New multifunctional heterobinuclear palladium (II) complexes based on organometallic dithiocarbazate ligands

In the research of new compounds with multifunctional applications, heterobinuclear palladium (II) complexes based on organometallic dithiocarbazates (DTCZs) have been isolated. The organometallic DTCZ ligands of the general formula [{(η⁵-C₅H₄)-CH=NNHC(S)SCH₃}]MLn [MLn = Re (CO)₃ ( 2a ); Mn (CO)₃ ( 2b ); FeCp ( 2c )] were prepared by the reaction between formyl organometallic precursors ( 1a−c ) with S-methyldithiocarbazate. Subsequently, a two-step reaction of 2a−c with: (i) K₂[PdCl₄] and (ii) PPh₃ yielded heterobinuclear complexes [Pd{MLn(η⁵-C₅H₄)-CH=NNHC(S)SCH₃}–(Cl)(PPh₃)] [MLn = Re (CO)₃ ( 3a ); Mn (CO)₃ ( 3b ); FeCp ( 3c )]. All compounds were characterized by conventional spectroscopic techniques (infrared spectroscopy, nuclear magnetic resonance spectroscopy, mass spectrometry and elemental analysis). In addition, the molecular structures of 2a , 2c and 3c were determined by single-crystal X-ray diffraction. The new palladium (II) complexes ( 3a−c ) were evaluated as antiproliferative agents against non-small cell lung cancer cells (H1299 cells). Complexes 3a and 3b containing cyrhetrenyl- and cymantrenyl-DTCZ ligands, respectively, were more active than their ferrocenyl analogue 3c . The activity was associated with the electron-withdrawing properties of the (η⁵-C₅H₄)M (CO)₃ moieties and their better lipophilicity than that of the ferrocenyl analogue. In addition, we studied the capacity of metalloligands ( 2a−c ) and palladium (II) complexes ( 3a−c ) to remove methylene blue in water under UV–visible light irradiation. The results established that the complexes showed moderate efficiency and were less active than their corresponding free ligands.     

Photocatalytic decolourization of a new water-insoluble organic dye based on phenothiazine by ZnO and TiO2 nanoparticles

A new water-insoluble organic dye, namely, 2-((10-decyl-10H-phenothiazin-3-yl)methylene)malononitrile, was synthesized and fully characterized. It was envisioned that photocatalytic decolourization of a dye-containing long chain would pave the way for the photocatalytic remediation of wastewater containing toxic hydrophobic organic pollutants. Two commercially available nanoparticles, ZnO and TiO₂, were selected, and their photocatalytic decolourization of the dye from aqueous medium were compared. The black UV light irradiation of the colored samples in the presence of TiO₂ (P25) or ZnO resulted in their decolourization and the photocatalytic activity observed for TiO₂ (P25) was better than that of ZnO. The kinetic of decolourization indicated that the process was first-order from which the rate constant was calculated. Also, the effect of pHs on the kinetic of decolourization revealed a negligible effect, indicating that the pH, although it affects the catalysts but has no effect on the organic-based hydrophobic dye and thus no effect on the photocatalytic process.     

Encapsulation-Controlled Photoisomerization of a Styryl Derivative: Stereoselective Formation of the Anti Z-Isomer in the Cucurbit[7]uril Cavity

The photochemical isomerization of a styrylpyridinium dye ( SP ) bearing an unsymmetrically attached benzo-15-crown-5 ether has been studied in aqueous solution in the absence and presence of cucurbit[7]uril (CB[7]). The detailed analysis of the UV/Vis and NMR spectra showes that the isomeric composition of the photostationary mixtures of SP can be modulated by the host-guest complexation with CB[7]. It was found that steric hindrance caused by encapsulation of SP in the host cavity induces the exclusive formation of the anti conformer of Z- SP in contrast with the mixture of both anti and syn conformers obtained during photoisomerization of the dye without CB[7]. Remarkably, the displacement of anti Z- SP from CB[7] does not lead to the transformation of the anti Z-isomer into the syn Z-isomer pointing out the conformational memory of the system. The results provide an interesting example of the supramolecular stereorecognition by the achiral CB[7] host.     

Novel local smoothness indicators for improving the third‐order WENO scheme

The local smoothness indicators play an important role in the performance of a weighted essentially nonoscillatory (WENO) scheme. Due to having only 2 points available on each substencil, the local smoothness indicators calculated by conventional methods make the third‐order WENO scheme too dissipative. In this paper, we propose a different method to calculate the indicators by using all the 3 points on the global stencil of the third‐order WENO scheme. The numerical results demonstrate that the WENO scheme with the new indicators has less dissipation and better resolution than the conventional third‐order WENO scheme of Jiang and Shu for both smooth and discontinuous solutions.     

利用CARS方法研究超短脉冲激光的脉冲宽度

在理论上提出了利用两光束CARS/CSRS方法测量超短脉冲激光的三阶相关函数。实验上在几种样品中测量了CARS/CSRS的时间特性,得到了泵浦光脉冲,SCDL输出光脉冲以及受激喇曼散射光脉冲的宽度。     

有机薄膜器件负电阻特性的影响因素

研究了影响有机染料掺杂聚合物薄膜器件负电阻特性的因素，为探索有机负电阻的机理提供实验依据。实验中制备了多种有机染料掺杂聚合物薄膜器件，研究了有机小分子染料、聚合物基体、薄膜组成及厚度、ITO和聚苯胺阳极等对有机染料掺杂聚合物薄膜器件负电阻特性的影响。在室温、大气环境下，所制备的多种有机染料掺杂聚合物器件在所加电压为3～4V时，观察到明显的负电阻特性，电流峰谷比最大约为8。负电阻现象及峰谷比的大小受膜厚和器件的结构、制备工艺等影响。提出用负电阻和二极管并联组成的等效电路模型解释影响负电阻特性的因素，认为负电阻特性与载流子的不平衡注入有关。在此基础上设计、合成了主链含唔二唑电子传输基团的可溶性聚对苯撑乙烯衍生物，该聚合物兼具空穴和电子传输功能，在空气中具有较稳定的N型负电阻特性。进一步控制相关材料和工艺条件，有可能得到易于控制的负阻效应，开发出新型的有机负电阻器件。     

Adsorption isotherms and kinetics of methylene blue on a low-cost adsorbent recovered from a spent catalyst of vinyl acetate synthesis

A regenerated activated carbon used as catalyst support in the synthesis of vinyl acetate has been tested as a low-cost adsorbent for the removal of dyes. After a thorough textural characterization of the regenerated activated carbon, its adsorption isotherms and kinetics were determined using methylene blue as model compound at different initial concentrations. Both Langmuir and Freundlich isotherm models were developed and then compared. It was found that the equilibrium data were best represented by the Langmuir isotherm model. The kinetic data were fitted to pseudo-first-order, pseudo-second-order and intraparticle diffusion models, and it was found that the best fitting corresponded to the pseudo-second-order kinetic model. The results showed that this novel adsorbent had a high adsorption capacity, making it suitable for use in the treatment of methylene blue enriched wastewater.     

The nonlinear optical response of a fluorine-containing azoic dye

The nonlinear optical nonlinearities of a fluorine-containing azoic dye in tetrahydrofuran have been investigated by using Z-scan technique with picosecond and nanosecond lasers. The experimental results reveal that the azoic dye has large optical nonlinearity under the excitations of picosecond and nanosecond 532 nm. At the picosecond 532 nm the solution presents negative nonlinear refraction due to the electronic effect, while the larger nonlinear refraction under nanosecond laser excitation is induced by thermal effect. Moreover, the different nonlinear absorption behavior under picosecond and nanosecond excitations is analyzed.     

LB膜混合聚集体中极性基团相互作用对光学非线性的影响

通过紫外－可见吸收光谱、压力－面积等温线、二次谐波的测量，研究了不同活性分子混合聚集体的形成对ＬＢ膜光学性质的影响。分子极性基团间的相互作用，使激发态能量及平均偶极矩发生变化，导致ＬＢ膜的光学非线性明显地增强或减弱。