化学

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化学

二苯基膦功能化氧化石墨固载铂催化剂的制备及其催化烯烃硅氢加成性能

邓圣军，郑强，饶福原，等

以氧化石墨为载体，采用二苯基膦配体对其进行改性，再利用膦配体对Pt的螯合配位作用合成了氧化石墨固载膦铂配合物催化剂（GO-P-Pt），并采用元素分析、FT-IR、XRD等方法对催化剂进行了表征，考察了催化剂催化不同烯烃与三乙氧基硅烷的硅氢加成反应性能.结果表明，该催化剂对烯烃与三乙氧基硅烷的硅氢加成反应具有良好的催化活性，在100℃，反应180 min后，1-辛烯的转化率为94.6%，β-加成产物的选择性高达99.4%；当底物为芳香烯烃时，β-加成产物的选择性比脂肪烯烃低.此外，催化剂在重复使用4次之后，活性基本保持不变.

硅氢加成；氧化石墨；铂催化剂；烯烃

来源出版物：无机化学学报，2015，31（6）： 1085-1090

联系邮箱：邓圣军，dshj1028@126.com

来源出版物：SCIENCE CHINA Chemistry，2015，58（6）： 937-946联系邮箱：Wang Jie-Yu，jieyuwang@pku.edu.cn

Zn物种对乙烯芳构化反应过程的影响

陈绪川，董梅，牛宪军，等

摘要：分别采用离子交换法和物理混合法制备了不同Zn含量的ZSM-5分子筛催化剂，采用X射线衍射、扫描电子显微镜、N2物理吸附、氨程序升温脱附、吡啶红外吸附光谱、紫外-可见光谱和X射线光电子能谱等技术研究了催化剂的结构、表面性质及Zn物种种类，探讨了Zn物种存在状态对乙烯芳构化反应的影响.结果表明，引入到HZSM-5中的Zn物种包括三种状态，即ZnO晶体、存在于分子筛孔道中的ZnO团簇以及Zn和分子筛质子酸中心通过固相反应生成的 Zn（OH）+物种；不同的制备方法显著影响 Zn物种的分布.比较了制备方法和Zn含量对ZSM-5分子筛催化剂在乙烯芳构化反应中性能的影响，发现Zn（OH）+物种是芳构化的主要活性中心，同时ZnO物种的存在有助于乙烯制芳烃反应的发生.

关键词：乙烯；芳构化；锌物种；HZSM-5；脱氢作用

来源出版物：催化学报，2015，36（6）： 880-888

联系邮箱：樊卫斌，fanwb@sxicc.ac.cn

封面介绍：K3PO4was used as a neutralized base in Koble-Schmitt reaction of o-cresol with 95.4% yield after 4 h under 150℃ and 3 MPa CO2. No CO2 was released during the following neutralization process，and the K3PO4could be recovered and recycled by the neutralization of KH2PO4with KOH. For details see pp647-651

磷酸钾中和法邻甲酚羧化反应的绿色合成

伍琳娟，朱大建，肖瑟，等

摘要：以邻甲酚和二氧化碳为原料，以磷酸钾为中和剂一步羧化合成邻甲基水杨酸及相关产物.探讨了反应条件对产率的影响.实验结果表明，当磷酸钾与邻甲酚物料比为2.5∶1，反应温度150℃，反应压力3.0 MPa时，羧化反应产物总收率达到95.4%，同时邻甲基水杨酸收率也达到最大.与传统碳酸钾中和法相比，磷酸钾中和法产物在后处理过程中无二氧化碳放出，后处理过程中的磷酸根可制备为磷酸钾使用，新工艺是一条绿色化工路线.

关键词：二氧化碳；磷酸钾；邻甲基水杨酸；绿色合成；邻甲酚

来源出版物：应用化学，2015，32（6）： 647-651联系邮箱：李光兴，ligxabc@163.com

封面介绍：A nickel-catalyzed cross-coupling of gem-difluoropropargyl bromide with aryl boronic acids has been developed. It features use of low-cost Ni-catalyst and good functional group compatibility，thus providing a facile route for application in drug discovery and development. ［Zhang Xin-gang et al. on page 383-387.］

镍催化的芳基硼酸偕二氟炔丙基化反应

肖玉兰，潘强，张新刚

摘要：偕二氟炔丙基取代的芳烃是一类非常重要的化合物，但传统合成该类化合物的方法却存在很大局限性.以过渡金属催化直接向芳烃偕二氟炔丙基化是一种高效简洁制备上述化合物的方法.以廉价易得的Ni（NO3）2·6H2O为催化剂，首次实现了镍催化下芳基硼酸与α，α-二氟炔丙基溴的偶联反应.该反应不仅温和高效、原料廉价易得、官能团兼容性良好，而且还能进行克量级放大和对生物活性分子的后期氟修饰，从而为新药研发提供了一种有效手段.

关键词：镍；芳基硼酸；α，α-二氟炔丙基溴；交叉偶联反应

来源出版物：化学学报，2015，73（5）： 383-387联系邮箱：张新刚，xgzhang@sioc.ac.cn

Renewable β-myrcene polymerization initiated by lutetium alkyl complexes ligated by imidophosphonamido ligand

LIU Bo，HAN Bao-yu，ZHANG Chun-ling，et al.

Abstract： β-Imidophosphonamido ligated lutetium alkyl complex（NPNDipp）Lu（CH2SiMe3）2（THF）（NPNDipp= Ph2P（NC6H3iPr2-2，6）2）with the activation of AliBu3and ［Ph3C］［B（C6F5）4］ exhibited high catalytic activity，medium syndio-（rr = 66%）but remarkably high 3，4-regioselectivity for the polymerization of β-myrcene（MY）. In sharp contrast，high isotactic 3，4-polymyrcene（PMY）（mm = 95%）was obtained by the precursor（NPNEt）Lu（CH2SiMe3）2（THF）（NPNEt= PPh2（NC6H3iPr2-2，6）（NC6H4-Et-2））with less bulky substituents on the N-aryl ring.

Keywords： Lutetium； β-Myrcene； Regioselectivity

来源出版物：Chinese Journal of Polymer Science，2015，33（5）： 792-796

联系邮箱：Li Shi-hui，shihui-li@ciac.ac.cn

Gel-incorporated PbS and PbI2single-crystals

LIU Wei，LIU Yu-jing，CHEN Liao，et al.

Abstract： Gel-incorporated single-crystals provide unique combinational properties of long-range order and composite structures，which is desired for semiconducting and conducting materials. However，the reported gel-incorporated single-crystals are limited to insulating crystals. Here，we examine crystals of two typical semiconductors，lead sulfide（PbS）and lead iodide（PbI2），grown from both silica gels and agarose gels. In all the four crystal-gel pairs，single-crystals of the cubic phase of PbS and the hexagonal phase of PbI2were obtained according to the X-ray diffraction analysis. Dissolution of the gel-grown crystals exposed insoluble materials with the shape similar to the original crystals，indicative of gelincorporation inside the crystals. As such，this work creates a facile strategy to construct 3D heterostructures inside semiconducting single-crystals without destroying their long-range order.

Keywords： Single crystals； Gel-incorporation； Semiconductor； PbS； PbI2

来源出版物：Chinese Chemical Letters，2015，26（5）： 504-508

联系邮箱：Han-Ying Li，hanying_li@zju.edu.cn

封面介绍：The cover picture shows a novel porous organic polymer（POP）which was constructed through the condensation of triptycene tricatechol and 1，3，5-benzenetris（4-phenylboronic acid）. POPs are a kind of organic materials which possess permanent porosity and thus have great potentials in the field of gas storage and separation. The as-prepared triptycene-based POP exhibits high H2uptake（up to 1.84 wt% at 77 K，1 bar），large CO2adsorption capacity（up to 18.1 wt% at 273 K，1 bar），and excellent CO2/N2adsorption selectivity（up to 120/1）. The influence of solvent on the gas adsorption performance of the POP has also been investigated. More details are discussed in the article by Zhao et al. on page 539-544.

A triptycene-based porous organic polymer that exhibited high hydrogen and carbon dioxide storage capacities and excellent CO2/N2selectivity

LU Xi-long，ZHOU Tian-you，WU Dou-feng，et al.

Abstract： A novel porous organic polymer（POP）has been constructed through the condensation of triptycene tricatechol and 1，3，5-benzenetris（4-phenylboronic acid）. This triptycene-based POP exhibited high H2uptake（up to 1.84 wt% at 77 K，1 bar），large CO2adsorption capacity（up to 18.1 wt% at 273 K，1 bar），and excellent CO2/N2adsorption selectivity（up to 120/1）. The influence of solvent on the gas adsorption performance of the POP has also been investigated.

Keywords： porous organic polymers； H2/CO2adsorption； CO2/N2selectivity

来源出版物：Chinese Journal of Chemistry，2015，33（5）： 539-544联系邮箱：Xin Zhao，XZhao@mail.sioc.ac.cn

封面介绍：On page 637-642，Wang et al developed a microfluidic approach for tumor tissue microarray construction. By using breast cancer MCF-7 cell as a model，the performance of the microfluidic tumor tissue microarray was investigated. Experimental results showed that the developed microfluidic approach was simple and efficient for tumor research.

微流控芯片上的肿瘤组织微阵列构建

王伟鑫，刘未平，吴斌，等

摘要：研发了一种多层复合微流控芯片，包含64细胞培养微孔阵列，该微阵列集成了细胞进样、水凝胶三维支架形成和持续灌流培养的过程.以MCF-7乳腺癌细胞为模型，连续培养中监测细胞存活率、细胞密度、增殖率和细胞内 pH值，并同时进行冰冻切片后免疫组化染色.实验结果显示，乳腺癌细胞在水凝胶微球中增殖形成了类组织结构.E-cadherin及Vinculin在细胞内、细胞间隙均出现较强表达，提示水凝胶微球中细胞建立了细胞-细胞、细胞-间质连接.芯片上连续培养15天内细胞存活率保持在85%以上，细胞增殖率随时间延长而递减.细胞内pH值检测显示芯片3D培养细胞内部呈现明显的酸化，其程度随着细胞密度增大而增加.这种芯片肿瘤组织微阵列构建方法简单高效，有望发展成为肿瘤研究的有力工具.

关键词：微流控芯片；肿瘤组织微阵列；微环境；三维细胞培养

来源出版物：分析化学，2015，43（5）： 637-642联系邮箱：刘大渔，dyliu@foxmail.com

封面介绍：Organic semiconductors have aroused great attention as optoelectronic materials due to their low cost，flexibility and solution processability. Thanks to the emergence of effective materials，including small molecules and conjugated polymers，the performance of organic materials experiences a blooming development. Due to more ordered packing with fewer defects compared with thin films，one-dimensional（1D）micro/nanostructures of organic semiconductors are generally believed to be potential candidates for showing intrinsic high carrier mobility of organic materials. Moreover，the packing structure in micro/nanostructures is clear and relatively easy to analyze，making these micro/nanostructures a good platform to study structure-property relationship. Both molecular structures and growing methods play an important role in obtaining desirable 1D micro/ nanostructures. In this mini review，a series of promising p-type and n-type organic small molecules which can pack into 1D micro-/nanostructures with outstanding device performance are discussed. Besides，different methods to obtain ideal micro/nanostructures are also involved.

One-dimensional（1D）micro/nanostructures of organic semiconductors for field-effect transistors

ZHENG Yu-qing，WANG Jie-yu，PEI Jian

Organic semiconductors have gradually become the super stars on the stage of optoelectronic materials，due to their low cost，flexibility and solution processability. Numerous organic semiconductors，including small molecules and conjugated polymers，have been designed and synthesized to explore the potential of organic materials in optoelectronic industry. One-dimensional micro/nanostructures of organic semiconductors generally have more ordered packing structure with fewer defects compared with thin films，and are thus thought to show intrinsic carrier mobility of organic materials. Moreover，the packing structure in micro/nanostructures is clear and relatively easy to analyze，which makes these micro/nanostructures a good platform to study structure-property relationship. Therefore，design of suitable organic molecules to form micro-/nanostructures and methods to obtain ideal micro/nanostructures for functional devices will be fully discussed in this mini review. Finally，the perspective and opportunity of 1D micro/nanostructured organic materials based OFETs in the near future are also addressed.

organic semiconductors； organic field-effect transistors； one-dimensional； micro/nanostructures； self-assembly