的CrO₃/Cr₂O₃催化剂经HF反应后生成了CrO_xF_y活性物种。然而,CrO_xF_y物种在反应中挥发或转化成稳定但无活性的CrF₃,从而导致催化剂失活。     

CuI‐Catalyzed Multicomponent Synthesis of Aminoindolizines from Aldehydes,Amines, and Alkynes under Solvent‐Free Conditions

A direct and efficient approach to 1‐aminoindolizines through three‐component one‐pot reaction of heteroaryl aldehydes, secondary amines and terminal alkynes catalyzed by CuI under solvent‐free conditions has been developed. This methodology provides a rapid access to substituted aminoindolizines with good yields (up to 97%).     

燃料电池铂钴锰合金催化剂的制备及性能

为提高PtCo/C合金催化剂的电化学性能,采用微波法合成铂钴锰催化剂前驱体,经高温热处理形成合金,最后通过酸处理得到铂钴锰合金催化剂(PtCoMn/C)。电化学测试结果表明:适量锰的添加可提升PtCo/C催化剂的活性和耐久性。PtCoMn/C催化剂在 0.9 V(vs RHE)电压下的质量比活性(MA)达到 0.666 A·mg_Pt^-1,是传统 Pt/C 的 2.66 倍,是 PtCo/C 催化剂的 1.30 倍。在30 000圈催化剂加速耐久性测试中,PtCoMn/C合金催化剂的电化学活性面积(ECSA)和质量比活性(MA)仅下降6.9%和27.1%,均远低于Pt/C催化剂。     

Distereoselective one-pot synthesis of pyrimidopyrimidines using sulfated tin oxide as a reusable catalyst： An extension of Biginelli-type reaction

The Biginelli-type compounds 4,5,8a-triarylhexahydropyrimido[4,5-d]pyrimidine-2,7（1H,3H）-diones were synthesized by a one-pot three-component reaction using sulfated tin oxide as a reusable catalyst. This method has the advantages of high yields, short reaction time, simple starting materials and reusability of catalyst for several times.     

Understanding the Initial Decomposition Pathways of the n‐Alkane/Nitroalkane Binary Mixture

Addition of nitroalkanes into n‐alkanes can lower the activation barriers of free‐radical production and accelerate the decomposition of n‐alkanes at relatively low temperatures. Four initial decomposition mechanisms of the n‐butane/nitroethane binary mixture were proposed for the promoting effect and considered theoretically at the B3LYP, BB1K, BMK, MPW1K, and M06‐2X levels with MG3S basis set. Energetics above was compared to high‐level CBS‐QB3 and G4 calculations. Calculated results confirm the feasibility of the four initial decomposition pathways: (I) the C? NO₂ bond rupture of nitroethane to produce ethyl and ·NO₂, (II) HONO elimination from nitroethane followed by decomposition to ·OH and ·NO, (III) rearrangement of nitroethane to ethyl nitrite which further dissociates into CH₃CH₂O· and ·NO, and (IV) direct hydrogen‐abstraction of nitroethane with n‐butane.     

Al-MCM-41 负载离子液体双酸位催化剂及制备生物柴油

采用不同硅铝比的MCM-41负载离子液体,制备得到一系列负载型双酸位催化剂,并用XRD、FTIR、N₂-吸脱附、热重分析及TEM对其进行表征,以大豆油与甲醇的酯交换反应为探针实验考察了其催化活性.结果表明,离子液体成功固载于介孔分子筛并能保持其介孔结构,且在酯交换反应中表现出良好的反应活性.在ILs负载量为30%,醇油物质的量的比为36:1,140 ℃下反应5 h,生物柴油收率在90%以上;而分子筛中Al的引入为活性组分离子液体构建了有益的酸环境,促进了其催化活性的提高;与均相离子液体相比,负载型催化剂又能明显提高生物柴油的收率,且回收利用4次后,生物柴油收率仍接近88%.