Synthesis, Characterization and Properties of Novel Star-Shaped π-Conjugated Oligomers with Triphenylamine Core

Four new star‐shaped π‐conjugated oligomers ( TPA‐CZ3 , TPA‐TPA3 , TPA‐PTZ3 and TPA‐BT3 ) with triphenylamine as a core and different electron‐donating ability groups, carbazole, triphenylamine, phenothiazine and bithiophene, as peripheral units have been designed and synthesized via the Heck reaction. These oligomers show good solubility in common organic solvents. Their photophysical, electrochemical, electronic structure and charge transfer properties between these star‐shaped π‐conjugated oligomers and N,N′‐bis(1‐ethylpropyl)‐3,4:9,10‐perylene bis(tetracarboxyl diimide) (EP‐PDI) have been investigated by UV‐vis absorption spectra, photoluminescence (PL) spectra, cyclic voltammetry (CV) measurement, theoretical calculations and fluorescence quenching. The results show that the absorptions and fluorescences of TPA‐CZ3 , TPA‐TPA3 and TPA‐PTZ3 are red shifted with the electron‐donating ability of the peripheral unit increasing from carbazole to triphenylamine and phenothiazine. In addition, although the bithiophene group has a weaker electron‐donating ability than carbazole, triphenylamine and phenothiazine, the absorption and fluorescence of TPA‐BT3 have a red shift than those of TPA‐CZ3 , TPA‐TPA3 and TPA‐PTZ3 because TPA‐BT3 has a longer conjugation length than TPA‐CZ3 , TPA‐TPA3 and TPA‐PTZ3 . The triphenylamine core and the peripheral units can constitute a large conjugated structure. The fluorescence quenching properties indicate that efficient charge transfer can happen between the star‐shaped oligomers and EP‐PDI.     

Quantitative fingerprinting by headspace—Two-dimensional comprehensive gas chromatography–mass spectrometry of solid matrices: Some challenging aspects of the exhaustive assessment of food volatiles

The study proposes an investigation strategy that simultaneously provides detailed profiling and quantitative fingerprinting of food volatiles, through a “comprehensive” analytical platform that includes sample preparation by Headspace Solid Phase Microextraction (HS-SPME), separation by two-dimensional comprehensive gas chromatography coupled with mass spectrometry detection (GC × GC–MS) and data processing using advanced fingerprinting approaches.     

The Influences of Polymers and Temperature on the Foam Properties of 3‐Dodecylalkoxyl‐2‐hydroxylpropyl Trimethylammonium Chloride

The foam performances of 3‐dodecoxy‐2‐hydroxypropyl trimethylammonium chloride (C₁₂TAC) have been determined in the existence of different relative amount of polymer. The experimental results show that the foaming ability of the mixture systems of the C₁₂TAC/PEG and C₁₂TAC/PVP is stronger than that of the surfactant solutions in the absence of polymer, and with the increase of relative amount of polymer both foaming efficiency and foam stability of the surfactant solutions are evidently enhanced. For the aqueous solution of the surfactant, effect of temperature on foaming properties has also been examined. The results show that both the foaming ability and stability of the foams of the surfactant solutions are highest (or strongest) at 30°C.     

Response surface optimisation applied to a headspace-solid phase microextraction-gas chromatography-mass spectrometry method for the analysis of volatile organic compounds in water matrices

A new method for the simultaneous determination of 12 volatile organic compounds (trans-1,2-dichloroethene, 1,1,1-trichloroethane, benzene, 1,2-dichloroethane, trichloroethene, toluene, 1,1,2-trichloroethane, tetrachloroethene, ethylbenzene, m-, p-, o-xylene) in water samples by headspace solid phase microextraction (HS–SPME)–gas chromatography mass spectrometry (GC–MS) was described, using a 100?µm PDMS (polydimethylsiloxane) coated fibre. The response surface methodology was used to optimise the effect of the extraction time and temperature, as well as the influence of the salt addition in the extraction process. Optimal conditions were extraction time and temperature of 30?min and ?20°C, respectively, and NaCl concentration of 4?mol?L^?1. The detection limits were in the range of 1.1?×?10^?3–2.3?µg?L^?1 for the 12 volatile organic compounds (VOCs). Global uncertainties were in the range of 4–68%, when concentrations decrease from 250?µg?L^?1 down to the limits of quantification. The method proved adequate to detect VOCs in six river samples.     

Molecularly imprinted nanoparticles-based electrochemical sensor for determination of ultratrace parathion in real samples

Molecularly imprinted polymer nanoparticles (nano-MIP), containing parathion selective sites, were synthesized by using suspension polymerization in silicon oil and then used for carbon paste electrode preparation. The obtained electrode was applied as an electrochemical sensor for parathion determination in different fruit and vegetable samples. Different factors including electrode composition, conditions of parathion extraction in the electrode and electrochemical measurement conditions were evaluated and then optimized by using various techniques of screening and response surface experimental designs. Electrode response to parathion (Res₁) and its selectivity for parathion (Res₂) were the desired responses. These responses were optimized simultaneously. After optimization, a sensor with high selectivity and picomolar detection limit were obtained. It was shown that the sensor response to parathion concentration was linear in the concentration range of 0.05 to 150?nmol?L^?1. The detection limit of designed sensor was calculated equal to 0.02?nmol?L^?1. The developed determination method was properly used for ultra-trace level assay of parathion in different fruit and cabbage samples.     

A Simple Approach for Multi‐fidelity Experimentation Applied to Financial Engineering

In practical applications, information about the accuracy or ‘fidelity’ of alternative surrogate systems may be ambiguous and difficult to determine. To address this problem, we propose to treat surrogate system fidelity level as a categorical factor in optimal response surface design. To design the associated experiments, we apply the Expected Integrated Mean Squared Error optimal design criterion, which takes into account both variance and bias errors. The performance of the proposed design was compared using three test cases to four types of alternatives using the Empirical Integrated Squared Error. Because of its ability to foster relatively accurate predictions, the proposed design is recommended in fidelity experimental design, particularly when the experimenters lack sufficient information about the fidelity levels of surrogate systems. The method was applied to the case of intraday trading optimization in which data were collected from the Taiwan Futures Exchange. We also calculated the implied volatility from the Merton's Jump‐diffusion model via the fast Fourier transform algorithm with three different models of varying fidelity levels. Copyright © 2014 John Wiley & Sons, Ltd.     

Molecular dynamics simulation of configurational ensembles compatible with experimental FRET efficiency data through a restraint on instantaneous FRET efficiencies

Förster resonance energy transfer (FRET) measurements are widely used to investigate (bio)molecular interactions or/and association. FRET efficiencies, the primary data obtained from this method, give, in combination with the common assumption of isotropic chromophore orientation, detailed insight into the lengthscale of molecular phenomena. This study illustrates the application of a FRET efficiency restraint during classical atomistic molecular dynamics simulations of a mutant mastoparan X peptide in either water or 7 M aqueous urea. The restraint forces acting on the donor and acceptor chromophores ensure that the sampled peptide configurational ensemble satisfies the experimental primary data by modifying interchromophore separation and chromophore transition dipole moment orientations. By means of a conformational cluster analysis, it is seen that indeed different configurational ensembles may be sampled without and with application of the restraint. In particular, while the FRET efficiency and interchromophore distances monitored in an unrestrained simulation may differ from the experimentally‐determined values, they can be brought in agreement with experimental data through usage of the FRET efficiency restraining potential. Furthermore, the present results suggest that the assumption of isotropic chromophore orientation is not always justified. The FRET efficiency restraint allows the generation of configurational ensembles that may not be accessible with unrestrained simulations, and thereby supports a meaningful interpretation of experimental FRET results in terms of the underlying molecular degrees of freedom. Thus, it offers an additional tool to connect the realms of computer and wet‐lab experimentation. © 2014 Wiley Periodicals, Inc.     

Studies of Synergism in Binary Alkylbenzene Sulfonate Mixtures for Producing Low Interfacial Tensions at Oil/Water Interface

In order to study the synergism between alkybenzene sulfonate and alkybenzene sulfonate, five di-n-alkylbenzene sulfonates were used and the interfacial tensions of single sulfonates and their binary mixtures against a series of alkane homologues were measured. The effects of hydrophilic-lipophilic abilities of sulfonates and mixing ratio on synergism were discussed. It is revealed that the synergistic mechanism derives from the amelioration of the hydrophilic-lipophilic ability of the surfactant system, and the method to achieve synergism is adding the hydrophilic alkybenzene sulfonate to the lipophilic alkylbenzene sulfonate, and ultralow interfacial tensions can be obtained in proper mixing ratios. The results are useful for enhanced oil recovery.      

分光光度法测定亚甲基蓝溶液浓度线上实验设计

基于朗伯-比尔定律与互补色原理,利用QQ截图读取色块RGB三原色组成的功能,获得不同亚甲基蓝浓度色阶对应的红色和绿色信号,设计了亚甲基蓝测定的简易紫外-可见分光光度法实验方案。该方案包括标准色阶制作、颜色信号读取、标准曲线绘制,以及待测样品测试等。通过学生实验,获得了满意的可靠性。该实验方案尤其适用于线上教学或缺少分光光度计的线下教学。     

计算化学在正丁醚制备实验教学中的应用*

正丁醚的制备是重要的大学有机化学实验,为提高学生对该实验所涉及的反应机理和关键操作要点的深入了解,采用Gaussian计算软件对正丁醇在酸催化下和无催化剂下的反应体系进行了研究,重点考察了酸催化下反应的主、副反应方向的反应机理。结果表明无催化剂下,正丁醇在常压液相下几乎不能发生反应;在酸催化下,正丁醇发生取代反应生成醚的反应路径是优势反应通道;酸催化下正丁醇的取代和消除反应速率常数均随温度增加而迅速增大,但消除反应的反应速率随温度增加更快,温度超过420 K消除反应将变得很明显,综合考虑,制备正丁醚的反应温度应控制在130~140 ℃之间较为合适。利用计算化学以图、表和动图等形式直观、动态、量化地解释了正丁醇成醚和成烯反应的竞争,该结果有助于更好地控制该反应体系,可用作实验教材的补充内容。