Water-Insensitive Synthesis of Poly-β-Peptides with Defined Architecture

Biocompatible and proteolysis-resistant poly-β-peptides have broad applications and are dominantly synthesized via the harsh and water-sensitive ring-opening polymerization of β-lactams in a glovebox or using a Schlenk line, catalyzed by the strong base LiN(SiMe₃)₂. We have developed a controllable and water-insensitive ring-opening polymerization of β-amino acid N-thiocarboxyanhydrides (β-NTAs) that can be operated in open vessels to prepare poly-β-peptides in high yields, with diverse functional groups, variable chain length, narrow dispersity and defined architecture. These merits imply wide applications of β-NTA polymerization and resulting poly-β-peptides, which is validated by the finding of a HDP-mimicking poly-β-peptide with potent antimicrobial activities. The living β-NTA polymerization enables the controllable synthesis of random, block copolymers and easy tuning of both terminal groups of polypeptides, which facilitated the unravelling of the antibacterial mechanism using the fluorophore-labelled poly-β-peptide.     

Degradation of Structurally Defined Graphene Nanoribbons by Myeloperoxidase and the Photo-Fenton Reaction

As an emerging member of the graphene family, structurally defined graphene nanoribbons (GNRs) have shown promising applications in various fields. The evaluation of the degradability of GNRs is particularly important for assessing the persistence level and risk of these materials in living organisms and the environment. However, there is a void in the study of the degradation of GNRs. Here, we report the degradation behavior of GNRs in the presence of human myeloperoxidase (hMPO) or treated with the photo-Fenton (PF) reaction. With the assistance of potassium hydroxide or imidazole, which facilitates the dispersion of GNRs in the aqueous solution, GNRs underwent only partial degradation after 25-hour incubation with hMPO, while, the PF reaction degraded GNRs almost completely after 120 hours. These results indicate that structurally precise GNRs can be efficiently degraded under suitable conditions, providing more opportunities for future applications in different fields.     

Molecular Photochemistry: Recent Developments in Theory

Photochemistry is a fascinating branch of chemistry that is concerned with molecules and light. However, the importance of simulating light‐induced processes is reflected also in fields as diverse as biology, material science, and medicine. This Minireview highlights recent progress achieved in theoretical chemistry to calculate electronically excited states of molecules and simulate their photoinduced dynamics, with the aim of reaching experimental accuracy. We focus on emergent methods and give selected examples that illustrate the progress in recent years towards predicting complex electronic structures with strong correlation, calculations on large molecules, describing multichromophoric systems, and simulating non‐adiabatic molecular dynamics over long time scales, for molecules in the gas phase or in complex biological environments.     

中国出境旅游的外交效应

2000年以来,中国出境旅游高增长、高消费,影响力不断增大,成为国家外交战略的重要内容,外交效应逐渐显现。通过辨析中国出境旅游外交效应的概念、表现形式和结果,基于10个中国主要出境目的国的旅游互动数据,采用DIF-GMM计量经济模型,实证检验了中国出境旅游外交效应。结果表明,中国通过有序推进ADS协议、加强经济援助、举办“旅游年”活动、实施旅游“制裁”,并积极参与国际制度建设等旅游外交行为,促进了与世界各国的友好交往,维护了自身核心利益,提升了外交软实力和国际影响力。国际旅游反作用于国际关系,对国际关系具有显著的正向促进作用,不仅是国际关系的结果,而且是其重要动因之一。中国出境旅游与政治、经济、社会、文化等联动,多方面提升了中国的国际影响力。     

Y2O3涂层负载Pd整体式催化剂的制备和催化性能

以Y(NO3)3为前驱体制备了Y2O3涂层的堇青石蜂窝陶瓷载体.扫描电子显微镜、X射线能谱和超声波振荡等表征结果表明,Y2O3涂层不但具有良好的抗振荡性和粘结强度,而且具有很强的吸附催化剂活性组分(H2PdCl4)的能力,适合制备负载型Pd催化剂.以甲苯和乙酸乙酯完全燃烧为模型反应考察了催化剂的活性,发现以Y2O3涂层堇青石蜂窝陶瓷为载体的整体式Pd/Y2O3催化剂具有良好的催化活性和热稳定性,甲苯和乙酸乙酯催化燃烧的T99分别为210和300℃;催化剂经900℃焙烧4 h后,T99仅提高20℃,表明催化剂具有很高的热稳定性.催化剂的X射线衍射、拉曼光谱和程序升温还原结果表明,Pd/Y2O3催化剂经低温焙烧时,Y2O3和PdO均高度分散在堇青石蜂窝陶瓷的表面,而高温焙烧使催化剂活性组分PdO晶粒增大,从而导致催化剂活性下降.     

人肝癌细胞系HLE细胞表面抗原多肽的纳升电喷雾串联质谱从头测序分析

肿瘤细胞表面的抗原多肽能够被细胞毒T淋巴细胞特异性识别而引起免疫应答,因此有可能用于研制基于多肽的抗肿瘤疫苗。用弱酸将人肝癌细胞系HLE细胞表面抗原多肽和人正常肝细胞表面多肽洗脱后,经RP-HPLC分离,选择HLE细胞表面特异性多肽进行纳升电喷雾串联质谱(nanoESI-MS/MS)测序,共测定5个色谱峰中的20个多肽序列,分子量分布范围为1000~2000 Da。借助M asSeq软件分析出其中12个多肽的序列。经数据库查寻,其中的3个肽段分别来自钙调节蛋白、核蛋白S19和伴侣蛋白10。这些多肽的生物学功能及与肿瘤的关系值得深入研究。该研究表明nanoESI-MS/MS是测定微量混合多肽序列的最有效方法。     

Highly Chemoselective Aerobic Oxidation of Amino Alcohols into Amino Carbonyl Compounds

The direct oxidation of unprotected amino alcohols to their corresponding amino carbonyl compounds has often posed serious challenges in organic synthesis and has constrained chemists to adopting an indirect route, such as a protection/deprotection strategy, to attain their goal. Described herein is a highly chemoselective aerobic oxidation of unprotected amino alcohols to their amino carbonyl compounds in which 2‐azaadamantane N‐oxyl (AZADO)/copper catalysis is used. The catalytic system developed leads to the alcohol‐selective oxidation of various unprotected amino alcohols, carrying a primary, secondary, or tertiary amino group, in good to high yield at ambient temperature with exposure to air, thus offering flexibility in the synthesis of nitrogen‐containing compounds.     

多壁碳纳米管-Nafion复合膜修饰玻碳电极测定硝苯地平的研究

研制了以Nafion分散羧基化多壁碳纳米管的化学修饰电极(Nafion-MWCNTs/GC),研究了硝苯地平(NIF)在修饰电极上的电化学行为和测定方法。实验结果表明,在0.1mol/LNH3-NH4Cl(pH9.6)溶液中,Nafion-MWCNTs/GC,对NIF具有明显的催化和增敏作用,还原峰电位由-0.85V(裸电极)正移到-0.75V(vs.AgCl/Ag)(修饰电极),灵敏度增加约7倍。对各种实验条件进行了优化。定量测定的线性范围为2.5×10-7~4.5×10-5mol/L,r为0.9974;检出限为8.0×10-8mol/L。探讨了NIF在Nafion-MWCNTs/GC上的电极过程和反应机理,测得在本体系中参与反应的质子数和电子转移数均为4,电子转移系数α为0.41。对NIF药片进行了测定,回收率为94.5%~101.0%。     

PBDEs研究的最新进展

多澳联苯醚(PBDEs)是一类环境中广泛存在的全球性有机污染物.由于其具有环境持久性、远距离传输、生物可累积性及对生物和人体具有毒害效应等特性,对其环境问题的研究已成为当前环境科学的一大热点.本文对最近几年来环境中PBDEs研究的进展进行综述,对多溴联苯醚在环境及生物体中的分布、时间趋势、人体暴露及途径、环境中的降解和生物代谢以及生物累积与生物放大方面的研究进行了总结,对目前存在问题及进一步的研究方向进行了讨论和展望.