Dehydrogenative Heck coupling of biologically relevant N-heteroarenes with alkenes: discovery of fluorescent core frameworks

A Pd/Cu-catalyzed dehydrogenative Heck coupling is established that allows direct alkenylation of various biologically relevant N-heteroarenes with alkenes. The resulting π-extended alkenylated N-heteroarenes exhibit interesting fluorescent properties and have proven to be potentially useful fluorescent probes for bioimaging.     

The first slipped pseudo-quadruple-decker complex of phthalocyanines

The first slipped pseudo-quadruple-decker complex of phthalocyanines was formed unexpectedly upon treatment of the protonated double-decker SmIIIH(Pc)[Pc(alpha-OC4H9)8] with NaOH. The supramolecular structure contains two double-decker units linked by two sodium ions by an extremely rare coordination mode of phthalocyanines in which an aza nitrogen atom and two oxygen atoms from neighboring alkoxy substituents form a tridentate ligand.     

Induced Potential in Porous Carbon Films through Water Vapor Absorption

Sustainable electrical potential of tens of millivolts can be induced by water vapor adsorption on a piece of porous carbon film that has two sides with different functional group contents. Integrated experiments, and Monte Carlo and ab initio molecular dynamics simulations reveal that the induced potential originates from the nonhomogeneous distribution of functional groups along the film, especially carboxy groups. Sufficient adsorbed water molecules in porous carbon facilitate the release of protons from the carboxy groups, resulting in a potential drop across the carbon film because of the concentration difference of the released free protons on the two sides. The potential utilization of such a phenomenon is also demonstrated by a self‐powered humidity sensor.     

Indirect biamperometric determination of o-phenylenediamine in lab-on-valve format using reversible indicating redox system

The miniaturized lab-on-valve (LOV) manifold well hyphenated with indirect biamperometry is presented for automated determination of trace level concentrations of organic environmental pollutants by programmable flow. The experimental procedure was carried out by means of taking o-phenylenediamine (OPDA) as a model analyte, relying on the Fe(iii)/Fe(ii) couple that served as an indicating redox system. The miniaturized electrochemical flow cell (EFC) designed and processed was integrated into the LOV module which is assembled with two identical polarized platinum electrodes between which a small potential difference (ΔE) was applied, to implement automated on-line analysis in a closed system. Factors affecting analytical performance are discussed, including indicating redox systems, concentration of indicating system, the acidity, the potential difference, and flow variables in the LOV. The calibration curve showed an excellent linearity in the concentration range of 5.0 × 10(-7) to 1.0 × 10(-4) mol L(-1) (R(2) = 0.9993). The limits of detection (LOD) and quantitation (LOQ) for OPDA were found to be 1.1 × 10(-7) and 3.7 × 10(-7) mol L(-1), respectively. A sampling frequency of 40 h(-1) was obtained along with an R.S.D. of 2.8% at 1.0 × 10(-6) mol L(-1) OPDA (n = 11). The proposed procedure was successfully applied to the assay of OPDA in industrial waste water.     

运用ESR方法测定一些地质样品年龄的尝试

本文介绍了用ESR测地质年代方法的发展、现状及基本原理。给出了用ESR方法测定四川鲜水河地震活动断裂带的泉华样品、泥河湾的丽蚌化石样品、北京周口店洞穴中石笋样品的天然辐射总剂量AD的初步结果。测定周口店洞穴中石笋样品的年龄为(6×10⁴)年。并对结果进行了讨论。最后,还就有关ESR测年代方法的一些有关问题进行了探讨。     

透明和吸收介质非线性参数n2,X^（3）及其时间响应特性研究

对透明和吸收介质的简并四波混频理论作了处理,实验上给出了掺半导体玻璃,无机和有机材料的三阶非线性极化率x~(3)和非线性折射率n_2的值,而且确定了非线性参数x~(3)的时间响应特性,实验装置的时间分辨率为5ps.     

Electron-donating or -withdrawing nature of substituents revealed by the electrochemistry of metal-free phthalocyanines

The effect of substituents on the electrochemistry of metal-free phthalocyanines was examined for 17 phthalocyanine compounds. This work also provides new information about the electron-donating or -withdrawing nature of various substituents, namely, alkoxy, alkylthio, alkyl, alkynyl, phenyloxy, and phenylthio groups attached to the phthalocyanine system, from the viewpoint of electrochemistry. Most of the effects of peripheral and nonperipheral substitution and changes in the ring (pi-conjugated system) size on the electrochemistry of metal-free phthalocyanines can be reasonably explained by considering the energy levels of frontier molecular orbitals of the corresponding compounds, which were obtained by calculations using the semiempirical PM3 method.     

Self‐Powered Multimodal Temperature and Force Sensor Based‐On a Liquid Droplet

Herein we report a self‐powered multimodal temperature and force sensor based on the reverse electrowetting effect and the thermogalvanic effect in a liquid droplet. The deformation of the droplet and the temperature difference across the droplet can induce an alternating pulse voltage and a direct voltage, respectively, which is easy to separate/analyze and can be utilized to sense the external force and temperature simultaneously. In addition, an integral display system that can derive information from external temperature/force concurrently is constructed. Combined with advantages of excellent sensing properties and a simple structure, the droplet sensor has promising applications in a wide range of intelligent electronics.     

Formation of phosphorus-nitrogen bonds by reduction of a titanium phosphine complex under molecular nitrogen

The reduction of high oxidation state metal complexes in the presence of molecular nitrogen is one of the most common methods to synthesize a dinitrogen complex. However, the presence of strong reducing agents combined with the poor binding ability of N2 can lead to unanticipated outcomes. For example, the reduction of [NPN]ZrCl2(THF) (where NPN = PhP(CH2SiMe2NPh)2) with KC8 under N2 leads to the formation of the side-on bridged dinuclear dinitrogen complex ([NPN]Zr(THF))2(mu-eta2:eta2-N2) with an N-N bond distance of 1.503(3) A; however, reduction of the corresponding titanium precursor, [NPN]TiCl2, under N2 does not generate a dinitrogen complex, rather the bis(phosphinimide) derivative, ([N(PN)N]Ti)2, is isolated in which the added N2 is incorporated between the titanium and phosphine centers. Performing the reaction under 15N2 results in the 15N label being incorporated in the phosphinimide unit. A suggested mechanism for this process involves an initially formed dinitrogen complex being over reduced to generate a species with bridging nitrides that undergoes nucleophilic attack by the coordinated phosphine ligands and formation of the P=N bond of the phosphinimide.