A multiaxial elastic potential with error-minimizing approximation to rubberlike elasticity

This study is concerned with a new,explicit approach by means of which forms of the large strain elastic potential for multiaxial rubberlike elasticity may be obtained based on data for a single deformation mode.As a departure from usual studies,here for the first time errors may be estimated and rendered minimal for all possible deformation modes and,furthermore,failure behavior may be incorporated.Numerical examples presented are in accurate agreement with Treloar's well-known data.     

Divergent Synthesis of Oxa-Cyclic Nitrones through Gold(I)-Catalyzed 1,3-Azaprotio Transfer of Propargylic α-Ketocarboxylate Oximes: Experimental and DFT Studies

1,3-Azaprotio transfer of propargylic α-ketocarboxylate oximes, a new type of alkynyl oximes featuring an ester tether, has been explored by taking advantage of gold catalysis. The incorporation of an oxygen atom to the chain of alkynyl oximes led to the formation of two different oxa-cyclic nitrones. It was found that internal alkynyl oximes with an E-configuration deliver five-membered nitrones, whereas terminal alkynyl oximes with an E-configuration afford six-membered nitrones. DFT calculations on four possible pathways supported a stepwise formation of C−N and C−H bonds, in which a 1,3-acyloxy-migration competes with the 1,3-azaprotio-transfer, especially in the case of internal alkynyl oximes. The relative nucleophilic properties of oxygen in the carbonyl group and the nitrogen in the oxime, the electronic effects of alkynes, and the influence of the ring system have been investigated computationally.     

Pattern时延差编码四信道水声通信技术研究

本文所研究的是基于Pattern时延差编码（PDS）体制下的水声通信技术.PDS水声编码体制利用Pattern码片出现在码元窗的时延差值进行时延编码,通过码元分割,有效的降低了水声信道的多途干扰;通过频率分割划分四个通信信道,增加通信速率至1000bit/s.在接收端利用带通滤波器来实现通信信道分割,每个信道再应用拷贝相关器实现码元分割并估计出时延差值,完成译码.仿真实验表明,该系统适合于大量不同水声信道高可靠性工作,为水声通信网络化打下坚实基础.     

碳纳米管电极超大容量离子电容器交流阻抗特性

采用碳纳米管作为超大容量离子电容器的电极材料,应用交流阻抗频谱法,研究了超大容量离子电容器的频率响应特性.结果表明,用碳纳米管块作电极,超大容量离子电容器在频率250 mHz以下出现“电荷饱和”；而用活性炭块作电极, 超大容量离子电容器在频率为100 mHz时仍未出现“电荷饱和”,这说明碳纳米管电极超大容量离子电容器的频率响应特性优于活性炭电极超大容量离子电容器的频率响应特性.上述两类超大容量离子电容器的阻抗谱中均出现倾角约为45°的直线段,其相位角均远小于理想电容器的相位角90°.     

Dimerizations of nitrile oxides to furoxans are stepwise via dinitrosoalkene diradicals: a density functional theory study

Density functional theory calculations at the B3LYP/6-31G* level on the dimerization reactions of acetonitrile oxide and para-chlorobenzonitrile oxide to form furoxans indicate that these processes are stepwise involving dinitrosoalkene intermediates that have considerable diradical character. The rate-determining steps for these two reactions correspond to C-C bond formation. The retardation of dimerization in aromatic nitrile oxides arises from the interruption of conjugation between the nitrile oxide and aryl groups in the C-C bond formation step. The present study also suggests that the isomerization of single-ring furoxans occurs via a diradical intermediate mechanism.     

5,10,15-Tris(pentafluorophenyl)corrole as highly selective neutral carrier for a silver ion-sensitive electrode

A new highly selective silver(I) electrode was prepared with a PVC membrane using 5,10,15-tris(pentafluorophenyl)corrole as an electroactive material, 2-nitrophenyl octyl ether (o-NPOE) as a plasticizer and sodium tetraphenylborate (NaTPB) as an additive in the percentage ratio of 3:3:62:32 (corrole:NaTPB:o-NPOE:PVC, w:w). The electrode exhibited linear response with a near Nernstian slope of 54.8 mV/decade within the concentration range of 5.1 × 10⁻⁶ to 1.0 × 10⁻¹ M silver ions, with a working pH range from 4.0 to 8.0, and a fast response time of <30 s. Selectivity coefficients for Ag(I) relative to a number of interfering ions were investigated. The electrode is highly selective for Ag(I) ions over a large number of mono-, bi-, and tri-valent cations. Common interferents like Hg²⁺ and Cd²⁺ show very low interfering effect on the silver assay, which is valuable property of the proposed electrode. Several electroactive materials and solvent mediators have been compared and the experimental conditions were optimized. The sensor was applied to the determination of silver in real ore samples with satisfied results.     

CH自由基与O2反应的从头算研究

采用量子化学从头算法（UMP2／6－31G**水平），从理论上研究了CH＋O2反应的两个主要通道.根据计算所得的反应诸途径（连接反应物Cn＋）及两个通道的最终产物）讨论了复杂的反应机理．发现反应过程涉及O2的第一激发态1△g，且沿反应途径有势能面相交，反应途径中包括多个中间体及过渡态．     

A donor–acceptor complex enables the synthesis of E-olefins from alcohols,amines and carboxylic acids

Olefins are prevalent substrates and functionalities. The synthesis of olefins from readily available starting materials such as alcohols, amines and carboxylic acids is of great significance to address the sustainability concerns in organic synthesis. Metallaphotoredox-catalyzed defunctionalizations were reported to achieve such transformations under mild conditions. However, all these valuable strategies require a transition metal catalyst, a ligand or an expensive photocatalyst, with the challenges of controlling the region- and stereoselectivities remaining. Herein, we present a fundamentally distinct strategy enabled by electron donor–acceptor (EDA) complexes, for the selective synthesis of olefins from these simple and easily available starting materials. The conversions took place via photoactivation of the EDA complexes of the activated substrates with alkali salts, followed by hydrogen atom elimination from in situ generated alkyl radicals. This method is operationally simple and straightforward and free of photocatalysts and transition-metals, and shows high regio- and stereoselectivities.

A visible-light-induced defunctionalization strategy for the synthesis of olefins by using easily available alcohols, amines and carboxylic acids as starting materials is demonstrated.     

Naphthodithiophene-based donor materials for solution processed organic solar cells

As an emerging donor building block, naphthodithiophene (NDT) is causing more concerns in the field of organic semiconductors. With the rigid and coplanar molecule structure, NDT will exhibit more application space relying on its own advantage for facilitating the charge carrier transport. In this review article, we have summarized the development progress on the NDT-based donor materials for solution processed organic solar cells. Discussions and comments on those representative NDT type materials about structure and property are also presented.     

Co-Catalyzed Asymmetric Intramolecular [3+2] Cycloaddition of Yne-Alkylidenecyclopropanes and its Reaction Mechanism

Developing new transition metal-catalyzed asymmetric cycloadditions for the synthesis of five-membered carbocycles (FMCs) is a research frontier in reaction development due to the ubiquitous presence of chiral FMCs in various functional molecules. Reported here is our discovery of a highly enantioselective intramolecular [3+2] cycloaddition of yne-alkylidenecyclopropanes (yne-ACPs) to bicyclo[3.3.0]octadiene and bicyclo[4.3.0]nonadiene molecules using a cheap Co catalyst and commercially available chiral ligand (S)-Xyl-BINAP. This reaction avoids the use of precious Pd and Rh catalysts, which are usually the choices for [3+2] reactions with ACPs. The enantiomeric excess in the present reaction can be up to 92 %. Cationic cobalt(I) species was suggested by experiments as the catalytic species. DFT calculations showed that this [3+2] reaction starts with oxidative cyclometallation of alkyne and ACP, followed by ring opening of the cyclopropyl (CP) group and reductive elimination to form the cycloadduct. This mechanism is different from previous [3+2] reactions of ACPs, which usually start from CP cleavage, not from oxidative cyclization.