Chemoselective and enantioselective transfer hydrogenation of β,β-disubstituted nitroalkenes catalyzed by a water-insoluble chiral diamine–rhodium complex in water

Asymmetric transfer hydrogenation of β,β-disubstituted nitroalkenes catalyzed by a chiral diamine–rhodium complex in combination with HCO₂Na–HCO₂H as a hydrogen source in water was successfully realized with high reactivity, excellent chemoselectivity and good enantioselectivity. The metal precursor and pH value of the aqueous solution have a large influence on the reactivity and chemoselectivity. The substituents on the benzene rings and the sulfonyl groups of TsDPEN have significant effects on the enantioselectivity. This catalytic asymmetric transformation is one of the most practical pathways to obtain optically active nitroalkanes.     

纤维素及其衍生物催化脱氧转化制化学品

纤维素是木质纤维素生物质中最为丰富的组分,将其催化转化制备高附加值化学品在生物质资源化利用中占据极为重要的一席之地。由于纤维素中氧含量过高,需选择性地脱除部分氧原子才可获得满足当前化学工业对各类高值化学品的要求。近年来,针对纤维素以及由其衍生的关键平台分子葡萄糖和5-羟甲基糠醛(HMF)等催化脱氧的研究已引起广泛关注,并取得诸多重要进展。在此,我们总结了具有代表性的多相催化剂体系,讨论了利用氢解或脱水脱氧策略分别将纤维素和葡萄糖等分子中一个或多个C―O键裁剪制备乙醇、烯烃或己二酸等的研究。我们还着重介绍了HMF和其衍生的呋喃化合物选择性剪切C―OH/C＝O键或呋喃环中的C―O―C键分别制备二甲基呋喃和1, 6-己二醇等催化体系。此外,对各多相催化剂的作用机制和特定C―O断键机理也分别进行了探讨,以期深入理解纤维素及其衍生物的催化脱氧反应。     

A Novel Ternary Composite of Polyurethane/Polyaniline/Nanosilica with Antistatic Property and Excellent Mechanical Strength: Preparation and Mechanism

Chinese Journal of Polymer Science - Antistatic and strength properties are of vital importance for polyurethane rubber used in moving parts of many industrial instruments. Herein, polyurethane was...     

Preparation of C-Terminal Epitope Imprinted Particles Via Reversible Addition-Fragmentation Chain Transfer Polymerization and Zn2+ Chelating Strategy: Selective Recognition of Cytochrome c

Chromatographia - The C-terminal epitope imprinted polymers on the silica were prepared by reversible addition-fragmentation chain transfer (RAFT) strategy with C-terminal nonapeptide of cytochrome...     

LiF and LiNO3 as synergistic additives for PEO-PVDF/LLZTO-based composite electrolyte towards high-voltage lithium batteries with dual-interfaces stability

Solid electrolytes with desirable properties such as high ionic conductivity,wide electrochemical stable window,and suitable mechanical strength,and stable electrode-electrolyte interfaces on both cathode and anode side are essential for high-voltage all-solid-state lithium batteries(ASSLBs)to achieve excellent cycle stability.In this work,a novel strategy of using LiF and LiNO₃ as synergistic additives to boost the performance of PEO-PVDF/LLZTO-based composite solid electrolytes(CSEs)is developed,which also promotes the assembled high-voltage ASSLBs with dual-interfaces stability characteristic.Specifically,LiF as an inactive additive can increase the electrochemical stability of the CSE under high cut-off voltage,and improve the high-voltage compatibility between cathode and CSE,thus leading to a stable cathode/CSE interface.LiNO₃ as an active additive can lead to an enhanced ionic conductivity of CSE due to the increased free-mobile Li+and ensure a stable CSE/Li interface by forming stable solid electrolyte interphase(SEI)on Li anode surface.Benefiting from the improved performance of CSE and stable dualinterfaces,the assembled NCM622/9[PEO₁₅-LiTFSI]-PVDF-15 LLZTO-2 LiF-3 LiNO₃/Li cell delivers a high rate capacity of 102.1 mAh g^-1 at 1.0 C and a high capacity retention of 77.4%after 200 cycles at 0.5 C,which are much higher than those of the ASSLB assembled with additive-free CSE,with only 60.0 mAh g^-1 and 52.0%,respectively.Furthermore,novel cycle test modes of resting for 5 h at different charge states after every 5 cycles are designed to investigate the high-voltage compatibility between cathode and CSE,and the results suggest that LiF additive can actually improve the high-voltage compatibility of cathode and CSE.All the obtained results confirm that the strategy of using synergistic additives in CSE is an effective way to achieve high-voltage ASSLBs with dual-interfaces stability.     

海水电解面临的挑战与机遇：含氯电化学中先进材料研究进展

氢气是一种清洁高效的能源载体,通过海水电解规模化制备氢气能够为应对全球能源挑战提供新的机遇。然而,缺乏高活性、高选择性和高稳定性的理想电极材料是在腐蚀性海水中连续电解过程的一个巨大挑战。为了缓解这一困境,需要从基础理论和实际应用两方面对材料进行深入研究。近年来,人们围绕电极材料的催化活性、选择性和耐腐蚀性进行了大量的探索。本文重点总结了高选择性和强耐腐蚀性材料的设计合成与作用机制。其中详细介绍了多种电极材料(如多金属氧化物、Ni/Fe/Co基复合材料、氧化锰包覆异质结构等)对氧气生成选择性的研究进展;系统论述了各种材料的抗腐蚀工程研究成果,主要讨论了本征抗腐蚀材料、外防护涂层和原位产生抗腐蚀物种三种情况。此外,提出了海水电解过程中存在的挑战和潜在的机遇。先进纳米材料的设计有望为解决海水电解中的氯化学问题提供新思路。     

Metal organic frameworks as advanced extraction adsorbents for separation and analysis in proteomics and environmental research

Science China Chemistry - Human health is always under global spotlight, but now it suffers from severe environmental issue and various diseases. Developing highly selective and effective...     

Large-area hydrated vanadium oxide/carbon nanotube composite films for high-performance aqueous zinc-ion batteries

Science China Chemistry - Synchronously reducing/self-assembling strategy on Zn substrate was designed to fabricate large-area cation-doped hydrated V2O5/multi-walled carbon nanotube (D-HVO/MWCNT)...     

In vitro and in vivo evaluation of a novel anti-EGFR antibody labeled with 89Zr and 177Lu

Journal of Radioanalytical and Nuclear Chemistry - There is an urgent need to develop more specific targeted therapies for lung cancer treatment due to the its low survival rate. EGFR is a...     

Activation of Au–Ag Plasmonic Bimetallic Nanocatalysts with Cold Plasma: The Role of Loading Sequence of Plasmonic Metals and Discharge Atmosphere

The activation of Au–Ag plasmonic bimetallic nanocatalyst can make the nanocatalyst exhibit superior visible-light (VL) photocatalytic activity. An efficient activation of Au–Ag nanocatalyst by cold plasma requires the restructuring of Au and Ag species over catalyst surface to form Au–Ag alloy nanoparticles while suppressing agglomeration of the nanoparticles. We here report that the loading sequence of Au and Ag components on titanium dioxide (TiO₂) support during catalyst preparation and discharge atmosphere play important roles in the plasma activation. Preparation of AuAg/TiO₂ nanocatalyst by depositing Ag and Au in sequence could avoid the undesired loss of Ag component, and ensure an effective restructuring of Au and Ag species in O₂ plasma activation. Compared with the reductive (H₂) and inert (Ar and N₂) plasmas, discharge in oxidative O₂ establishes Coulomb field with the negatively charged species over catalyst surface and enable the restructuring and intimate interaction of Au and Ag species. The catalyst characterization and density functional theory calculations suggest that O₂ plasma endows AuAg/TiO₂ nanocatalyst with large numbers of Au–Ag alloy nanoparticles, small size of plasmonic nanoparticles, high density of coordinatively unsaturated sites, and high content of surface oxygen species in the activation, which facilitates the adsorption and activation of O₂, and thus CO oxidation reaction under VL irradiation.