化学

化学

来源出版物：Chinese Journal of Chemistry，2015，33（6）： 632-636联系邮箱：Wang Jun，wang.j@sustc.edu.cn

不饱和半夹芯式16e化合物Cp*Ir（S2C2B10H10）与邻、间位取代苯基叠氮的反应性

钟伟，燕红

考虑取代基的位置和电子效应对反应体系的影响，本文系统地研究了 16e化合物Cp*Ir（S2C2B10H10）（1）与邻、间位取代苯基叠氮的反应.研究结果表明：与邻、间位取代苯基叠氮反应均生成苯环邻位碳发生C—H活化形成C—S键的金属配合物.这些配合物通过核磁（1H、11B、13C）、红外、质谱、元素分析和单晶结构解析进行了全面地表征.在光照反应结果的基础上，提出了形成这类产物的自由基机理.

半夹芯式配合物；取代苯基叠氮；反应性；机理

来源出版物：无机化学学报，2015，31（7）： 1305-1314

联系邮箱：钟伟，weizhong@mail.zjxu.edu.cn

封面介绍：Benzimidazole compounds are widely used in the field of medicine and pesticide，so new methods for the synthesis of these compounds have attracted enormous attentions worldwide. The recent advances in the synthetic method of benzimidazole compounds based on different raw materials are reviewed by Cheng，Zhang，Xu and Li on page 1189.

苯并咪唑类化合物催化合成的研究进展

程正，张群峰，许孝良，等

摘要：苯并咪唑类化合物在医药、农药等方面具有广泛的应用，因此这类化合物合成的新方法备受关注.从合成苯并咪唑类化合物的不同的原料出发，综述了近年来催化合成苯并咪唑化合物的研究新进展.

关键词：苯并咪唑；邻苯二胺；合成；催化剂

来源出版物：有机化学，2015，35（6）： 1189-1203

联系邮箱：张群峰，zhangqf@zjut.edu.cn

封面介绍：Due to their inherent porosity，large specific surface area，light weight and easy functionalization at the molecular level，porous organic polymers have recently received significant attention for potential applications in heterogeneous catalysis，the progress of which has been reviewed herein. ［Wang，Wei et al. on page 498-529.］

有机多孔催化研究进展

王昌安，王为

摘要：有机多孔材料POPs（Porous Organic Polymers）成为近年来的研究前沿之一.有机多孔材料包括非晶型（如CMP，HCP，PIM等）和晶型（比如COFs等）有机多孔材料两类，它们具有优异的孔性质、较大的比表面积、稳定性好、重量轻以及易于功能化等诸多优点，被广泛应用于气体存储分离、传感、有机光电和多相催化等重要领域.这里对有机多孔材料在多相催化领域中的应用做一综述. 目前，有机多孔催化领域的研究工作主要有三类：一类是通过“自下而上”策略将金属-配体类催化剂嵌入有机多孔骨架来构建多相催化剂；另一类是将有机多孔材料作为载体，通过后修饰方式负载金属纳米颗粒构建多相催化剂；最后一类是通过“自下而上”策略将不含金属的有机小分子催化剂嵌入材料骨架来构建多孔有机催化剂.受益于其结构的优越性，有机多孔材料在多相催化中表现出优异的催化性能.借鉴于均相催化的发展，具有催化活性的有机多孔材料在多相催化领域中的应用也将会有更大的发展空间.

关键词：有机多孔材料；“自下而上”策略；后修饰；多相催化；不对称催化

来源出版物：化学学报，2015，73（6）： 498-529联系邮箱：王昌安，wangcha_chem@163.com

封面介绍：On page 802-807，GAO et al developed a novel system for detection and quantification of D-limer in human plasma based on sandwich immunoassays，microfluidic and GMR sensor. The system is an in vitro-liagnostic platform which can be easily converted for detecting multi-arget biomarkers with fast，highly sensitivity，specificity and reproducibility.

巨磁阻微流体免疫传感器快速定量检测D-二聚体

高宇哲，张磊，霍卫松，等

摘要：将巨磁阻（GMR）传感器集成在微流体通道中，以100 nm磁颗粒为信号探针，研制了可快速检测血栓标志物D-二聚体的免疫传感器.用GMR传感器在线检测免疫反应后被捕捉在芯片上的磁颗粒的信息，测定血浆中D-二聚体的含量.通过对反应条件的优化，建立了GMR微流体传感器检测血浆中D-二聚体的方法.本方法的线性检测范围为5～6500 ng/mL，检出限为5 ng/mL.批内相对标准偏差 ＜ 12%；批间相对标准偏差 ＜14%，具有良好的稳定性和重现性.本方法可在9 min内完成检测，临床血浆样本的测试结果与日本Sysmex公司的CA1500血凝仪测试结果一致，具有灵敏度高、检测时间短、检测结果准确等优点.

关键词：巨磁阻效应；微流体免疫传感器；D-二聚体；磁颗粒

来源出版物：分析化学，2015，43（6）： 802-807联系邮箱：高云华，yhgao@mail.ipc.ac.cn

Toward rational and modular molecular design in soft matter engineering

ZHANG Wen-bin，Stephen Z.D. Cheng

Abstract： This essay discusses some preliminary thoughts on the development of a rational and modular approach for molecular design in soft matter engineering and proposes ideas of structural and functional synthons for advanced functional materials. It echoes the Materials Genome Initiative by practicing a tentative retro-functional analysis（RFA）scheme. The importance of hierarchical structures in transferring and amplifying molecular functions into macroscopic properties is recognized and emphasized. According to the role of molecular segments in final materials，there are two types of building blocks： structural synthon and functional synthon. Guided by a specific structure for a desired function，these synthons can be modularly combined in various ways to construct molecular scaffolds. Detailed molecular structures are then deduced，designed and synthesized precisely and modularly. While the assembled structure and property may deviate from the original design，the study may allow further refinement of the molecular design toward the target function. The strategy has been used in the development of soft fullerene materials and other giant molecules. There are a few aspects that are not yet well addressed：（1）function and structure are not fully decoupled and（2）the assembled hierarchical structures are sensitive to secondary interactions and molecular geometries across different length scales. Nevertheless，the RFA approach provides a starting point and an alternative thinking pathway by provoking creativity with considerations from both chemistry and physics. This is particularly useful for engineering soft matters with supramolecular lattice formation，as in giant molecules，where the synthons are relatively independent of each other.

Keywords： Molecular design； Materials genome； Molecular nanoparticles； Soft matter； Synthon

来源出版物：Chinese Journal of Polymer Science，2015，33（6）： 797-814联系邮箱：ZHANG Wen-bin，wenbin@pku.edu.cn

Bis-triarylamine with a cyclometalated diosmium bridge： A multi-stage redox-active system

SUN Meng-jia，NIE Hai-jing，YAO Jian-nian，et al.

Abstract： A tetra（pyrid-2-yl）-pyrazine-bridged cyclometalated diosmium complex 1（PF6）2with two distal redox-active organic amine substituents has been synthesized and characterized. This complex displays four consecutive and separated anodic redox waves at +0.24，+0.38，+0.64，and +0.71 V vs. Ag/AgCl. Upon stepwise oxidation，four-step absorption spectral changes in the visible to near-infrared region have been observed. The different redox states of 1（12+through 16+）can be distinguished by the significantly different absorption spectra in the visible and near-infrared region. DFT calculations of 13+show that the spin is delocalized on both osmiumamine components.

Keywords： Mixed-valent compounds； Spectroelectrochemistry； Near-infrared electrochromism；Redox-active compounds； Triarylamines

来源出版物：Chinese Chemical Letters，2015，26（6）： 649-652

联系邮箱：ZHONG Yu-wu，zhongyuwu@iccas.ac.cn

封面介绍：The formation of tendon adhesion after tendon trauma and tendon repair surgery always threatens the rehabilitation efficacy seriously. The cover picture presents a beautiful blueprint，in which the electrospun polyester membrane is employed to prevent the postoperative adhesion and reduce the inflammatory response in the tendon recovery process. The produced electrospun polyester mats exhibit high surface area，tunable aperture，controllable degradation，and excellent biocompatibility. More importantly，the implantation treatment with the electrospun polyester membrane reduces the complication and enhances the repair of tendon injury. The meticulous zoopery demonstrates a bright future of electrospun polyester membranes as a barrier of postoperative tendon adhesion，which is conducive to the recovery of motor function.（see the article by Zhiming Song，Bo Shi，Jianxun Ding，Xiuli Zhuang，Xiaonan Zhang，Changfeng Fu & Xuesi Chen on page 1159-1168）.

A comparative study of preventing postoperative tendon adhesion using electrospun polyester membranes with different degradation kinetics

SONG Zhi-ming，SHI Bo，DING Jian-xun，et al.

Abstract： Complications arising from tendon injury include tendon sheath infection and peritendinous adhesion，in which tendon adhesion often leads to serious motor dysfunction. In this work，the electrospun membranes of poly（L-lactide）（PLA）and poly（e-caprolactone）（PCL）with different degradation kinetics were used to investigate their efficacy for anti-adhesion toward Achilles tendon repair. Compared with the PCL membrane，the PLA sample showed a faster rate of degradation in 42 d，and all the degradation media（i.e.，phosphate-buffered saline）maintained at a constant pH of around 7.4. Meanwhile，the superior biocompatibility of both the PLA and PCL membranes were proved by the in vitro cellular adhesion tests and in vivo histopathological assays. Simultaneously，the PLA membrane was more effective than the PCL sample in decreasing adhesion and promoting functional recovery. Furthermore，the experiment result was further confirmed by hematoxylin-eosin and Masson’s trichrome staining，and type I collagen immunohistochemical analysis. All results revealed that the model treated with the electrospun PLA membrane was obviously better with regard to both anti-adhesion and tendon repair than that in the PCL membrane group. Considering the results of degradation and adhesion prevention efficacy，the electrospun polyester membranes，especially the PLA one，would be applied with fascinating potential in clinical prevention of postoperative tendon adhesion.

Keywords： anti-adhesion； Achilles tendon repair； biodegradability； electrospun membrane； poly（L-lactide）； poly（e-caprolactone）

来源出版物：SCIENCE CHINA Chemistry，2015，58（7）： 1159-1168联系邮箱：DING Jian-xun，jxding@ciac.ac.cn

封面介绍：The cover picture shows a direct synthesis of 26-thio steroidal sapogenins from natural steroidal sapogenins，which serve as an important kind of resource compounds and basic starting materials in steroidal pharmaceutical industry. This method was based on a key and magic BF3·Et2O promoted C-26 sulfuration of steroidal sapogenins，which resulted in the direct replacement of the oxygen atom in F-ring of steroidal sapogenins by sulfur. The synthesis not only provides a concise method for 26-thio steroidal sapogenins，but also presents an ideal model of the utilization of steroidal sapogenins. More details are discussed in the article by Wang and Tian et al. on page 632-636.

BF3·Et2O Promoted Sulfuration of Steroidal Sapogenins

WANG Jun，WU Jing-jing，TIAN Wei-sheng，et al.

A reaction between steroidal sapogenins and hydrogen sulfide promoted by BF3·Et2O is described. The thiodiosgenin and thiotigogenin comprising a sulfur atom on the F ring can be easily afforded in one step under this mild reaction condition. Furthermore，a hypothetical mechanism is also shown.

steroidal sapogenin； hydrogen sulfide； sulfuration； spiroketal； resource chemistry