Beyond Stereoselectivity,Switchable Catalysis: Some of the Last Frontier Challenges in Ring‐Opening Polymerization of Cyclic Esters

Metal‐based catalysts and initiators have played a pivotal role in the ring‐opening polymerization (ROP) of cyclic esters, thanks to their high activity and remarkable ability to control precisely the architectures of the resulting polyesters in terms of molar mass, dispersity, microstructure, or tacticity. Today, after two decades of extensive research, the field is slowly reaching maturity. However, several challenges remain, while original concepts have emerged around new types or new applications of catalysis. This Review is not intended to comprehensively cover all of these aspects. Rather, it provides a personal overview of the very recent progress achieved in some selected, important aspects of ROP catalysis—stereocontrol and switchable catalysis. Hence, the first part addresses the development of new metal‐based catalysts for the isoselective ROP of racemic lactide towards stereoblock copolymers, and the use of syndioselective ROP metal catalysts to control the monomer sequence in copolymers. A second part covers the development of ROP catalysts—primarily metal‐based catalysts, but also organocatalysts—that can be externally regulated by the use of chemical or photo stimuli to switch them between two states with different catalytic abilities. Current challenges and opportunities are highlighted.     

A new strategy for synthesis of branched cyclic peptide by Asn side-chain hydrazide ligation

Here, we report a new strategy for rapid synthesis of branched peptide by side-chain hydrazide ligation at Asn. The hydrazide was converted to thioester at Asn side chain by NaNO₂ and thiol reagent, and sequential ligation with an N-terminus Cys-peptide efficiently afforded the branched peptide. A branched cyclic peptide was successfully synthesized by side-chain ligation with a two-Cys-peptide and formation of a disulfide bond. This approach provides a new way for expeditious synthesis of branched peptides and facilitates the design of neopeptides as functional bio-mimics.     

原位液相透射电子显微镜及其在 纳米粒子表征方面的应用

近年来,基于透射电子显微技术、微纳加工技术和薄膜制造技术的发展,原位液相透射电子显微技术产生,为构建多种纳米级分辨率尺度下的微实验平台,发展新型纳米表征技术和众多领域的相关研究提供了途径.本文首先介绍了应用于原位液相透射电子显微技术的液体腔设计要求,然后介绍了液体腔的发展和典型的制备工艺,最后综述了近年来液体腔透射电子显微镜在纳米粒子成核和生长方面的应用研究,并探讨了该技术前沿发展面临的机遇和挑战.本文将为提高我国先进纳米表征技术和原子精准构筑技术提供相关讨论和支持.     

Sensitive chemically amplified electrochemical detection of ruthenium tris-(2,2′-bipyridine) on tin-doped indium oxide electrode

Optimized combination of chemical agents was selected for sensitive electrochemical detection of dissolved ruthenium tris-(2,2′-bipyridine) (Ru-bipy). The detection was based on the chemical amplification mechanism, in which the anodic current of a redox-active analyte was amplified by a sacrificial electron donor in solution. On indium-doped tin oxide (ITO) electrodes, electrochemical reaction of the analyte was reversible, but that of the electron donor was greatly suppressed. Several transition metal complexes, such as ferrocene and tris-(2,2′-bipyridine) complexes of osmium, iron and ruthenium, were evaluated as model analyte. A correlation between the amplified current and the standard potential of the complex was observed, and Ru-bipy generated the largest current. A variety of organic bases, acids and zwitterions were assessed as potential electron donor. Sodium oxalate was found to produce the largest amplification factor. With Ru-bipy as the model analyte and oxalate as the electron donor, the analyte concentration curve was linear up to 50 μM, with a lower detection limit of approximately 50 nM. Preliminary work was presented in which a Ru-bipy derivative was attached to bovine serum albumin and detected electrochemically. Although the combination of Ru-bipy, oxalate and ITO electrode has been used before for electrochemiluminescent detection of Ru-bipy and oxalate, as well as electrochemical detection of oxalate, its utility in amplified voltammetric detection of Ru-bipy as a potential electrochemical label has not been reported previously.     

完全非相干白光一维光生伏打暗空间孤子

使用白炽灯作光源在LiNbO₃∶Fe晶体内实验观察到一维白光光生伏打暗空间孤 子. 由奇数 和偶数初始条件分别产生了灰孤子和灰孤子对，它们所感应的波导能导向白光和相干光. 用 相干光清楚地探测到它们内部的多模结构. 该实验证明了白光光生伏打暗空间孤子的存在， 并指出了用完全非相干的白光暗孤子控制和导向相干光的可能性. 关键词： 光生伏打效应 自陷 完全非相干孤子 波导     

Stability of Semiconductor States with Insulating and Contact Boundary Conditions

We prove the existence of global smooth solutions near a given steady state of the hydrodynamic model of the semiconductors in a bounded domain with physical boundary conditions. The steady state and the doping profile are permitted to be of large variation but the initial velocity must be small. Two cases are considered. In the first one the problem is three-dimensional, the boundary conditions are insulating and the steady state velocity vanishes. In the second one, the problem is one-dimensional, the boundary is of contact type and the steady state velocity does not vanish.