In-situ polymerized cross-linked binder for cathode in lithium-sulfur batteries

Volume expansion and polysulfide shuttle effect are the main barriers for the commercialization of lithium-sulfur(Li-S) battery.In this work,we in-situ polymerized a cross-linked binder in sulfur cathode to solve the aforementioned problems using a facile method under mild conditions.Polycarbonate diol(PCDL),triethanolamine(TEA) and hexamethylene diisocyanate(HDI) were chosen as precursors to prepare the cross-linked binder.The in-situ polymerized binder(PTH) builds a strong network in sulfur cathode,which could restrain the volume expansion of sulfu r.Moreover,by adopting functional groups of oxygen atoms and nitrogen atoms,the binder could effectively facilitate transportation of Li-ion and adsorb polysulfide chemically.The Li-S battery with bare sulfur and carbon/sulfur composite cathodes and cross-linked PTH binder displays much better electrochemical performance than that of the battery with PVDF.The PTH-bare S cathode with a mass loading of 5.97 mg/cm^2 could deliver a capacity of 733.3 mAh/g at 0.2 C,and remained 585.5 mAh/g after 100 cycles.This in-situ polymerized binder is proved to be quite effective on restraining the volume expansion and suppressing polysulfide shuttle effect,then improving the electrochemical performance of Li-S battery.     

MALDI质谱技术在酶活性分析中的应用

酶作为生物催化剂参与很多重要的生理过程,同时也是一类重要的生物分子。酶的活性分析对于疾病诊断和治疗具有重要意义。基质辅助激光解吸电离飞行时间质谱(MALDI-TOF MS)具有操作简单、分析速度快、灵敏度高和易于实现高通量分析的特点,已被广泛用于各种组学研究和生物分子的检测,在酶的检测和活性分析中亦发挥了重要作用。该文综述了国内外利用MALDI-TOF MS分析酶活性和进行药物筛选的策略,总结了各种方法的优缺点,提出了MALDI质谱技术在酶活性分析领域存在的问题和挑战,并对其发展前景进行了展望。     

Recent Advances in Atomic-scale Storage Mechanism Studies of Two-dimensional Nanomaterials for Rechargeable Batteries Beyond Li-ion

Developing new types of rechargeable batteries with high energy densities and low cost have received increasing attentions, aiming to reduce the dependence on high-priced lithium. Beyond Li-ion batteries, the potential alternatives including Na-ion batteries, Li-S batteries and Li-air batteries have been investigated recently, which are required to be viable for commercial applications. From this point of view, to understand the electrochemical reaction mechanisms and kinetics of these batteries has become the key challenge to make breakthroughs in the field of new energy storage. In this review, we present a critical overview of the two dimensional nanomaterials-based batteries (except Li-ion-based batteries) that could meet such demonds. To develop new energy storage devices with more promising performances, the microstructure evolution and atomic scale storage mechanism of these batteries are comprehensively summarized. In addition, the major challenges and opportunities of advanced characterization techniques are finally discussed. We do hope that this review will give the readers a clear and profound understanding of the electrochemical reaction mechanisms and kinetics of the as-discussed batteries, thus effectively contributing to the smart design of future-generation energy storage devices.     

聚合物前驱体3D打印制备高性能陶瓷

3D打印制备陶瓷可以实现结构-材料设计一体化,为复杂形状陶瓷材料快速成型提供了新途径。但是传统的3D打印制备陶瓷是以陶瓷粉末或陶瓷颗粒为打印材料,存在陶瓷构件尺寸精度差、表面光洁度低和力学性能不佳等问题。近年来,以聚合物前驱体为打印材料,通过3D打印成型、高温裂解等工艺制备高性能陶瓷技术的出现为改善这些不足提供了新方法,成为3D打印陶瓷领域的研究热点。本文概述了聚合物前驱体3D打印制备高性能陶瓷的研究进展,重点阐述了本体聚合物前驱体、聚合物前驱体/光敏化合物、聚合物前驱体/巯基化合物、光敏基团改性聚合物前驱体、增强体/聚合物前驱体五种典型材料体系的研究现状,并对其今后的发展方向进行了展望。     

一种基于分子内质子转移发色团的硫化氢荧光探针的合成及其生物成像研究

硫化氢在许多生理过程中扮演十分重要的角色,因此检测和成像生物体内的硫化氢具有十分重要的意义。该研究成功制备了一种基于分子内质子转移发色团的硫化氢荧光探针(DHCD)。在PBS-DMSO(磷酸盐-二甲基亚砜,99∶1,体积比,pH 7.45)缓冲溶液中,DHCD的荧光强度与NaHS的浓度在0～10μmol/L范围内呈现良好的线性关系,检出限为0.84μmol/L。该探针对硫化氢的响应具有较大的Stokes位移(～165 nm)、高灵敏度和选择性。此外,合成的探针拥有良好的细胞渗透性和低的毒性,可用于HeLa细胞中硫化氢的荧光成像,在生物分析中具有潜在应用价值。     

Real‐Time Atomic‐Scale Visualization of Reversible Copper Surface Activation during the CO Oxidation Reaction

By using in situ aberration‐corrected environmental transmission electron microscopy, for the first time at atomic level, the dynamic evolution of the Cu surface is captured during CO oxidation. Under reaction conditions, the Cu surface is activated, typically involving 2–3 atomic layers with the formation of a reversible metastable phase that only exists during catalytic reactions. The distinctive role of CO and O₂ in the surface activation is revealed, which features CO exposure to lead to surface roughening and consequently formation of low‐coordinated Cu atoms, while O₂ exposure induces a quasi‐crystalline CuOx phase. Supported by DFT calculations, it is shown that crystalline CuOx reversibly transforms into the amorphous phase, acting as an active species to facilitate the interaction of gas reactants and catalyzing CO oxidation.     

Modular Synthesis of Nona‐Decasaccharide Motif from Psidium guajava Polysaccharides: Orthogonal One‐Pot Glycosylation Strategy

The synthesis of long, branched, and complex carbohydrate sequences remains a challenging task in chemical synthesis. Reported here is an efficient and modular one‐pot synthesis of a nona‐decasaccharide and shorter sequences from Psidium guajava polysaccharides, which have the potent α‐glucosidase inhibitory activity. The synthetic strategy features: 1) several one‐pot glycosylation reactions on the basis of N‐phenyltrifluoroacetimidate (PTFAI) and Yu glycosylation to streamline the chemical synthesis of oligosaccharides, 2) the successful and efficient assembly sequences (first O3′, second O5′, final O2′) toward the challenging 2,3,5‐branched Araf motif, 3) the stereoselective 1,2‐cis‐glucosylation by reagent control, and 4) the convergent [6+6+7] one‐pot coupling reaction for the final assembly of the target nona‐decasaccharide. This orthogonal one‐pot glycosylation strategy can streamline the chemical synthesis of long, branched, and complicated carbohydrate chains.     

Phenanthrene‐Fused‐Quinoxaline as a Key Building Block for Highly Efficient and Stable Sensitizers in Copper‐Electrolyte‐Based Dye‐Sensitized Solar Cells

Dye‐sensitized solar cells (DSSCs) based on Cu^II/I bipyridyl or phenanthroline complexes as redox shuttles have achieved very high open‐circuit voltages (V_OC, more than 1 V). However, their short‐circuit photocurrent density (J_SC) has remained modest. Increasing the J_SC is expected to extend the spectral response of sensitizers to the red or NIR region while maintaining efficient electron injection in the mesoscopic TiO₂ film and fast regeneration by the Cu^I complex. Herein, we report two new D‐A‐π‐A‐featured sensitizers termed HY63 and HY64 , which employ benzothiadiazole (BT) or phenanthrene‐fused‐quinoxaline (PFQ), respectively, as the auxiliary electron‐withdrawing acceptor moiety. Despite their very similar energy levels and absorption onsets, HY64 ‐based DSSCs outperform their HY63 counterparts, achieving a power conversion efficiency (PCE) of 12.5 %. PFQ is superior to BT in reducing charge recombination resulting in the near‐quantitative collection of photogenerated charge carriers.     

Enantioselective Catalytic Aldehyde α‐Alkylation/Semipinacol Rearrangement: Construction of α‐Quaternary‐δ‐Carbonyl Cycloketones and Total Synthesis of (+)‐Cerapicol

An enantioselective aldehyde α‐alkylation/semipinacol rearrangement was achieved through organo‐SOMO catalysis. The catalytically generated enamine radical cation serves as a carbon radical electrophile that can stereoselectively add to the alkene of an allylic alcohol and initiate ensuing ring‐expansion of cyclopropanol or cyclobutanol. This tandem reaction enables the production of a wide range of nonracemic functionalizable α‐quaternary‐δ‐carbonyl cycloketones in high yields and excellent enantioselectivity from simple aldehydes and allylic alcohols. As a key step, the intramolecular reaction was also successfully applied in the asymmetric total synthesis of (+)‐cerapicol.     

Rhodium(III)‐Catalyzed Asymmetric Access to Spirocycles through C−H Activation and Axial‐to‐Central Chirality Transfer

Axial‐to‐central chirality transfer is an important strategy to construct chiral centers, where the axially chiral reagents are mostly limited to atropomerically stable ones. Reported herein is a Rh^III‐catalyzed enantioselective spiroannulative synthesis of nitrones. The coupling proceeds via C?H arylation to give an atropomerically metastable biaryl, followed by intramolecular dearomative trapping under oxidative conditions with high degree of chirality transfer.