Integration of [(Co(bpy)3]2+ Electron Mediator with Heterogeneous Photocatalysts for CO2 Conversion

An efficient chemical system for electron generation and transfer is constructed by the integration of an electron mediator ([Co(bpy)₃]²⁺; bpy=2,2′‐bipyridine) with semiconductor photocatalysts. The introduction of [Co(bpy)₃]²⁺ remarkably enhances the photocatalytic activity of pristine semiconductor photocatalysts for heterogeneous CO₂ conversion; this is attributable to the acceleration of charge separation. Of particular interest is that the excellent photocatalytic activity of heterogeneous catalysts can be developed as a universal photocatalytic CO₂ reduction system. The present findings clearly demonstrate that the integration of an electron mediator with semiconductors is a feasible process for the design and development of efficient photochemical systems for CO₂ conversion.     

Asymmetric Michael Addition/Intramolecular Cyclization Catalyzed by Bifunctional Tertiary Amine–Squaramides: Construction of Chiral 2‐Amino‐4H‐chromene‐3‐Carbonitrile Derivatives

The efficient asymmetric Michael addition/intramolecular cyclization of malononitrile with dienones catalyzed by a chiral bifunctional tertiary amine–squaramide catalyst for the synthesis of chiral 2‐amino‐4H‐chromene‐3‐carbonitrile derivatives was developed. The corresponding products were obtained in good to excellent yields (up to 99 %) with excellent enantioselectivities (up to 98 % ee) for most of the bisarylidenecyclopentanones.     

Flame atomic absorption spectrometry determination of trace amount of gold after separation and preconcentration onto ion-exchange polyethylenimine coated on Al2O3

The object of this work is to develop a simple and selective method for efficient extraction of Au(III) ions in aqueous solution using a new solid-phase extraction sorbent. Polyethylenimine (PEI) ion-exchange polymer was coated on alumina in the presence of NaNO₃. The method is based on sorption of Au³⁺ ions on 50 mg PEI/Al₂O₃. A solution of 0.5 M thiourea, then 1.0 M HCl effectively eluted the gold ion and then aspirated into flame atomic absorption spectroscopy (FAAS). The influence of flow rate of sample solution and eluent, the pH effect, eluent type and sorption capacity was investigated. The effects of various diverse ions for preconcentration and separation of the gold ion were investigated. Relative standard deviation of 4.0 μg mL⁻¹ of gold was 1.46% (n = 10). The detection limit was 26.2 ng L⁻¹ in original solution. The method has been applied successfully for the recovery of trace amount of Au(III) ions from water samples.     

Ligand‐Free Palladium‐Catalyzed Aerobic Oxidative Coupling of Carboxylic Anhydrides with Arylboronic Acids

We report a new, effective and environmentally friendly protocol for selective aerobic oxidative coupling of arylboronic acids with carboxylic anhydrides in the presence of ligand‐free palladium catalyst. The aryl benzoates are obtained in good to excellent yields.     

N-Aryl Isoleucine Derivatives as Angiotensin?II AT2 Receptor Ligands

A novel series of ligands for the recombinant human AT₂ receptor has been synthesized utilizing a fast and efficient palladium-catalyzed procedure for aminocarbonylation as the key reaction. Molybdenum hexacarbonyl [Mo(CO)₆] was employed as the carbon monoxide source, and controlled microwave heating was applied. The prepared N-aryl isoleucine derivatives, encompassing a variety of amide groups attached to the aromatic system, exhibit binding affinities at best with K_i values in the low micromolar range versus the recombinant human AT₂ receptor. Some of the new nonpeptidic isoleucine derivatives may serve as starting points for further structural optimization. The presented data emphasize the importance of using human receptors in drug discovery programs.     

有机催化吲哚碳环上的不对称Friedel⁃Crafts烷基化反应

将金鸡纳碱衍生物双功能催化剂用于有机催化羟基吲哚与靛红的不对称Friedel-Crafts反应, 筛选出最佳反应条件: 催化剂为5%(摩尔分数)6′-脱甲基奎尼丁(1b), 溶剂为四氢呋喃, 反应温度 0 ℃. 以67%~91%的产率和最高达97%的对映选择性获得了苯环上取代的羟基烷基化产品. 拓宽了该反应的催化剂类型和底物范围.     

单原子材料类酶催化及生物医学应用研究进展

纳米酶因其经济、 稳定、 性质可调和可循环利用等诸多优势, 成功地克服了天然酶在实际应用中的不足. 单原子材料的出现使得对纳米酶的研究迈入原子水平, 其较高的原子利用率、 独特的配位环境和较强的金属-载体相互作用为揭示纳米酶构效关系及调控类酶活性提供了可能. 本文总结了近年来单原子材料类酶催化的研究进展, 重点讨论了单原子材料类酶活性的调控策略和催化机理, 概述了单原子类酶材料在癌症治疗、 抗氧化治疗、 抗菌以及生物传感等方面的应用, 并对单原子类酶材料的发展前景进行了展望.     

铱单原子和纳米粒子在N2O分解反应中的协同催化

原子捕获法是在高温条件下制备高热稳定单原子催化剂的有效方法之一. 但该方法制备的单原子催化剂通常面临着催化活性低、 反应适用范围窄的问题. 因此, 拓展这类单原子催化剂的应用是亟待解决的难点. 本文采用高温捕获法制备的铱(Ir)单原子催化剂在氮氧化物分解反应中的催化活性较低, 但是在继续负载纳米粒子后, 单原子与纳米粒子之间表现出显著的协同催化作用. X射线光电子能谱(XPS)和CO吸附的原位漫反射红外光谱(CO-DRIFTs)表征结合反应动力学分析揭示了反应的活性中心是金属态的Ir纳米粒子. 虽然氧化态的Ir单原子不能直接活化N₂O分子, 但是可以改变Ir纳米粒子的电子结构和吸附性能. 氧气程序升温脱附(O₂-TPD)实验证实, 单原子的存在可以促进O₂从Ir纳米粒子上脱附, 从而提高催化剂的反应活性.     

石墨炔零价金属原子催化剂的合成及应用

原子催化剂是零价金属原子锚定于载体上的一种新型催化剂, 具有原子利用率高、 选择性高以及反应活性和稳定性高等优点, 一直是催化领域的研究前沿, 在催化和能量转换领域具有广阔的发展前景. 石墨炔与金属原子之间独特的不完全电荷转移性质实现了零价过渡金属原子的稳定锚定, 解决了传统单原子催化剂易迁移和聚集的问题, 被认为是新一代催化剂. 本综述从石墨炔原子催化剂的结构性质、 表征以及应用等方面出发, 综合评述了相关领域的最新研究成果, 介绍了石墨炔原子催化剂在电催化固氮制氨、 产氢、 全水解和CO₂固定等方面的应用和发展前景, 为实现新概念高性能催化材料的设计合成提供了研究思路.     

载酶纳米催化体系用于疾病诊疗的研究进展

酶作为一种具有高度特异性和高效性的催化剂, 可在细胞器中通过复杂有序的生化反应调节细胞的代谢过程. 受细胞区隔化结构的启发, 仿生设计纳米酶催化体系、 构筑限域酶催化微环境从而提高酶催化活性的研究为酶催化应用开辟了新思路. 纳米催化体系保留了小尺寸、 大比表面积、 肿瘤部位选择性富集等优势, 在疾病的诊疗方面发挥了巨大的优势. 本文首先总结了天然酶、 模拟酶和级联酶体系的催化机理, 对仿生构筑的纳米酶催化材料的载体体系进行了概述, 介绍了纳米酶催化体系在生物成像方面的应用, 讨论了其在相关代谢类疾病的作用途径, 并对纳米酶催化体系用于生物诊疗的发展前景进行了展望.