Surface of room temperature ionic liquid [bmim][PF6] studied by polarization- and experimental configuration-dependent sum frequency generation vibrational spectroscopy

Understanding and control of the surface properties such as molecular orientations are of great importance in numerous applications of ionic liquids. However, there remain discrepancies among the previous experimental and theoretical studies on the surface orientation and structures of room temperature ionic liquids(RTIL) systems. In this article, the orientation of 1-butyl-3-methylimidazolium([bmin]) cation at the air/liquid interface of a characteristic RTIL, 1-butyl-3-methylimidazolium hexafluorophosphate([bmim][PF6]), was investigated by the sum frequency generation vibrational spectroscopy(SFG-VS). Detailed polarization and experimental configuration analyses of the SFG-VS spectra showed the possibility of a small spectral splitting in the CH3 symmetric stretching region, which can be further attributed to the probable existence of multiple orientations for the interfacial [bmim] cations. In addition, the(N)–CH3 vibrations were absent, ruling out the prediction by several recent molecular dynamics simulations which state that portions of the [bmim] cations orient with a standing-up(N)–CH3 group at the ionic liquid surface. Hence, new realistic theoretical models have to be developed to reflect the complex nature of the ionic liquid surface.     

Ferroelectric Coordination Polymers Self‐Assembled from Mesogenic Zinc(II) Porphyrin and Dipolar Bridging Ligands

A new class of ferroelectric coordination‐based polymers has been developed by the self‐assembly of lipophilic zinc porphyrin ( ZnP ) and ditopic bridging ligands. The ligands contain dipolar benzothiadiazole or fluorobenzene units, which are axially coordinated to ZnP with the dipole moments oriented perpendicular to the coordination axes. The coordination‐based polymers show ferroelectric characteristics in the liquid crystalline state, as revealed by distinctive hysteresis in the polarization–electric field (P–E) loops and inversion current peaks in current–voltage (I–V) loops. The observed ferroelectric properties are explainable by flip–flop rotation of the dipolar axle ligands induced by the applied electric field, as demonstrated by the positive‐up–negative‐down (PUND) measurements. The present system provides a new operating principle in supramolecular ferroelectrics.     

Chemical equilibrium controlled synthesis of polyoxymethylene dimethyl ethers over sulfated titania

The chemical equilibrium and reaction kinetic behavior in the synthesis of polyoxymethylene dimethyl ethers(DMMn) were investigated over sulfated titania in order to reveal the decisive factor controlling the reaction. The results showed that the molar ratio of adjacent DMMn products in equilibrium solution had the same value, which depended absolutely on the reaction temperature. Meanwhile, the reactions had the same DMMn products distributions under varied reaction conditions. The equilibrium constants of the related step-wise reactions for DMMn formation were equal, which were calculated based on the bulk compositions of the reaction solution. And thus, the selectivity to DMMn was mainly controlled by the chemical equilibrium, i.e., thermodynamic control. In brief, the present results provide some guidance for future synthesis of DMMn.     

Surface modification of polyolefin separators for lithium ion batteries to reduce thermal shrinkage without thickness increase

Surface chemical modification of polyolefin separators for lithium ion batteries is attempted to reduce the thermal shrinkage, which is important for the battery energy density. In this study, we grafted organic/inorganic hybrid crosslinked networks on the separators, simply by grafting polymerization and condensation reaction. The considerable silicon-oxygen crosslinked heat-resistance networks are responsible for the reduced thermal shrinkage. The strong chemical bonds between networks and separators promise enough mechanical support even at high temperature. The shrinkage at 150 C for 30 min in the mechanical direction was 38.6% and 4.6% for the pristine and present graft-modified separators, respectively. Meanwhile, the grafting organic-inorganic hybrid crosslink networks mainly occupied part of void in the internal pores of the separators, so the thicknesses of the graft-modified separators were similar with the pristine one. The half cells prepared with the modified separators exhibited almost identical electrochemical properties to those with the commercial separators, thus proving that, in order to enhance the thermal stability of lithium ion battery, this kind of grafting-modified separators may be a better alternative to conventional silica nanoparticle layers-coated polyolefin separators.     

A Pronounced Halogen Effect on the Organogelation Properties of Peripherally Halogen Functionalized Poly(benzyl ether) Dendrons

An interesting halogen‐substituent effect on the organogelation properties of poly(benzyl ether) dendrons is reported. A new class of poly(benzyl ether) dendrons with halo substituents decorating their periphery was synthesized and fully characterized. A systematic study on the gelation abilities, thermotropic behaviors, aggregated microstructures, and mechanical properties of self‐assembled organogels was performed to elucidate the halogen‐substituent effects on their organogelation propensity. It was found that the exact halogen substitutions on the periphery of dendrons exert a profound effect on the organogelation propensity, and dendrons G _n ‐Cl (n=2, 3) and G₂‐I proved to be highly efficient organogelators. The cooperation of multiple π–π, dispersive halogen, CH–π, and weak C?H ??? X hydrogen‐bonding interactions were found to be the key contributor to forming the self‐assembled gels. Dendritic organogels formed from G _n ‐Cl (n=2, 3) in 1,2‐dichloroethane exhibited thixotropic‐responsive properties, and such thixotropic organogels are promising materials for future research and applications.     

Tailorable PC71BM Isomers: Using the Most Prevalent Electron Acceptor to Obtain High‐Performance Polymer Solar Cells

Despite being widely used as electron acceptor in polymer solar cells, commercially available PC₇₁BM (phenyl‐C₇₁‐butyric acid methyl ester) usually has a “random” composition of mixed regioisomers or stereoisomers. Here PC₇₁BM has been isolated into three typical isomers, α‐, β₁‐ and β₂‐PC₇₁BM, to establish the isomer‐dependent photovoltaic performance on changing the ternary composition of α‐, β₁‐ and β₂‐PC₇₁BM. Mixing the isomers in a ratio of α/β₁/β₂=8:1:1 resulted in the best power conversion efficiency (PCE) of 7.67 % for the polymer solar cells with PTB7:PC₇₁BM as photoactive layer (PTB7=poly[[4,8‐bis[(2‐ethylhexyl)oxy]benzo[1,2‐b:4,5‐b′]dithiophene‐2,6‐diyl][3‐fluoro‐2‐[(2‐ethylhexyl)carbonyl]thieno[3,4‐b]thiophenediyl]]). The three typical PC₇₁BM isomers, even though sharing similar LUMO energy levels and light absorption, render starkly different photovoltaic performances with average‐performing PCE of 1.28–7.44 % due to diverse self‐aggregation of individual or mixed PC₇₁BM isomers in the otherwise same polymer solar cells.     

椭圆偏振法测定在线Low-E玻璃的可见-近红外光学常数与膜厚

从在线Low-E玻璃光学机理出发,用椭圆偏振光谱仪对在线Low-E玻璃功能层和过渡层的可见-近红外波段的光学常数进行研究.测量了样品在三个不同入射角的椭偏参数,分别用Lorentz双振子模型和Cauchy模型来描述Low-E玻璃功能层和过渡层的光学色散特性.通过拟合椭偏参数获得在线Low-E玻璃的光学常数及每层膜厚度,并用扫描电镜对样品的膜厚进行表征.结果表明,Lorentz双振子模型和Cauchy模型能很好地解释在线Low-E玻璃的光学特性;同时,椭圆偏振法也为多层膜系统提供了一种测定光学常数和膜厚的可靠方法.     

Dual‐signal amplification strategy for ultrasensitive chemiluminescence detection of PDGF–BB in capillary electrophoresis

Many efforts have been made toward the achievement of high sensitivity in capillary electrophoresis coupled with chemiluminescence detection (CE‐CL). This work describes a novel dual‐signal amplification strategy for highly specific and ultrasensitive CL detection of human platelet‐derived growth factor–BB (PDGF–BB) using both aptamer and horseradish peroxidase (HRP) modified gold nanoparticles (HRP–AuNPs–aptamer) as nanoprobes in CE. Both AuNPs and HRP in the nanoprobes could amplify the CL signals in the luminol–H₂O₂ CL system, owing to the excellent catalytic behavior of AuNPs and HRP in the CL system. Meanwhile, the high affinity of aptamer modified on the AuNPs allows detection with high specificity. As proof‐of‐concept, the proposed method was employed to quantify the concentration of PDGF–BB from 0.50 to 250 fm with a detection limit of 0.21 fm. The applicability of the assay was further demonstrated in the analysis of PDGF–BB in human serum samples with acceptable accuracy and reliability. The result of this study exhibits distinct advantages, such as high sensitivity, good specificity, simplicity, and very small sample consumption. The good performances of the proposed strategy provide a powerful avenue for ultrasensitive detection of rare proteins in biological sample, showing great promise in biochemical analysis. Copyright © 2015 John Wiley & Sons, Ltd.