Laser spectroscopic investigation of a new precursor-type polyparaphenylenevinylene

Optical, structural and morphological properties of thin films of polyparaphenylenevinylene (PPV) formed by an alkyl sulfinyl precursor route have been studied. Thin films were fabricated on an optical glass and on quartz glass either by spin-coating of the precursor solution or by layer-by-layer deposition using Langmuir–Blodgett technique. PPV precursor films were also spin-coated on gold-coated glass in order to study thin-film optical parameters by surface plasmon spectroscopy. We have been successful in forming about 40 precursor mono layers on quartz glass by Langmuir–Blodgett technique using optimized surface pressure and dipping conditions. After thermal conversion of the precursor layers good quality fluorescent PPV films of yellow colour have been obtained. Optical characterization of the films was carried out by linear absorption and emission spectroscopy, ellipsometry, and surface plasmon spectroscopy. Structural and morphological studies on the thin films were carried out by using X-ray scattering and atomic force microscopy. Wave-guided travelling-wave laser action has been achieved in a PPV film on quartz glass. The sample was transversally pumped with picosecond laser pulses (wavelength 347.15 nm, duration 35 ps). Laser emission occurred at 550 nm for pump pulse energy densities above .     

Nanorings in planar confinement: the role of repulsive surfaces on the formation of lacuna smectics

ABSTRACT

We study the structure and liquid-crystalline phase behaviour of a model of confined non-convex circular soft-repulsive nanorings in a planar slit geometry using molecular-dynamics simulation. The separation distance between the structureless parallel soft-repulsive walls is made large enough to allow for the formation of a distinct bulk phase in the central region of the box which is in coexistence with the adsorbed fluid thus allowing the analysis of single-wall effects. As the density of the particles is increased, the fluid adsorbs (wets) onto the planar surfaces leading to the formation of well-defined smectic-A layers with a spacing proportional to the diameter of the rings. An analysis of the nematic order parameter at distances perpendicular to the surface reveals that the particles in each layer exhibit anti-nematic behaviour and planar (edge-on) anchoring relative to the short symmetry axis of the rings. This behaviour is in stark contrast to the behaviour observed in convex disc-like particles that have the tendency to form nematic (discotic) structures with homeotropic (face-on) anchoring. The smectic phases formed by nanorings in the bulk and under confinement are characterised by the formation of low-density layered liquid-crystalline states with large voids, referred to here as lacuna smectic phases. In contrast to what is typically found for confined liquid-crystalline systems involving convex particles, no apparent biaxiality is found for nanorings in planar confinement. We argue that formation of the low-density lacuna smectic layers with planar anchoring is a consequence of the non-convex shape of the circular rings that allow for interpenetration between the particles as observed for nanorings under bulk conditions [C. Avendaño, G. Jackson, E.A. Müller and F.A. Escobedo, Proc. Natl. Acad. Sci. U.S.A. 113, 9699 (2016); H.H. Wensink and C. Avendaño, Phys. Rev. E 94, 062704 (2016)].     

利用钆配合物调节激基复合物发光颜色的一种有机发光二极管

报道一种可用钆配合物[Gd（DBM）3bath]调节电致发光（EL）颜色的有机发光二极管（OLED）。该有机发光二极管是在空穴传输层（m-MTDATA）和电子传输层（TPBI）之间插入-薄层Gd（DBM）3bath。随着Cd（DBM）3bath厚度增加,二极管的发光颜色呈现出绿色（主峰525nm）-黄色-橙色（主峰593rim）变化。该二极管的电致发光主要来自界面激基复合物的发射而不是来自各有机功能层;而发光颜色的变化是由于两种激基复合物发射的相对强度的改变。     

Mild synthesis of a Zn(II) metal organic polymer and its hybrid with activated carbon: Application as antibacterial agent and in water treatment by using sonochemistry: Optimization,kinetic and isotherm study

In this work, a room temperature and short method (30 min) for synthesis of nanosized rod-like metal organic polymer (MOP) has been described. Reaction of 1,4-phenylenedioxy diacetic acid with zinc salt leads to the formation of [Zn(C₁₀H₈O₆)(H₂O)₄]_n and subsequently was loaded on activated carbon following sonication and structurally characterized by FTIR, SEM, EDX and XRD analysis. The combination of this new composite with sonication was applied for rapid and efficient adsorption of Bromocresol Purple (BCP). Effects of initial BCP concentration, mass of adsorbent and sonication time on response were investigated and optimized by central composite design (CCD). Analysis of variation (ANOVA) was adapted to experimental data to find best optimum conditions which was set at 15.22 mg L⁻¹, 2.41 min, 0.02 g and 0.009 mg for initial BCP concentration, sonication time and adsorbent mass, respectively. Conduction of similar experiments at specified condition permit achievement of 98.69% removal percentage. 1,4-phenylenedioxy diacetic acid and Zn(NO3)₂.4H₂O which have applied for preparation of MOP are interesting antibacterial properties and accordingly MOP was screened in vitro for their antibacterial actively against Proteus vulgaris bacteria and experimental results reveal this MOP was able to inhibit growth of the tested bacteria. The experimental data were best fitted by pseudo-second order and Langmuir for kinetic model and the adsorption equilibrium isotherm, respectively.     

PARAFAC法解析太湖水体DOM三维荧光光谱

采用平行因子法(PARAFAC法)对太湖水样溶解性有机质(DOM)三维荧光光谱进行解析。通过比较因子数分别为3,4和5时,PARAFAC模型的核一致函数、 激发和发射光谱误差平方和、 各水样模拟的三维荧光光谱和残差谱图等情况,选择因子数为3作为太湖水样DOM三维荧光光谱PARAFAC模型的最佳因子数。太湖水样DOM的3类主要荧光组分分别是类腐殖质荧光物质、 类色氨酸荧光物质、 类酪氨酸荧光物质。     

电控液晶光阀中的指向矢分布特性

液晶分子具有介电和光学各向异性,在外电场作用下,液晶指向矢将会重新分布,具有高效的光学相位调制能力.本文从实验和理论角度对电控液晶光阀的光学调制特性进行了研究,结果表明:光阀阈值电压约为4V,且当外加电压高于阈值电压时,液晶光阀的透射强度随外加电压表现出非周期性特性.根据液晶连续体弹性理论,对电场作用下液晶光阀的指向矢分布特性进行数值分析,分析结果表明液晶光阀对透射光强的非周期调制特性取决于液晶体系的偏转状态,为研究液晶的偏振光调制特性提供理论依据及实验基础.     

Field-induced phase transitions and reversible field-induced inversion of chirality in tilted smectic phases of bent-core mesogens

Three homologous achiral five-ring bent-core mesogens are presented where 4-chlororesorcinol is the central core and the aromatic rings are linked by ester groups. These compounds form smectic phases with a tilted arrangement of the molecules (tilt angle ≈ 45^°). On cooling the isotropic liquid this phase adopts a fan-like texture which shows for two homologues at relatively high electric fields ( 25-35V μm^-1) an antiferroelectric electro-optical response based on the collective rotation of the molecules around their long axes. At lower temperature the application of a sufficiently high electric field leads to a continuous transition into a non-birefringent texture which exhibits randomly distributed domains of opposite handedness. These domains can be reversibly switched into a state of opposite chirality by reversal of the field polarity. This switching is bistable and shows a current response typical for a ferroelectric ground state. The possible mechanism of the field-induced phase transition, of the ferroelectric switching and of the field-induced inversion of the chirality is discussed on the base of XRD, ¹³C- and ¹H-NMR investigations, dielectric and electro-optical measurements.     

Frustrated structure of an anticlinic-like smectic-C phase

We present a polarising optical microscopy study of the low-temperature anticlinic-like tilted mesophase of the liquid-crystal compound octylphenyl-2-chloro-4-(p-cyano-benzoyloxy) (DB₈Cl). This mesophase has been described as a bilayer smectic structure in which the molecules within each layer are organised in an anticlinic way. The optical textures observed in samples with planar orientation show a double stripe pattern, with the lines aligned parallel to the rubbing direction, characteristic of a double periodic modulation of the refractive index of the material. The long-period modulation is temperature dependent and disappears for thin sample cells (< 5μm). The short-period modulation is nearly independent of the thickness of the cells. The experimental results are analysed in terms of a model which considers that there is a special distribution of the principal optical axis which may be in or out of the polariser-analyser plane. The observed periodic variation of the principal optical axis could not be interpreted in terms of the original structure proposed for this phase. DB₈Cl presents a structure formed by dimers that can be viewed as flexible bent-core-like molecules, showing similarities with phases found in banana-like systems, but exhibiting a much more complex structure.     

PTCDA/P-Si光电探测器欧姆接触层的XPS测试分析

在光电探测器PTCDA/P-Si芯片的有机层表面,成功制作出了比接触电阻为4.5×10-5Ω·cm2的低阻欧姆接触层。利用X射线光电子能谱(XPS)对Al/Ni/ITO的欧姆接触层界面的电子状态进行了测试和分析。结果表明,ITO中的In3d及Sn3d各出现两个分裂能级的谱峰,它们是In和Sn原子处于氧化环境的结合能。Ni2p有两个谱峰Ni2p(1)及Ni2p(2),低结合能位置Ni2p(1)对应于Ni原子被X射线激发产生的谱峰,说明NiITO之间没有发生化学反应,Ni层阻止了Al层被氧化成Al2O3;高结合能Ni2p(2)谱峰说明已形成了Al3Ni冶金相,有利于低阻欧姆接触层的形成。     

The pKa theoretical estimation of C―H,N―H,O―H and S―H acids in dimethylsulfoxide solution

A scheme for the pK_a estimation of organic acids in dimethylsulfoxide (DMSO) solution based on quantum chemical calculations is proposed. The procedure of pK_a calculation requires several steps. The first is the calculation of the gas phase acidity of the compound. The G3MP2B3, G4MP2 as well as CBS‐QB3 composite methods made it possible to estimate values of gas phase acidities of an extensive set of structures with a high confidence level (standard deviations equal to 1.15, 1.13 and 1.29 kcal mol^?1, respectively; the test set included 91 compounds). The second step is the computation of the solvation correction with the integral equation formalism version of polarizable continuum model (IEF‐PCM)–B3LYP/6‐311+G(d,p) approximation. Within the bounds of our approach, the medium properties were covered only by the PCM model, i.e. the proposed procedure neglects specific interactions between DMSO and the solute. It was determined that the approach to pK_a estimation mentioned above is the most balanced in terms of accuracy, resource intensity and computation time cost. In the third step, the error of the pK_a calculation was decreased by correlation allowances. Correlation allowances were determined for each acid class (62 С―Н, 55 N―Н, 24 O―Н and 5 S―Н acids) in the range of 50 units in terms of logarithmic scale using the test set including 146 compounds. Seven O―H acids showing the ability to form cyclic dimers were separated into a discrete group. The proposed methodology was applied to the estimation of pK_a for trans‐ and cis‐dimethyl‐4,5‐dihydro‐3H‐pyrazol‐3,5‐dicarboxylates as well as for 5‐fluorouracil subject to competitive dissociation, the latter by N1―H or N3―H bonds. Copyright © 2014 John Wiley & Sons, Ltd.