封面文章

化學(xué)

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

聯(lián)系郵箱：DU Binyang, duby@zju.edu.cn

封面介紹：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.

密度泛函活性理論中的Rényi熵，Tsallis熵和Onicescu信息能

劉述斌，榮春英，吳澤民，等

根據(jù)密度泛函理論，分子的電子密度確定了該體系基態(tài)下的所有性質(zhì)，其中包括結(jié)構(gòu)和反應(yīng)活性。如何運(yùn)用電子密度泛函有效地預(yù)測(cè)分子反應(yīng)活性仍然是一個(gè)有待解決的難題。密度泛函活性理論（DFRT）傾力打造這樣一個(gè)理論和概念架構(gòu)，使得運(yùn)用電子密度以及相關(guān)變量準(zhǔn)確地預(yù)測(cè)分子的反應(yīng)特性成為可能。信息理論方法的香農(nóng)熵和費(fèi)舍爾信息就是這樣的密度泛函，研究表明，它們均可作為反應(yīng)活性的有效描述符。本文將在DFRT框架中介紹和引進(jìn)三個(gè)密切相關(guān)的描述符，Rényi熵、Tsallis熵和Onicescu信息能。我們準(zhǔn)確地計(jì)算了它們?cè)谝恍┲行栽雍头肿又械臄?shù)值并討論了它們隨電子數(shù)量和電子總能量的變化規(guī)律。此外，以第二階Onicescu信息能為例，在分子和分子中的原子兩個(gè)層面上，系統(tǒng)地考察了其隨乙烷二面角旋轉(zhuǎn)的變化模式。這些新慨念的引入將為我們深入洞察和預(yù)測(cè)分子的結(jié)構(gòu)和反應(yīng)活性提供額外的描述工具。

Rényi熵；Tsallis熵；Onicescu信息能；香農(nóng)熵；密度泛函活性理論

來(lái)源出版物：物理化學(xué)學(xué)報(bào), 2015, 31(11): 2057-2063聯(lián)系郵箱：劉述斌，shubin@email.unc.edu

封面介紹：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

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

聯(lián)系郵箱：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；

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

聯(lián)系郵箱：CUI Xiuling, cuixl@hqu.edu.cn

封面介紹：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.

脫氧核酶-納米材料復(fù)合物用于生物傳感研究進(jìn)展

趙旭華，孟紅敏，龔亮，等

摘要：脫氧核酶（DNAzyme或DNA酶）是一類(lèi)具有高效催化活性和特異性識(shí)別功能的DNA分子，可以通過(guò)體外篩選方式從隨機(jī)脫氧核苷酸單鏈庫(kù)中獲得，它具有催化效率高、特異性高、穩(wěn)定性好、合成簡(jiǎn)單且修飾方便等優(yōu)點(diǎn)。脫氧核酶與納米材料的結(jié)合，既保留了脫氧核酶的催化特性和識(shí)別能力，又引入了納米材料的信號(hào)轉(zhuǎn)導(dǎo)功能，實(shí)現(xiàn)了識(shí)別與信號(hào)轉(zhuǎn)導(dǎo)功能的一體化，大大促進(jìn)了生物傳感器的快速發(fā)展。本文主要介紹了金納米顆粒、石墨烯、量子點(diǎn)、磁性納米顆粒等納米材料結(jié)合脫氧核酶用于生物傳感的研究進(jìn)展。

關(guān)鍵詞：脫氧核酶；納米材料；生物傳感器；評(píng)述

來(lái)源出版物：分析化學(xué), 2015, 43(11): 1611-1619聯(lián)系郵箱：張曉兵，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