Chemometric tools improving the determination of anti-inflammatory and antiepileptic drugs in river and wastewater by solid-phase microextraction and liquid chromatography diode array detection

An analytical method for the simultaneous determination of seven non-steroidal anti-inflammatory drugs (naproxen, ketoprofen, diclofenac, piroxicam, indomethacin, sulindac and diflunisal) and the anticonvulsant carbamazepine in river and wastewater is reported. The method involves pre-concentration and clean-up by solid-phase microextraction using polydimethylsiloxane/divinylbenzene fibers, followed by liquid chromatography with diode array detection analysis. Owing to the fact that river water samples did not contain interferences and no sensitivity changes due to sample matrix were observed, external calibration was implemented. Standardization was also applied in order to carry out the prediction step by preparing only two diluted standards that were subjected to the pre-concentration step and a set of standards prepared in solvent. For the analysis of wastewater samples, in contrast, it was necessary to implement standard addition calibration in combination with the multivariate curve resolution-alternating least squares (MCR-ALS) algorithm, which allowed us to overcome matrix effect and exploit the second order advantage. Recoveries ranging from 72% to 125% for all pharmaceuticals proved the accuracy of the proposed method in river water samples. On the other hand, wastewater sample recoveries ranged from 83% to 140% for all pharmaceuticals, showing an acceptable performance – considering this sample contains no modeled interferences.     

Differentiation between Shallow and Deep Charge Trap States on Single Poly(3‐hexylthiophene) Chains through Fluorescence Photon Statistics

Blinking of the photoluminescence (PL) emitted from individual conjugated polymer chains is one of the central observations made by single‐molecule spectroscopy (SMS). Important information, for example regarding excitation energy transfer, can be extracted by evaluating dynamic quenching. However, the nature of trap states, which are responsible for PL quenching, often remains obscured. We present a detailed investigation of the photon statistics of single poly(3‐hexylthiophene) (P3HT) chains obtained by SMS. The photon statistics provide a measure of the number and brightness of independently emitting areas on a single chain. These observables can be followed during blinking. A decrease in PL intensity is shown to be correlated with either 1) a decrease in the average brightness of the emitting sites; or 2) a decrease in the number of emitting regions. We attribute these phenomena to the formation of 1) shallow charge traps, which can weakly affect all emitting areas of a single chain at once; and 2) deep traps, which have a strong effect on small regions within the single chains.     

Design of liquid crystals with ‘de Vries-like’ properties: the effect of an ethynyl spacer in the core structure

We investigate the origins of ‘de Vries-like’ liquid crystalline behaviour by introducing an ethynyl spacer in the core of the tricarbosilane-terminated 5-phenylpyrimidine mesogens QL16-6 and QL17-6. The rationale for this structural change is based on the assumption that an ethynyl spacer would create more free volume in the core sub-layer and therefore decrease the orientational order parameter S₂ in the SmA phase. The tricarbosilane-terminated mesogens WL41-5 and WL42-6 with a 5-(phenylethynyl)pyrimidine core in either a normal or inverted orientation were synthesised, and their mesomorphic and ‘de Vries-like’ properties characterised using polarised optical microscopy, differential scanning calorimetry, birefringence measurements, small–angle (SAXS) and 2D X-ray scattering. Reduction factors R derived from SAXS and optical tilt angle measurements suggest that neither WL41-5 (R = 0.49) nor WL42-6 (R = 0.80) exhibit ‘de Vries-like’ properties. The S₂(T) profiles show an increase in orientational order with decreasing temperature and a sharp discontinuity at the SmA-SmC transition, which is consistent with ‘de Vries-like’ behaviour. However, the L_eff(T) profiles suggest an increase in interdigitation that reduces the positive effect of increasing S₂ in compensating for the molecular tilt.     

Post‐Treatment of CH3NH3PbI3/PbI2 Composite Films with Methylamine to Realize High‐Performance Photoconductor Devices

Organometallic halide perovskites have attracted great research interest as light‐active materials for use in optoelectronics. Here, we report a high‐performance photoconductor based on a methylammonium lead iodide (MAPbI₃) film that was prepared from a methylamine‐treated MAPbI₃/PbI₂ perovskite film. An ultrahigh responsivity of 3.6 A W^?1 and detectivity of 5.4×10¹² Jones were obtained for the film under 0.5 mW cm^?2 white‐light illumination. In addition, under 420 nm light irradiation, the film exhibited its highest responsivity and detectivity of 30 A W^?1 and 2.4×10¹⁴ Jones, respectively. The excellent photo‐response performance results from the improved electronic quality and suppressed nonradiative recombination channels of the treated perovskite thin film.     

Effect of cage size on the third‐order optical properties of endohedral metallofullerenes Sc3N@C2n (2n = 68, 70, 78, and 80): A theoretical study

Geometrical structures of the investigated endohedral metallofullerenes Sc₃N@C_2n (2n = 68, 70, 78, and 80) were optimized at the B3LYP/6‐31G* level. The analyses of electronic structures display that the contribution of fullerene cage to the lowest unoccupied molecular orbital decreases as the cage size increases. Based on the optimized structures, the time‐dependent density functional theory combined with the sum‐over‐states method was used to investigate their nonlinear optical properties. Calculated third‐order polarizabilities γ and two‐photon absorption (TPA) cross‐section δ do not present the monotone variation with the size of fullerene cage, with largest γ of 0.48 × 10^?34 esu for Sc₃N@C₇₈ in static state, and largest δ of 12.374 GM for Sc₃N@C₇₀ in the wavelength of 902.5 nm. However, the obtained TPA resonant peaks shift red with the size of fullerene cage. By analyzing the electronic origin of the third‐order optical properties, it is found that the charge transfers from the fullerene cage to the encapsulated Sc₃N cluster make important contributions to the studied properties. © 2011 Wiley Periodicals, Inc. Int J Quantum Chem, 2011     

气固相法合成的Ti-ZSM-5催化剂上苯乙烯氧化反应的宏观动力学

 采用TiCl4气固相同晶取代法制得的Ti－ZSM－5作催化剂,对H2O2氧化苯乙烯反应的宏观动力学进行了研究,考察了催化剂、苯乙烯和H2O2用量及反应温度对苯乙烯氧化反应速率的影响．结果表明,催化剂Ti－ZSM－5和底物苯乙烯对苯乙烯氧化反应速率的贡献均为一级,而H2O2为1／2级;苯乙烯氧化反应的表观活化能Ea＝48．14kJ／mol．当以丙酮为溶剂,在n（PhCH∶CH2）／n（H2O2）＝7．91,催化剂用量为20g／L,反应温度为343K的条件下,反应360min时,苯乙醛选择性和H2O2利用率分别可达91．9％和88．6％．     

设计非线性光学材料的新思路:质子转移增强光学非线性

从酸的电子给体HO-C₆H₄-CHCH-C₆H₄-NO₂(OSN)可以向碱的电子受体Me₂N-C₆H₄-CHCH-C₅H₄N(DAMS)发生质子转移,质子转移后形成的相应离子与其中性分子相比,光学非线性增强.采用ZINDO-SOS,FF/PM₃及CPHF/PM₃三种方法对其进行了系统的理论研究.三种方法研究结果均表明,质子转移后所产生的离子和相应的中性分子相比,其第一超极化率β和第二超极化率γ-都显著增强.     

用HRS技术研究CdS/Cd纳米粒子的二阶光学非线性

用新发展的超瑞利散射（HRS）技术（一种非相干的方法）研究了表面富镉的CdS纳米粒子的二阶非线性光学性质。结果表明每个纳米粒子的二次非线性极化率β值在10^-26esu量级,这是目前报导的具有最大β值的溶液物种之列。探讨了CdS纳米粒子产生二阶非线性的机制。认为纳米粒子大的比表面及表面缺陷结构对CdS纳米粒子的二阶光学非线性有很大影响。另外,双光子吸收诱导的共振增强作用亦可能贡献CdS纳米粒子的HRS信号,这种双光子共振吸收被其双光子荧光谱所证实。     

芯片毛细管电泳-激光诱导荧光-电荷耦合器件检测系统

采用自组建的芯片毛细管电泳－激光诱导荧光－电荷耦合器件（CCD）检测系统在数十秒内满意地分离了曙红和荧光素。设计了一种进样、分 离电路,可以有效地消除进样通道的样品溶液向分离通道的渗漏。解决了由这种渗漏所引起的电泳峰变宽、拖尾等问题。提高了芯片毛细管电泳的分辨率和分离效率。