TBAI‐Catalyzed/Water‐Assisted Double C−S Bond Formations: An Efficient Approach to Sulfides through Metal‐Free Three‐Component Reactions

An aqueous catalytic method for double C?S bond formations that involves alcohol derivatives, organic halides, and sodium thiosulfate has been developed. A diverse range of functionalized sulfides, including pharmaceutical and biological derivatives, can be obtained in an efficient and eco‐friendly manner under air. The mechanistic studies revealed that this tetrabutylammonium‐iodide‐catalyzed/water‐assisted reaction generated a mercaptan species as the key intermediate.     

2,4-二甲基吡咯-3,5-二羧酸二乙酯的合成——推荐一个大学有机化学实验

采用Knorr吡咯合成法，以乙酰乙酸乙酯和亚硝酸钠为原料，在醋酸和锌粉作用下采用“一锅法”得到2,4-二甲基吡咯-3,5-二羧酸二乙酯。本实验涉及到控温、回流、重结晶、熔点测定、红外光谱及核磁共振等实验操作和分析检测方法。该实验原料简单易得、产物收率高，结合波谱解析方法，可以培养和提高学生合成实验的能力，加强学生对杂环合成和波谱解析的理解与分析。     

Enhanced Catalytic Activity in Liquid‐Exfoliated FeOCl Nanosheets as a Fenton‐Like Catalyst

A facile liquid‐phase exfoliation method to prepare few‐layer FeOCl nanosheets in acetonitrile by ultrasonication is reported. The detailed exfoliation mechanism and generated products were investigated by combining first‐principle calculations and experimental approaches. The similar cleavage energies of FeOCl (340 mJ m^?2) and graphite (320 mJ m^?2) confirm the experimental exfoliation feasibility. As a Fenton reagent, FeOCl nanosheets showed outstanding properties in the catalytic degradation of phenol in water at room temperature, under neutral pH conditions, and with sunlight irradiation. Apart from the increased surface area of the nanosheets, the surface state change of the nanosheets also plays a key role in improving the catalytic performance. The changes of charge density, density of states (DOS), and valence state of Fe atoms in the exfoliated FeOCl nanosheets versus plates illustrated that surface atomistic relationships made the few‐layer nanosheets higher activity, indicating the exfoliation process of the FeOCl nanosheets also brought about surface state changes.     

High‐Level Incorporation of Silver in Gold Nanoclusters: Fluorescence Redshift upon Interaction with Hydrogen Peroxide and Fluorescence Enhancement with Herbicide

High‐level incorporation of Ag in Au nanoclusters (NCs) is conveniently achieved by controlling the concentration of Ag⁺ in the synthesis of bovine serum albumin (BSA)‐protected Au NCs, and the resulting structure is determined to be bimetallic Ag₂₈Au₁₀‐BSA NCs through a series of characterizations including energy‐dispersive X‐ray spectroscopy, mass spectroscopy, and X‐ray photoelectron spectroscopy, together with density functional theory simulations. Interestingly, the Ag₂₈Au₁₀ NCs exhibit a significant fluorescence redshift rather than quenching upon interaction with hydrogen peroxide, providing a new approach to the detection of hydrogen peroxide through direct comparison of their fluorescence peaks. Furthermore, the Ag₂₈Au₁₀ NCs are also used for the sensitive and selective detection of herbicide through fluorescence enhancement. The detection limit for herbicide (0.1 nm ) is far below the health value established by the U.S. Environmental Protection Agency; such sensitive detection was not achieved by using AuAg NCs with low‐level incorporation of Ag or by using the individual metal NCs.     

Design and synthesis of cyclic acylguanidines as BACE1 inhibitors

Based on the lead compound 1 reported in literature, a series of novel BACE1 inhibitors were designed and synthesized, among which compound 11 exhibited a 14-fold improvement in potency over the lead compound 1. This represents a good lead for the discovery of more promising BACE1 inhibitors for the potential treatment of AD.     

Metabolic profiles of dioscin in rats revealed by ultra‐performance liquid chromatography quadrupole time‐of‐flight mass spectrometry

Dioscin (DIS), one of the most abundant bioactive steroidal saponins in Dioscorea sp., is used as a complementary medicine to treat coronary disease and angina pectoris in China. Although the pharmacological activities and pharmacokinetics of DIS have been well demonstrated, information regarding the final metabolic fates is very limited. This study investigated the in vivo metabolic profiles of DIS after oral administration by ultra‐performance liquid chromatography quadrupole time‐of‐flight mass spectrometry method. The structures of the metabolites were identified and tentatively characterized by means of comparing the molecular mass, retention time and fragmentation pattern of the analytes with those of the parent compound. A total of eight metabolites, including seven phase I and one phase II metabolites, were detected and tentatively identified for the first time. Oxidation, deglycosylation and glucuronidation were found to be the major metabolic processes of the compound in rats. In addition, a possible metabolic pathway on the biotransformation of DIS in vivo was proposed. This study provides valuable and new information on the metabolism of DIS, which will be helpful for further understanding its mechanism of action. Copyright © 2015 John Wiley & Sons, Ltd.