Nankai University

About: Nankai University is a education organization based out in Tianjin, China. It is known for research contribution in the topics: Catalysis & Enantioselective synthesis. The organization has 42964 authors who have published 51866 publications receiving 1127896 citations. The organization is also known as: Nánkāi Dàxué.

Graphene, inorganic graphene analogs and their composites for lithium ion batteries

Abstract: In recent years, two-dimensional (2D) materials, including graphene and inorganic graphene analogs (IGAs), have been the subject of intensive studies due to their novel chemical and physical properties. With apparent high surface-to-volume ratio, 2D materials are promising electrode candidates for lithium ion batteries (LIBs). Compared with three-dimensional bulk crystals, 2D materials have superior structural characteristics, and thus can exhibit higher specific capacity and better high-rate stability. In particular, composites consisting of graphene and IGAs could have enhanced electrochemical performances due to the specific synergic effects, which open up new frontiers in fundamental science and technology. Although the explorations of using IGAs for lithium storage have begun very recently, a timely overview in this field is necessary for developing improved electrode candidates. In this feature article, we summarize the ongoing efforts and studies from both experimental and theoretical communities on developing graphene and IGAs as LIB electrodes. Compared with graphene, we put more emphasis on IGAs, such as transition metal oxides, dichalcogenides, and MXenes, and illustrate the significant advantages of IGAs as electrodes. We also show that due to the effective synergic interactions between graphene and IGAs, their composites step further to achieve reversible high-capacity LIBs. Finally, we discuss the problems and limitations for the practical application of 2D materials to LIBs.

Asymmetric NH Insertion Reaction Cooperatively Catalyzed by Rhodium and Chiral Spiro Phosphoric Acids

Abstract: Nitrogen-containing organic compounds, such as a-amino acids and alkaloids, are important biologically active compounds, thus the development of efficient and enantioselective methods for the construction of carbon–nitrogen bonds is a fundamental goal in modern organic synthesis. Transitionmetal-catalyzed carbene insertion into N H bonds is one of the most efficient methods to construct carbon–nitrogen bonds and the development of asymmetric versions of the N H insertion reaction has attracted considerable attention. In initial studies, chiral dirhodium catalysts were tested in intramolecular and intermolecular N H insertion reactions, however, only low to modest enantioselectivities (< 50% ee) were achieved. Since these reports, other transition metals including copper and silver have been used as catalysts, and gave enantioselectivities up to 48% ee. Recently, we reported a highly enantioselective N H insertion reaction (up to 98% ee) using a copper complex with chiral spiro bisoxazoline ligands. Subsequently, two other types of chiral copper catalysts have been developed, one with a planar chiral bipyridine ligand and the other with a binolderivative ligand, and both of these catalysts give high enantioselectivities in N H insertion reactions. Although progress on copper-catalyzed asymmetric N H insertion reactions has been substantial, they still have serious limitations. For instance, all the copper-catalyzed N H insertion reactions require high catalyst loading (5– 10 mol%) for satisfactory yields and enantioselectivities, thus more-efficient chiral catalysts are highly desirable. Because the activity of dirhodium(II) catalysts is usually superior to that of copper catalysts in nonenantioselective N H insertion reactions, the possibility of using dirhodium catalysts to achieve highly enantioselective N H insertion reactions is an intriguing one. Recently, Saito et al. reported that dirhodium(II) carboxylates and cinchona alkaloids cooperatively catalyze the asymmetric N H insertion reactions of a-diazo-a-arylacetates with anilines. The combined catalysts exhibit excellent reactivity but only modest enantioselectivity (up to 71% ee). It is generally accepted that the rhodium-catalyzed N H insertion most likely proceeds via an ylide intermediate (Scheme 1A). We speculated that the subsequent protontransfer step could be facilitated by a chiral phosphoric acid species via a seven-membered-ring transition state, and that, consequently, chiral induction could be accomplished in this step (Scheme 1B). The groups of Yu and Platz have reported that either water or alcohols can assist proton transfer in O H insertion reactions, as indicated by density functional theory calculations and ultrafast time-resolved IR spectroscopy studies. These studies stimulated our interest in exploring asymmetric N H insertion in the presence of a proton-transfer catalyst. As part of our ongoing work on the development of asymmetric carbene insertion reactions, we report herein the asymmetric N H insertion reaction cooperatively catalyzed by dirhodium(II) carboxylates and chiral spiro phosphoric acids (SPAs). Excellent reactivity and high enantioselectivity (up to 95% ee) were achieved in the presence of as little as 0.1 mol% of catalyst. In our initial study, we carried out the insertion of methyl a-diazo-a-phenylacetate (3a) into the N H bond of tert-butyl carbamate (BocNH2) in CHCl3 at 25 8C using 1 mol% of [Rh2(OAc)4] and 10 mol% of chiral SPAs 1 as the catalysts (Table 1). SPAs 1 were prepared by a simple condensation of P(O)Cl3 with 6,6’-disubstituted-1,1’-spirobiindane-7,7’-diols 2, followed by hydrolysis (Scheme 2). Diols 2 were synthesized from spinol (1,1’-spirobiindane-7,7’-diol), as described previously. In the presence of (R)-1a, the N H insertion reaction proceeded within 5 minutes to afford the insertion product in excellent yield with 11% ee (Table 1, entry 2). Control experiments showed that the SPAs alone did not promote the insertion reaction. A range of SPAs with various substituents at the 6 and 6’ positions were evaluated (Table 1, entries 3–9). All the tested SPAs afforded high yields in the N H insertion reaction. SPA (R)-1h, which bears a 6,6’-di(naphth-2-yl) group, afforded the Scheme 1. Proposed mechanism for chiral phosphoric acid induced asymmetric N H insertion.

Single Mo1(Cr1) Atom on Nitrogen-Doped Graphene Enables Highly Selective Electroreduction of Nitrogen into Ammonia

Abstract: Searching for new types of electrocatalysts with high stability, activity, and selectivity is essential for the production of ammonia via electroreduction of nitrogen. Using density functional theo...

Genomic and Proteomic Analyses of the Fungus Arthrobotrys oligospora Provide Insights into Nematode-Trap Formation

Abstract: Nematode-trapping fungi are “carnivorous” and attack their hosts using specialized trapping devices. The morphological development of these traps is the key indicator of their switch from saprophytic to predacious lifestyles. Here, the genome of the nematode-trapping fungus Arthrobotrys oligospora Fres. (ATCC24927) was reported. The genome contains 40.07 Mb assembled sequence with 11,479 predicted genes. Comparative analysis showed that A. oligospora shared many more genes with pathogenic fungi than with non-pathogenic fungi. Specifically, compared to several sequenced ascomycete fungi, the A. oligospora genome has a larger number of pathogenicity-related genes in the subtilisin, cellulase, cellobiohydrolase, and pectinesterase gene families. Searching against the pathogen-host interaction gene database identified 398 homologous genes involved in pathogenicity in other fungi. The analysis of repetitive sequences provided evidence for repeat-induced point mutations in A. oligospora. Proteomic and quantitative PCR (qPCR) analyses revealed that 90 genes were significantly up-regulated at the early stage of trap-formation by nematode extracts and most of these genes were involved in translation, amino acid metabolism, carbohydrate metabolism, cell wall and membrane biogenesis. Based on the combined genomic, proteomic and qPCR data, a model for the formation of nematode trapping device in this fungus was proposed. In this model, multiple fungal signal transduction pathways are activated by its nematode prey to further regulate downstream genes associated with diverse cellular processes such as energy metabolism, biosynthesis of the cell wall and adhesive proteins, cell division, glycerol accumulation and peroxisome biogenesis. This study will facilitate the identification of pathogenicity-related genes and provide a broad foundation for understanding the molecular and evolutionary mechanisms underlying fungi-nematodes interactions.