化学

封面文章

化学

来源出版物：Chinese Journal of Polymer Science, 2015, 33(11): 1516-1526

联系邮箱：DU Binyang, duby@zju.edu.cn

封面介绍：The cover image presents a new idea of expanding the scope of density functional reactivity theory. On page 2057, LIU et al. demonstrate that Rényi entropy, Tsallis entropy, and Onicescu information energy can be introduced and they serve as additional descriptors to provide in-depth insights for the accurate prediction of structure and reactivity properties for molecular systems.

密度泛函活性理论中的Rényi熵，Tsallis熵和Onicescu信息能

刘述斌，荣春英，吴泽民，等

根据密度泛函理论，分子的电子密度确定了该体系基态下的所有性质，其中包括结构和反应活性。如何运用电子密度泛函有效地预测分子反应活性仍然是一个有待解决的难题。密度泛函活性理论（DFRT）倾力打造这样一个理论和概念架构，使得运用电子密度以及相关变量准确地预测分子的反应特性成为可能。信息理论方法的香农熵和费舍尔信息就是这样的密度泛函，研究表明，它们均可作为反应活性的有效描述符。本文将在DFRT框架中介绍和引进三个密切相关的描述符，Rényi熵、Tsallis熵和Onicescu信息能。我们准确地计算了它们在一些中性原子和分子中的数值并讨论了它们随电子数量和电子总能量的变化规律。此外，以第二阶Onicescu信息能为例，在分子和分子中的原子两个层面上，系统地考察了其随乙烷二面角旋转的变化模式。这些新慨念的引入将为我们深入洞察和预测分子的结构和反应活性提供额外的描述工具。

Rényi熵；Tsallis熵；Onicescu信息能；香农熵；密度泛函活性理论

来源出版物：物理化学学报, 2015, 31(11): 2057-2063联系邮箱：刘述斌，shubin@email.unc.edu

封面介绍：The cover picture shows a short and efficient synthesis of clionamine D. Steroidalα-methylene-γ-lactones are versatile intermediates for synthesizing related natural products such as clionamines A-D, a family of marine natural alkaloids with potent autophagy bioactivities and unprecedented chemical structures. Employing single oxygen to break the C22-C23 double bond via a [2+2]/retro-[2+2] process, Shi and Tianet al. have developed a scalable, four-step procedure to prepareα-methylene-γ-lactone directly from steroidal sapogenin-needn't prepare dinorcholanic lactone first. A synthesis of clionamine D was therefore achieved in eight steps with an overall yield of 31%.

A short synthesis of clionamine D

HAO Xiang, WU Jingjing, TIAN Hailong, et al

Abstract:Herein we describe a scalable four-step preparation ofα-methylene-γ-lactone 3 from steroidal sapogenin. This method allowed a facile synthesis of clionamine D, a natural aminosteroid with potent autophagy bioactivity and unprecedented chemical structure.

Keywords:clionamine D;α-methylene-γ-lactone; singlet oxygen; natural product; synthesis

来源出版物：Chinese Journal of Chemistry, 2015, 33(11): 1235-1238

联系邮箱：SHI Yong, shiong81@sioc.ac.cn

Iridium-catalyzed directortho-C-H amidation of benzoic acids with sulfonylazides

WEI Minge, WANG Lianhui, LI Yudong, et al.

Abstract:Amild and efficient iridium-catalyzedortho-C-H amidation with sulfonyl azides by weakly coordinating carboxylic acid was demonstrated, which provided a novel approach to anthranilic acid derivatives.

Keywords:Ir-catalysis; benzoic acid; sulfonyl azides; C-H bond amination；

来源出版物：Chinese Chemical Letters, 2015, 26(11): 1336-1340

联系邮箱：CUI Xiuling, cuixl@hqu.edu.cn

封面介绍：On page 1611, Zhao et al reviewed the recent progress of DNAzyme－nanomaterialbased biosensors and nanomaterials included gold nanoparticles, graphene, quantum dots, magnetic nanomaterials, and so on. This paper also reviewed that the combination of DNAzymes with nanomaterials could retain the DNAzyme activity and realized the functional integration of recognition and signal transduction, promoting rapid development of biosensors.

脱氧核酶-纳米材料复合物用于生物传感研究进展

赵旭华，孟红敏，龚亮，等

摘要：脱氧核酶（DNAzyme或DNA酶）是一类具有高效催化活性和特异性识别功能的DNA分子，可以通过体外筛选方式从随机脱氧核苷酸单链库中获得，它具有催化效率高、特异性高、稳定性好、合成简单且修饰方便等优点。脱氧核酶与纳米材料的结合，既保留了脱氧核酶的催化特性和识别能力，又引入了纳米材料的信号转导功能，实现了识别与信号转导功能的一体化，大大促进了生物传感器的快速发展。本文主要介绍了金纳米颗粒、石墨烯、量子点、磁性纳米颗粒等纳米材料结合脱氧核酶用于生物传感的研究进展。

关键词：脱氧核酶；纳米材料；生物传感器；评述

来源出版物：分析化学, 2015, 43(11): 1611-1619联系邮箱：张晓兵，xbzhang@hnu.edu.cn

Thermo-sensitive poly(DEGMMA-co-MEA) microgels: Synthesis, characterization and interfacial interaction with adsorbed protein layer

LI Zhenbing, XIANG Yanhui, ZHOU Xianjing, et al.

The novel microgels, poly[di(ethylene glycol) methyl ether methacrylate-co-2-methoxyethyl acrylate] poly(DEGMMA-co-MEA) microgels, were synthesized. The poly (DEGMMA-co-MEA) microgels were thermo-sensitive and exhibited a volume phase transitive temperature (VPTT) of 14-22℃. The incorporation of hydrophobic comonomer MEA shifted the VPTT of poly(DEGMMA-co-MEA) microgels to lower temperatures. The interfacial interaction of poly(DEGMMA-co-MEA) microgels and three model proteins, namely fibrinogen, bovine serum albumin and lysozyme, was investigated by quartz crystal microbalance (QCM). An injection sequence of “microgel-after-protein” was then established for the real-time study of the interaction of proteins and the microgels at their swollen and collapsed states by using QCM technique. The results indicated that the interfacial interaction of poly(DEGMMA-co-MEA) microgels and adsorbed protein layers was mainly determined by the electrostatic interaction. Because poly(DEGMMA-co-MEA) microgels were negatively charged in Tris-HCl buffer solution (pH=7.4), the microgels did not adsorb on negatively charged fibrinogen and bovine serum albumin layers but strongly adsorbed on positively charged lysozyme layer. Stronger interaction between lysozyme and the microgels at collapsed state (i.e.at 37℃) was observed. Furthermore, the incorporation of MEA might weaken the interaction between poly(DEGMMA-co-MEA) microgels and proteins.

QCM; poly(DEGMMA-co-MEA) microgels; thermosensitive; proteins; interfacial interaction