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901.
The anion of 2-aryl acetonitrile derivatives reacted with a variety of heteroaryl chlorides or bromides in an S(N)Ar manifold to afford intermediate anions which were susceptible to oxidation. The addition of sodium peroxide and aqueous NH(4)OAc solution effected oxidation to afford aryl heteroaryl ketones in good yields. Aryl acetonitrile derivatives are thus umpolung-type synthons of the corresponding aryl carbonyl functionality. 相似文献
902.
Samorì P Yin X Tchebotareva N Wang Z Pakula T Jäckel F Watson MD Venturini A Müllen K Rabe JP 《Journal of the American Chemical Society》2004,126(11):3567-3575
We report the synthesis and characterization of covalent dyads and multiads of electron acceptors (A) and donors (D), with the purpose of exploiting their nanophase separation behavior toward (a) two-dimensional (2D) surface patterning with well-defined integrated arrays of dissimilar molecular electronic features and (b) bulk self-assembly to noncovalent columnar versions of the so-called "double cable" systems, the likes of which could eventually provide side-by-side percolation pathways for electrons and holes in solar cells. Soluble, alkylated hexa-peri-hexabenzocoronenes (HBCs) bearing tethered anthraquinones (AQs) are shown by scanning tunneling microscopy (STM) to self-assemble at the solution-graphite interface into either defect-rich polycrystalline monolayers or extended 2D crystalline domains, depending on the number of tethered AQs. In the bulk, the thermal stability of the room-temperature HBC columnar phase is increased, which is attributed to the desired nanotriphase separation of HBC columns, insulating alkyl sheaths, and AQ units. Homeotropic alignment (columns normal to surfaces), predicted to be ideal for potential exploitation of such "double cables" in photovoltaic devices, is demonstrated. 相似文献
903.
An efficient method is presented for the synthesis of novel donor-acceptor silole chromophores through selective monohalogenation of 2,5-dimetallosiloles followed by Negishi alkyne cross-coupling reactions. The electronic properties and crystal packing of these new siloles can be controlled through judicious combinations of peripheral functional groups. 相似文献
904.
A simple aptamer molecular beacon assay for rapid detection of aflatoxin B1 (AFB1) was achieved. AFB1-binding induced formation of a hairpin structure and closeness of fluorophore label and quencher probe, causing fluorescence decrease. 相似文献
905.
Meizhen Yin Yong Ye Mengmeng Sun Naiwen Kang Wantai Yang 《Macromolecular rapid communications》2013,34(7):616-620
A polyvinylpyrrolidone (PVP)‐based fluorescent film with stable optical properties is successfully prepared in one pot without any additive. The reaction mechanism of ring‐opening and self‐crosslinking of linear PVP is proposed and demonstrated. The morphologies and the nanostructures of the fluorescent film as well as the unmodified film are investigated. The dye is incorporated into the film networks via covalent linkages, thus leading to the highly stable optical properties. The facile and effective synthesis approach opens a new way for the design of other multi‐functional composite materials based on linear PVP.
906.
为探讨和比较炸药黑索金(RDX)和奥克托今(HMX)晶体的结构、 能量和力学性质随温度的递变规律, 在COMPASS力场和NPT系综下, 对其合适的等原子数超晶胞模型分别进行5个温度(195, 245, 295, 345和395 K)下的分子动力学(MD)周期性模拟研究. 结果表明, 随着温度的升高, RDX和HMX晶体引发键N-NO2的最大键长(Lmax)的逐渐增大以及引发键连双原子作用能(EN-N)和内聚能密度(CED)的逐渐减小均与感度随温度升高而增大的实验结果一致; 且在各温度下, RDX晶体的Lmax均大于HMX晶体的Lmax, 与HMX相比, RDX的EN-N和CED均较小, 上述结果与RDX比HMX感度大的实验结果相符. 由此表明, 在一定条件下, Lmax, EN-N和CED可用于高能物质的热和撞击感度的相对大小的判别. 基于MD模拟原子运动轨迹, 用静态法求得2种晶体的弹性力学性能, 发现拉伸、 体积和剪切模量均随温度的升高而递减, 与实验结果一致. 相似文献
907.
Xianpeng Yin Hao Dong Shiqiang Wang Yun Liang Ning Gao Wanlin Zhang Li Tian Fuwei Sun Guangtao Li 《中国化学快报》2019,30(1):179-182
In this work, large area gold-nanoparticle-cluster pillar array with a gold mirror as high-performance SERS substrate was facilely fabricated by combined use of nanosphere lithography and self-assembly approach. 相似文献
908.
Yu‐Yang Xie Zhi‐Min Chen Hui‐Yun Luo Hui Shao Yong‐Qiang Tu Xiaoguang Bao Ren‐Fei Cao Shu‐Yu Zhang Jin‐Miao Tian 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(36):12621-12626
An enantioselective sulfenylation/semipinacol rearrangement of 1,1‐disubstituted and trisubstituted allylic alcohols was accomplished with a chiral Lewis base and a chiral Brønsted acid as cocatalysts, generating various β‐arylthio ketones bearing an all‐carbon quaternary center in moderate to excellent yields and excellent enantioselectivities. These chiral arylthio ketone products are common intermediates with many applications, for example, in the design of new chiral catalysts/ligands and the total synthesis of natural products. Computational studies (DFT calculations) were carried out to explain the enantioselectivity and the role of the chiral Brønsted acid. Additionally, the synthetic utility of this method was exemplified by an enantioselective total synthesis of (?)‐herbertene and a one‐pot synthesis of a chiral sulfoxide and sulfone. 相似文献
909.
Ag2Se quantum dots (QDs) with near‐infrared (NIR) fluorescence have been widely utilized in NIR fluorescence imaging in vivo because of their narrow bulk band gap and excellent biocompatibility. However, most of synthesis methods for Ag2Se QDs are expensive and the reactants are toxic. Herein, a new protein‐templated biomimetic synthesis approach is proposed for the preparation of Ag2Se QDs by employing bovine serum albumin (BSA) as a template and dispersant. The BSA‐templated Ag2Se QDs (Ag2Se@BSA QDs) showed NIR fluorescence with high fluorescence quantum yield (≈21.2 %), excellent biocompatibility and good dispersibility in different media. Moreover, the obtained Ag2Se@BSA QDs exhibited remarkable photothermal conversion (≈27.8 %), which could be used in photothermal therapy. As a model application in biomedicine, the Ag2Se@BSA QDs were used as “gatekeepers” to cap mesoporous silica nanoparticles (MSNs) by means of electrostatic interaction. By taking the advantages of NIR fluorescence and photothermal property of Ag2Se@BSA QDs, the obtained MSN‐DOX‐Ag2Se nanoparticles (MDA NPs) were employed as a nanoplatform for combined chemo‐photothermal therapy. Compared with free DOX and MDA NPs without NIR laser, the laser‐treated MDA NPs exhibited lower cell viability in vitro, implying that Ag2Se@BSA QDs are highly promising photothermal agents and the MDA NPs are potential carriers for chemo–photothermal therapy. 相似文献
910.
Lead is a highly toxic metal, which can persist in the natural environment and enrich in biological bodies. It can cause many severe diseases in the human body even at extremely low concentration. Here, we developed a new biosensor using single‐walled carbon nanotubes (SWNTs) modified with a specific Pbzyme (Pbzyme/SWNTs/FET) to detect lead ion (Pb2+), which can monitor the lead pollution. This biosensor used 3‐aminopropyltriethoxysilane to immobilize SWNTs on the area between the source and the drain of single‐gap microelectrode (FET), and the duplex DNA (Pbzyme) consisted of DNAzyme (GR‐5) and complementary DNA (CS‐DNA) was functionalized with the SWNTs’ surface through a peptide bond. The use of GR‐5 DANzyme and Pb2+ to form a stable complex structure to cleave the CS‐DNA can change radically the Pbzyme's structure on the SWNTs’ surface, which will further affect the number of carriers in SNWTs and the conductivity of the Pbzyme/SWNTs/FET. The change in conductivity can be used to evaluate the Pb2+ concentration. Under the optimal conditions, the relative resistances presented a positive correlation with the Pb2+ concentrations, showing a good linear relationship in the range of 10 pM to 50 nM, where the linear regression equation was y=10.104log [CPb]+5.8656, and the detection limit was 7.4 pM. Finally, the biosensor was applied to measure the Pb2+ contents in the soil collected from the forest grass green belt and paint, and the results were compared with the results of atomic fluorescence spectrometry. 相似文献