化學(xué)

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化學(xué)

二苯基膦功能化氧化石墨固載鉑催化劑的制備及其催化烯烴硅氫加成性能

鄧圣軍，鄭強(qiáng)，饒福原，等

以氧化石墨為載體，采用二苯基膦配體對其進(jìn)行改性，再利用膦配體對Pt的螯合配位作用合成了氧化石墨固載膦鉑配合物催化劑（GO-P-Pt），并采用元素分析、FT-IR、XRD等方法對催化劑進(jìn)行了表征，考察了催化劑催化不同烯烴與三乙氧基硅烷的硅氫加成反應(yīng)性能.結(jié)果表明，該催化劑對烯烴與三乙氧基硅烷的硅氫加成反應(yīng)具有良好的催化活性，在100℃，反應(yīng)180 min后，1-辛烯的轉(zhuǎn)化率為94.6%，β-加成產(chǎn)物的選擇性高達(dá)99.4%；當(dāng)?shù)孜餅榉枷阆N時，β-加成產(chǎn)物的選擇性比脂肪烯烴低.此外，催化劑在重復(fù)使用4次之后，活性基本保持不變.

硅氫加成；氧化石墨；鉑催化劑；烯烴

來源出版物：無機(jī)化學(xué)學(xué)報，2015，31（6）： 1085-1090

聯(lián)系郵箱：鄧圣軍，dshj1028@126.com

來源出版物：SCIENCE CHINA Chemistry，2015，58（6）： 937-946聯(lián)系郵箱：Wang Jie-Yu，jieyuwang@pku.edu.cn

Zn物種對乙烯芳構(gòu)化反應(yīng)過程的影響

陳緒川，董梅，牛憲軍，等

摘要：分別采用離子交換法和物理混合法制備了不同Zn含量的ZSM-5分子篩催化劑，采用X射線衍射、掃描電子顯微鏡、N2物理吸附、氨程序升溫脫附、吡啶紅外吸附光譜、紫外-可見光譜和X射線光電子能譜等技術(shù)研究了催化劑的結(jié)構(gòu)、表面性質(zhì)及Zn物種種類，探討了Zn物種存在狀態(tài)對乙烯芳構(gòu)化反應(yīng)的影響.結(jié)果表明，引入到HZSM-5中的Zn物種包括三種狀態(tài)，即ZnO晶體、存在于分子篩孔道中的ZnO團(tuán)簇以及Zn和分子篩質(zhì)子酸中心通過固相反應(yīng)生成的 Zn（OH）+物種；不同的制備方法顯著影響 Zn物種的分布.比較了制備方法和Zn含量對ZSM-5分子篩催化劑在乙烯芳構(gòu)化反應(yīng)中性能的影響，發(fā)現(xiàn)Zn（OH）+物種是芳構(gòu)化的主要活性中心，同時ZnO物種的存在有助于乙烯制芳烴反應(yīng)的發(fā)生.

關(guān)鍵詞：乙烯；芳構(gòu)化；鋅物種；HZSM-5；脫氫作用

來源出版物：催化學(xué)報，2015，36（6）： 880-888

聯(lián)系郵箱：樊衛(wèi)斌，fanwb@sxicc.ac.cn

封面介紹：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

磷酸鉀中和法鄰甲酚羧化反應(yīng)的綠色合成

伍琳娟，朱大建，肖瑟，等

摘要：以鄰甲酚和二氧化碳為原料，以磷酸鉀為中和劑一步羧化合成鄰甲基水楊酸及相關(guān)產(chǎn)物.探討了反應(yīng)條件對產(chǎn)率的影響.實驗結(jié)果表明，當(dāng)磷酸鉀與鄰甲酚物料比為2.5∶1，反應(yīng)溫度150℃，反應(yīng)壓力3.0 MPa時，羧化反應(yīng)產(chǎn)物總收率達(dá)到95.4%，同時鄰甲基水楊酸收率也達(dá)到最大.與傳統(tǒng)碳酸鉀中和法相比，磷酸鉀中和法產(chǎn)物在后處理過程中無二氧化碳放出，后處理過程中的磷酸根可制備為磷酸鉀使用，新工藝是一條綠色化工路線.

關(guān)鍵詞：二氧化碳；磷酸鉀；鄰甲基水楊酸；綠色合成；鄰甲酚

來源出版物：應(yīng)用化學(xué)，2015，32（6）： 647-651聯(lián)系郵箱：李光興，ligxabc@163.com

封面介紹：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.］

鎳催化的芳基硼酸偕二氟炔丙基化反應(yīng)

肖玉蘭，潘強(qiáng)，張新剛

摘要：偕二氟炔丙基取代的芳烴是一類非常重要的化合物，但傳統(tǒng)合成該類化合物的方法卻存在很大局限性.以過渡金屬催化直接向芳烴偕二氟炔丙基化是一種高效簡潔制備上述化合物的方法.以廉價易得的Ni（NO3）2·6H2O為催化劑，首次實現(xiàn)了鎳催化下芳基硼酸與α，α-二氟炔丙基溴的偶聯(lián)反應(yīng).該反應(yīng)不僅溫和高效、原料廉價易得、官能團(tuán)兼容性良好，而且還能進(jìn)行克量級放大和對生物活性分子的后期氟修飾，從而為新藥研發(fā)提供了一種有效手段.

關(guān)鍵詞：鎳；芳基硼酸；α，α-二氟炔丙基溴；交叉偶聯(lián)反應(yīng)

來源出版物：化學(xué)學(xué)報，2015，73（5）： 383-387聯(lián)系郵箱：張新剛，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

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

聯(lián)系郵箱：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

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

聯(lián)系郵箱：Han-Ying Li，hanying_li@zju.edu.cn

封面介紹：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

來源出版物：Chinese Journal of Chemistry，2015，33（5）： 539-544聯(lián)系郵箱：Xin Zhao，XZhao@mail.sioc.ac.cn

封面介紹：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.

微流控芯片上的腫瘤組織微陣列構(gòu)建

王偉鑫，劉未平，吳斌，等

摘要：研發(fā)了一種多層復(fù)合微流控芯片，包含64細(xì)胞培養(yǎng)微孔陣列，該微陣列集成了細(xì)胞進(jìn)樣、水凝膠三維支架形成和持續(xù)灌流培養(yǎng)的過程.以MCF-7乳腺癌細(xì)胞為模型，連續(xù)培養(yǎng)中監(jiān)測細(xì)胞存活率、細(xì)胞密度、增殖率和細(xì)胞內(nèi) pH值，并同時進(jìn)行冰凍切片后免疫組化染色.實驗結(jié)果顯示，乳腺癌細(xì)胞在水凝膠微球中增殖形成了類組織結(jié)構(gòu).E-cadherin及Vinculin在細(xì)胞內(nèi)、細(xì)胞間隙均出現(xiàn)較強(qiáng)表達(dá)，提示水凝膠微球中細(xì)胞建立了細(xì)胞-細(xì)胞、細(xì)胞-間質(zhì)連接.芯片上連續(xù)培養(yǎng)15天內(nèi)細(xì)胞存活率保持在85%以上，細(xì)胞增殖率隨時間延長而遞減.細(xì)胞內(nèi)pH值檢測顯示芯片3D培養(yǎng)細(xì)胞內(nèi)部呈現(xiàn)明顯的酸化，其程度隨著細(xì)胞密度增大而增加.這種芯片腫瘤組織微陣列構(gòu)建方法簡單高效，有望發(fā)展成為腫瘤研究的有力工具.

關(guān)鍵詞：微流控芯片；腫瘤組織微陣列；微環(huán)境；三維細(xì)胞培養(yǎng)

來源出版物：分析化學(xué)，2015，43（5）： 637-642聯(lián)系郵箱：劉大漁，dyliu@foxmail.com

封面介紹：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