Structure and temperature controlled synthesis of novel thiazolidin-4-one derivatives bearing an azasugar

Novel thiazolidin-4-one linked pseudo-aza-disaccharides and thiazolidin-4-ones containing C-pseudo-aza-nucleosides were synthesized via a one-pot three component reaction. The former was synthesized stereoselectively by the tandem Staudinger/aza-Wittig/cyclization reaction of azasugar aldehyde 1, an azidosugar, and mercaptoacetic acid. The reaction was structure and temperature controlled, and could be performed stereospecifically under 40 °C. It was the first report of a stereospecific synthesis of thiazolidin-4-one linked derivatives. However, these derivatives were synthesized with low stereoselectivity by involving the condensation reaction of azasugar aldehyde 1, aniline, and mercaptoacetic acid.     

Theoretical and Experimental Study of the Diffraction Intensity of Gradient Refractive-Index Lenses

We develop the wave-optics approach for calculating the diffraction distribution of gradient refractiveindex lenses and observing the diffraction pattern of gradient refractive-index lenses in the experiments. The results of our calculation are in good agreement with the experimental results obtained. We show that the diffraction can be regarded as a method to check the quality of the refractive-index distributions of gradient refractive-index lenses.     

Quantitative study of cellular heterogeneity in doxorubicin uptake and its pharmacological effect on cancer cells

Cellular heterogeneity in doxorubicin (DOX) uptake and its relationship with pharmacological effect on cancer cells were quantitatively investigated for the first time. An in vitro experimental model was established by treating human leukemia K562 and breast cancer MCF‐7 cells with different schedules of DOX with or without surface P‐glycoprotein (P‐gp) inhibitor verapamil (VER). The cellular heterogeneity in DOX uptake was quantitatively examined by single‐cell analysis using capillary electrophoresis coupled with laser‐induced fluorescence detection. The corresponding cytotoxic effect was tested by cellular morphology, 3‐(4,5‐dimethylthiazol‐2‐yl)‐2,5‐diphenyl‐tetrazolium and flow cytometry assays. The expression of cellular membrane surface P‐gp was determined by flow cytometry. Results showed that the cellular heterogeneity exists in DOX uptake. The single‐high DOX schedule leads to lower uptake heterogeneity and higher mean drug uptake. The cellular heterogeneity in DOX uptake was found to be negatively correlated with drug cytotoxicity and surface P‐gp expression, with r = ?0.7680 to ~ ?0.9587. VER reduces the cellular variation in DOX uptake, suggesting that surface P‐gp may be one of the causes of the cellular heterogeneity in DOX uptake. This research demonstrates the importance of quantitative study of cellular heterogeneity in drug uptake and its potential application in drug schedule design, response prediction and therapy modulation. Copyright © 2014 John Wiley & Sons, Ltd.     

Two-photon dual-channel fluorogenic probe for in situ imaging the mitochondrial H2S/viscosity in the brain of drosophila Parkinson’s disease model

H₂S is an essential gas signal molecule in cells, and viscosity is a key internal environmental parameter. Recent studies have shown that H₂S acts as a cytoarchitecture agent and gas transmitter in many tissues, e.g., as a regulator of neuroendocrine in the brain for mediating vascular tone in blood vessels. Mitochondrial viscosity is an important parameter for judging whether mitochondrial function is normal. It has been reported that oxidative stress and mitochondrial dysfunction are connected with Parkinson’s disease (PD), and the protective role of H₂S in PD models has been extensively demonstrated. Herein, Mito-HS, a new two-photon fluorescent probe was demonstrated to detect cross-talk between the two channels of mitochondrial viscosity and H₂S content. Moreover, this probe could detect the relative amount of and changes in mitochondrial H₂S in situ due to the reduced mitochondrial targeting ability after reaction with H₂S. The results show that H₂S in mitochondria is inversely related to viscosity. The PD model has a lower H₂S in mitochondria and a higher mitochondrial viscosity than did the normal. This result is important for our deep understanding of PD and its causes.     

Dual template method to prepare hierarchical porous carbon nanofibers for high-power supercapacitors

Hierarchical porous carbon nanofibers serving as electrode materials are prepared through carbonization and hydrofluoric acid treatment of polyacrylonitrile-based electrospinning involving dual templates. The hierarchical porous structures are synergistically tailored by varying template contents in the spinning solution. The carbon nanofibers prepared from the electrospinning of polyacrylonitrile containing 15/15 wt.% polymethylmethacrylate/tetraethyl orthosilicate exhibit the largest specific surface area (699 m² g^?1) and microporous volume (0.196 cm³ g^?1). In 6 M KOH electrolyte, a symmetrical supercapacitor equipped with the hierarchical porous carbon nanofibers demonstrates its high-end specific capacitance of 170 F g^?1, superior rate capability, and high-power density output up to 14.7 kW kg^?1. Cycling evolution indicates capacitance fading is only 5.8 % of initial capacitance at a current density of 1 A g^?1 even after 8,000 cycles. The excellent electrochemical performances of the carbon nanofiber are mainly ascribed to the optimized pore size distributions of both micropores and mesopores and the unique hierarchical pore structures possessed by abundant micropores.     

ICP-AES测定电解镍中的杂质元素

采用电感耦合等离子体发射原子发射光谱法(ICP-AES)测定了电解镍中锰、磷、钴、铁、铜、镁、铝、锌、镉、硅和锡等11种元素的含量,对仪器各项参数进行优化,采用基体匹配办法克服基体干扰,通过选择合适的分析谱线和背景校正消除共存元素间干扰。方法应用于实际样品分析,11种元素的回收率为92.0%—107.0%,相对标准偏差0.3%—5.1%,测定结果与标准方法的测定值相符。     

Synthesis,structural characterization,and olefin polymerization behavior of vanadium(III) complexes bearing bidentate phenoxy‐phosphine ligands

Vanadium(III) complexes bearing phenoxy‐phosphine ligands ( 2a–g ) (2‐R₁‐4‐R₂‐6‐PPh₂‐C₆H₂O)VCl₂(THF)₂ ( 2a : R₁ = R₂ = H; 2b : R₁ = F, R₂ = H; 2c : R₁ = Ph, R₂ = H; 2d : R₁ = tBu, R₂ = H; 2e : R₁ = R₂ = Me; 2f : R₁ = R₂ = tBu; 2g : R₁ = R₂ = CMe₂Ph) were prepared from VCl₃(THF)₃ by treating with 1.0 equiv of the ligand in tetrahydrofuran (THF) in the presence of excess triethylamine (TEA). The reaction of VCl₃(THF)₃ with 2.0 equiv of the ligand in THF in the presence of excess TEA afforded vanadium(III) complexes bearing two phenoxy‐phosphine ligands ( 3c–f ). These complexes were characterized by FTIR and mass spectrum as well as elemental analyses. Structures of 2f and 3c were further confirmed by X‐ray crystallographic analyses. Complexes 2a–g and 3c–f were employed as the catalysts for ethylene polymerization under various reaction conditions. On activation with Et₂AlCl, these complexes exhibited high catalytic activities (up to 41.3 kg PE/mmol_V·h·bar) even at high temperature (70°C), and produced high molecular weight polymer with unimodal molecular weight distributions, indicating the polymerization took place in a single‐site nature. Complexes 3c–f displayed better thermal stability than the corresponding complexes 2a–g under similar conditions. In addition, copolymerizations of ethylene and 1‐hexene with precatalysts 2a–g were also explored in the presence of Et₂AlCl. Catalytic activity, comonomer incorporation, and properties of the resultant polymers can be controlled over a wide range by tuning catalyst structures and reaction parameters.© 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Synthesis and photovoltaic properties of conjugated side chains polymers with different electron‐withdrawing and donating end groups

A series of novel low band gap polymers containing conjugated side chains with 4,7‐dithien‐5‐yl‐2,1,3‐benzodiathiazole and different electron‐withdrawing end groups of aldehyde ( PT‐DTBTCHO ), 2‐ethylhexyl cyanoacetate ( PT‐DTBTCN ), 1,3‐diethyl‐2‐thiobarbituric acid ( PT‐DTBTDT ), and electron‐donating end group of 2‐methylthiophene ( PT‐DTBTMT ) have been designed and synthesized. All polymers exhibit good solubility in common organic solvents, film‐forming ability, and thermal stability. These conjugated polymers show the broad ultraviolet‐visible absorption and the narrow optical band gaps in the range of 1.65–1.90 eV. Through changing the end group of conjugated side chains, the photophysical properties and energy levels of the polymers were tuned effectively. Bulk heterojunction solar cells based on the blend of these polymers and (6,6)‐phenyl‐C₆₁‐butyric acid methyl ester (PC₆₁BM) reached the best power conversion efficiency (PCE) of 2.72%. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Palladium-catalyzed cycloaromatization polymerization of enediynes

Bergman cyclization has shown great promise in constructing conjugated polymers.However,the application of this reaction in polymer science is still limited due to the harsh reaction condition and ill-defined structure of the achieved polymers.To this end,the cycloaromatization polymerization of enediynes catalyzed by a series of transition metal catalysts is investigated in this work,by taking advantage of the coordination chemistry of the enediyne with the transition metal complexes.According to the nuclear magnetic resonance (NMR),Fourier transform infrared (FTIR),ultraviolet-visble (UV-Vis) spectroscopies and matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS) analysis,the cycloaromatization polymerization of enediynes proceeds under milder conditions and in a more controlled manner in the presence of palladium(Ⅱ) complexes,giving structurally regulated conjugated polymers in high yields.