化學(xué)

來源出版物：Chinese Journal of Chemistry，2015，33（6）： 632-636聯(lián)系郵箱：Wang Jun，wang.j@sustc.edu.cn

不飽和半夾芯式16e化合物Cp*Ir（S2C2B10H10）與鄰、間位取代苯基疊氮的反應(yīng)性

鐘偉，燕紅

考慮取代基的位置和電子效應(yīng)對反應(yīng)體系的影響，本文系統(tǒng)地研究了 16e化合物Cp*Ir（S2C2B10H10）（1）與鄰、間位取代苯基疊氮的反應(yīng).研究結(jié)果表明：與鄰、間位取代苯基疊氮反應(yīng)均生成苯環(huán)鄰位碳發(fā)生C—H活化形成C—S鍵的金屬配合物.這些配合物通過核磁（1H、11B、13C）、紅外、質(zhì)譜、元素分析和單晶結(jié)構(gòu)解析進(jìn)行了全面地表征.在光照反應(yīng)結(jié)果的基礎(chǔ)上，提出了形成這類產(chǎn)物的自由基機(jī)理.

半夾芯式配合物；取代苯基疊氮；反應(yīng)性；機(jī)理

來源出版物：無機(jī)化學(xué)學(xué)報(bào)，2015，31（7）： 1305-1314

聯(lián)系郵箱：鐘偉，weizhong@mail.zjxu.edu.cn

封面介紹：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.

苯并咪唑類化合物催化合成的研究進(jìn)展

程正，張群峰，許孝良，等

摘要：苯并咪唑類化合物在醫(yī)藥、農(nóng)藥等方面具有廣泛的應(yīng)用，因此這類化合物合成的新方法備受關(guān)注.從合成苯并咪唑類化合物的不同的原料出發(fā)，綜述了近年來催化合成苯并咪唑化合物的研究新進(jìn)展.

關(guān)鍵詞：苯并咪唑；鄰苯二胺；合成；催化劑

來源出版物：有機(jī)化學(xué)，2015，35（6）： 1189-1203

聯(lián)系郵箱：張群峰，zhangqf@zjut.edu.cn

封面介紹：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.］

有機(jī)多孔催化研究進(jìn)展

王昌安，王為

摘要：有機(jī)多孔材料POPs（Porous Organic Polymers）成為近年來的研究前沿之一.有機(jī)多孔材料包括非晶型（如CMP，HCP，PIM等）和晶型（比如COFs等）有機(jī)多孔材料兩類，它們具有優(yōu)異的孔性質(zhì)、較大的比表面積、穩(wěn)定性好、重量輕以及易于功能化等諸多優(yōu)點(diǎn)，被廣泛應(yīng)用于氣體存儲分離、傳感、有機(jī)光電和多相催化等重要領(lǐng)域.這里對有機(jī)多孔材料在多相催化領(lǐng)域中的應(yīng)用做一綜述. 目前，有機(jī)多孔催化領(lǐng)域的研究工作主要有三類：一類是通過“自下而上”策略將金屬-配體類催化劑嵌入有機(jī)多孔骨架來構(gòu)建多相催化劑；另一類是將有機(jī)多孔材料作為載體，通過后修飾方式負(fù)載金屬納米顆粒構(gòu)建多相催化劑；最后一類是通過“自下而上”策略將不含金屬的有機(jī)小分子催化劑嵌入材料骨架來構(gòu)建多孔有機(jī)催化劑.受益于其結(jié)構(gòu)的優(yōu)越性，有機(jī)多孔材料在多相催化中表現(xiàn)出優(yōu)異的催化性能.借鑒于均相催化的發(fā)展，具有催化活性的有機(jī)多孔材料在多相催化領(lǐng)域中的應(yīng)用也將會(huì)有更大的發(fā)展空間.

關(guān)鍵詞：有機(jī)多孔材料；“自下而上”策略；后修飾；多相催化；不對稱催化

來源出版物：化學(xué)學(xué)報(bào)，2015，73（6）： 498-529聯(lián)系郵箱：王昌安，wangcha_chem@163.com

封面介紹：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.

巨磁阻微流體免疫傳感器快速定量檢測D-二聚體

高宇哲，張磊，霍衛(wèi)松，等

摘要：將巨磁阻（GMR）傳感器集成在微流體通道中，以100 nm磁顆粒為信號探針，研制了可快速檢測血栓標(biāo)志物D-二聚體的免疫傳感器.用GMR傳感器在線檢測免疫反應(yīng)后被捕捉在芯片上的磁顆粒的信息，測定血漿中D-二聚體的含量.通過對反應(yīng)條件的優(yōu)化，建立了GMR微流體傳感器檢測血漿中D-二聚體的方法.本方法的線性檢測范圍為5～6500 ng/mL，檢出限為5 ng/mL.批內(nèi)相對標(biāo)準(zhǔn)偏差 ＜ 12%；批間相對標(biāo)準(zhǔn)偏差 ＜14%，具有良好的穩(wěn)定性和重現(xiàn)性.本方法可在9 min內(nèi)完成檢測，臨床血漿樣本的測試結(jié)果與日本Sysmex公司的CA1500血凝儀測試結(jié)果一致，具有靈敏度高、檢測時(shí)間短、檢測結(jié)果準(zhǔn)確等優(yōu)點(diǎn).

關(guān)鍵詞：巨磁阻效應(yīng)；微流體免疫傳感器；D-二聚體；磁顆粒

來源出版物：分析化學(xué)，2015，43（6）： 802-807聯(lián)系郵箱：高云華，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

來源出版物：Chinese Journal of Polymer Science，2015，33（6）： 797-814聯(lián)系郵箱：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

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

聯(lián)系郵箱：ZHONG Yu-wu，zhongyuwu@iccas.ac.cn

封面介紹：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）

來源出版物：SCIENCE CHINA Chemistry，2015，58（7）： 1159-1168聯(lián)系郵箱：DING Jian-xun，jxding@ciac.ac.cn

封面介紹：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