Photophysical,Electrochemical, Thermal and Morphological Properties of Polyurethanes Containing Azomethine Bonding

In this paper, three new low band gap Schiff bases were prepared by using 3-etoxy-4-hydroxybenzaldehyde and different o-phylene diamines. Then, these Schiff bases were converted to low band gap polyurethane derivatives, and their photophysical, electrochemical, thermal, mechanical and morphological properties were investigated. Photophysical properties of the compounds were investigated by using UV-Vis and photoluminescence (PL) spectroscopy. Electrochemical properties of Schiff bases and polyurethanes containing azomethine were investigated by using cyclic voltammetry (CV). Thermal decomposition and transitions were determined by using TG-DTA, DMA and DSC techniques, respectively. Morphological properties of the compounds were also determined by using scanning electron microscopy (SEM). SEM images showed that polyurethanes containing azomethine consist of semi-crystalline particles.     

Controlled synthesis of nonspherical microparticles using microfluidics

The controlled synthesis of nonspherical microparticles using microfluidics processing is described. Polymer droplets, formed by shearing a photopolymer using a continuous water phase at a T-junction, were constrained to adopt nonspherical shapes by confining them using appropriate microchannel geometries. Plugs were obtained by shearing the polymer phase at low shear rates, while disks were obtained by flattening droplets using a channel of low height. The nonspherical shapes formed were permanently preserved by photopolymerizing the constrained droplets in situ using ultraviolet light. Monodisperse plugs and disks of different lengths and diameters were obtained by varying the flow rates of the two phases.     

微柱液相色谱和电化学检测法测定鼠脑微透析液中神经传递物质

报道了使用微柱色谱和电化学检测器测定鼠脑微透析液中神经传递物质的方法。儿茶酚胺，５－羟色胺和代谢物的检测限为 ０． １～０． ５ ｐｇ。含有乙酰胆碱酯酶和胆碱氧化酶的柱后反应器使分离后的乙酰胆碱和胆碱转化成过氧化氢．再用铂电极或过氧化物酶修饰过的玻碳电极检测过氧化氢。乙酰胆碱的检测限当使用怕电极时是５０× １０－１５ｍｏｌ，当使用酶修饰电极时是１０×１０－１５ｍｏｌ。     

Study of the influence of surfactants on the transfer of gases into liquids by inverse gas chromatography

Analyses of amino acids and peptides were performed using a quartz microchip and an interface for microchip electrophoresis-electrospray ionization mass spectrometry (MCE-ESI-MS). In MCE-ESI-MS, negative pressure caused by ESI increased band broadening and deteriorated separation. We tried to suppress the negative pressure and improve separation using a microchip with a long separation channel. Separations of peptide standards were compared using two microchips with long separation channel (58.9 mm) and short one (22.9 mm). Theoretical plate numbers and resolution were improved significantly using the former. The theoretical plate numbers of [Val4]angiotensin was 8600 using the former and 1700 using the latter. When background electrolytes of low pH were used in an uncoated quartz microchip, electrokinetic injection was difficult because of weak electroosmotic flow. The use of successive multiple ionic polymer layers coating of the microchip channel stabilized electrokinetic injection and permitted analysis of amino acids and peptides even under low pH conditions. Separation of amino acids was successfully performed using formic acid solution (pH 2.5) as background electrolyte.     

Optimizing the extraction and analysis of DHEA sulfate, corticosteroids and androgens in urine: application to a study of the influence of corticosteroid intake on urinary steroid profiles

A method of detecting and quantifying dehydroepiandrosterone (DHEA) sulfate, corticosteroids, and androgens has been developed. All of the compounds were first extracted from urine using solid phase extraction (SPE), enzymatically hydrolyzed, and separated into three samples using a second SPE. A DHEA sulfate sample was acetylated and re-extracted using SPE for purification before analysis. Corticosteroid samples were oxidized and re-extracted using liquid/liquid extraction for analysis. Androgen samples were acetylated and re-extracted using SPE prior to analysis. The extraction and analysis methods were investigated and optimized. Analyses were performed with gas chromatography/mass spectrometry (GC/MS) and gas chromatography/flame ionization detection (GC/FID). The entire procedure was then applied to the study of urine profiles of healthy volunteers and patients treated with corticosteroids. The results showed that the quantities of androgens found in patient urines were lower than in those of healthy volunteers. In addition, other metabolites were detected in patient urines.     

A Comparative Study of Elution Gradients in UPLC-TOF-MS-Based Metabonomics Research

Serum and urine samples from patients with type 2 diabetes mellitus and control samples were analyzed by UPLC-TOF-MS; fast and slow separation gradients were compared using both positive and negative ionization modes. The resulting data were analyzed using partial least squares discriminant analysis (PLS-DA), and models were developed to differentiate between patient and control samples. The models were evaluated using external test sets to classify their predictive ability. Under both fast and slow gradient conditions, the PLS-DA models generated using serum samples were more robust than those generated using urine samples, and the positive ionization mode produced better differentiation and higher classification rates than negative ionization mode. In addition, fast gradient conditions were found to have a comparable ability for differentiation to slow gradient conditions.     

Low Temperature Bonding of Ceramics by Sol-Gel Processing

Silicon, sapphire and polycrystalline wafers have been bonded using a sol-gel process involving spin-coating solutions containing partially hydrolysed silicon or modified aluminium alkoxides. The two coated-substrates were assembled and the resulting sandwich was fired at temperatures ranging from 60 to 600°C. The sol-gel coatings were characterised using ellipsometry and AFM, while the corresponding bonded specimens were investigated using cross-sectional TEM. Their mechanical properties were characterised using both micro-indentation and tensile testing.Bond strengths of 0.8 MPa were achieved at 60°C between silicon wafers using a methacrylate/alumina hybrid system. The strength was increased to 1.3 MPa by using a nano-particulate sol, produced by hydrolysis of Al(O^sC₄H₉)₃ modified with ethylacetoacetate, and firing at 600°C. However, significantly lower bond strengths were achieved with sapphire and polycrystalline alumina substrates (0.4 and 0.1 MPa, respectively). The effect of precursor chemistry on the bonds produced is discussed.     

Comparison of aqueous and non-aqueous capillary electrochromatography for the separation of basic solutes

The analysis of basic compounds by capillary electrochromatography (CEC) on silica-based materials using conventional HPLC stationary phases has failed to address the problem of severe peak tailing and non-reproducible chromatography. Several new generation stationary phases were evaluated using aqueous and non-aqueous mobile phases. The best results were obtained in the aqueous mode using Waters Symmetry Shield RP-8, a material in which the residual silanol groups were shielded by an octylcarbamate function. For comparison, experiments were carried out using unmodified silica.     

分子三维投影法在苯酚类化合物构效关系研究中的应用

对苯酚类化合物进行三维投影得到了5个形状参数,将其与3个Am指数及8个量子化学参数相结合.由最佳变量子集回归法对变量进行了压缩与选择,运用多元回归分析和人工神经网络法分别构造了预测数学模型,得到了满意的结果.     

超高效液相色谱-电喷雾串联质谱法分离鉴定烟草中5种糖苷类香味前体物质

采用超高效液相色谱-电喷雾串联质谱法(UPLC-ESI MS/MS)并结合气相色谱-质谱法分离鉴定了烟草中5种主要的糖苷类香味前体物质。烟样经甲醇提取、XAD-2柱净化,得到初步纯化的糖苷,在pH 5条件下将其酶解,释放出糖苷配基。采用气相色谱-质谱分析并通过标准谱库检索确定了5种挥发性苷元;然后通过电喷雾质谱(负离子模式)确定糖苷母离子并作碎片离子扫描(MS2),确定了5种糖苷类香味前体物质的存在形式;最后采用UPLC-ESI MS/MS,以甲醇和乙酸-乙酸铵水溶液为流动相,通过RP-C18柱分离,在多反应监测(MRM)模式下,鉴定了烟草中5种主要的糖苷类香味前体物质,为应用液相色谱-质谱分析缺乏标准样品的糖苷类香味前体物质奠定了基础。     

DECREASED HOST CELL REACTIVATION OF UV-IRRADIATED ADENOVIRUS 5 BY FIBROBLASTS FROM COCKAYNE'S SYNDROME PATIENTS

Abstract— Over a period of 5 years, we performed 29 experiments in which survival curves of UV-irradiated adenovirus were determined using fibroblast strains from 10 normal persons and from 7 persons having Cockayne's syndrome. In all of these, the survival of UV-irradiated adenovirus 5 was less when assayed using monolayers of fibroblasts from Cockayne's syndrome patients than from normal persons. Survival curves using normal fibroblasts were, within error, straight lines on a log survival vs. linear fluence plot. Survival curves obtained using Cockayne's syndrome fibroblasts showed 2 components: an initial sensitive component, reflecting the behavior of approx. 75% of the infected cells, followed by a component having normal sensitivity. In the 28 experiments that were considered reliable, 58 curves were done using Cockayne's fibroblasts, 41 using normal human fibroblasts. Although experimental variation was encountered, there was no individual case in which sensitivity as measured using Cockayne's was equal to (or less than) the sensitivity measured using normal fibroblasts.     

Temperature and concentration dependence of diffusion coefficients in ethylene–propylene-diene copolymers

Self-diffusion and partition coefficients were measured for two commercial ethylene–propylene-diene copolymers (EPDM) and five solvents at infinite dilution using inverse gas chromatography. Mutual diffusion coefficients for solvents in EPDM also were measured for finite concentration using gravimetric sorption for three of the solvents. From the inverse gas chromatography experimental values for self-diffusion coefficients were obtained. Free-volume parameters were obtained through regression of the self-diffusion coefficient as a function of temperature. Mutual diffusion coefficients as a function of concentration were predicted using free volume theory and compared with experimental data obtained using gravimetric sorption. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 1713–1719, 1998     

手性分子与手性拓扑指数

应用自制的有机化合物结构解析专家系统ESESOC, 对与28个外消旋类化合物(特殊的氨基酸)分子手性中心有关的对称性问题进行了判别, 如对称面、对称点和对称轴等. 同时用的开发的程序对这些化合物的构型进行了自动识别和标示. 在此基础上, 以手性拓扑指数为参数, 利用Fisher意义下的分析和人工神经网络法, 对这些化合物的对映体进行了高效液相色谱分离中先后淋洗出的的对映体进行分类判别. 结果表明, 人工神经网络法优于Fisher意义下的判别分析.     

Track etch membranes (TEMs) for separation sciences from BARC-TIFR Pelletron accelerator

Track etch membranes (TEMs) program at 14 UD Pelletron accelerator at TIFR, Mumbai, India using 25 micron thick polyethylene terepthalate film is described. Large scale preparation of TEMs by scanning heavy ion beams using a electromagnetic scanner and rolling mechanism using a geared D.C. motor and vacuum rotary feed through are presented. The selection of ions of suitable energy and etching parameters for making various pore sizes were investigated using Rutherford scattered beam from Pelletron accelerator. Pore size and pore density were measured using scanning electron microscope. Scanning width up to 35 cm and irradiation up to 22 m were successfully carried out using this facility. Some applications carried out using these membranes are also mentioned.     

Spherulite growth rates of in situ prepared poly(propylene terephthalate)/SiO2 nanocomposites

The spherulite growth rates of in situ prepared PPT/SiO₂ nanocomposites containing 2–5 wt% nano-silica were studied. Measurements of the spherulite growth rates were carried out by applying non-isothermal experiments using polarized light microscopy (PLM). Comparison with results from isothermal PLM tests showed good agreement. Isothermal crystallizations after self-nucleation were also performed using differential scanning calorimetry (DSC) and the inverse crystallization half-times were estimated. The Lauritzen–Hoffman analysis was applied by using data from both isothermal and non-isothermal PLM experiments and the DSC results. Regimes II–III transition were observed at critical breakpoint close to 195 °C. The regimes I–II transition was not so clear, because of the semi-rigid macromolecular chains of the polymers. Results using DSC data were in satisfactory agreement to those using PLM spherulite growth data.     

Air pollution monitoring of an urban dust in Daejeon city,Korea by using instrumental neutron activation analysis

For air pollution monitoring, about 1300 airborne particulate matter samples were collected by using a low volume air sampler and a polycarbonate filter at two sampling sites in an urban region, Daejeon, the middle of Korea from 2003 to 2006. Mass concentrations of the black carbon were measured using a smoke stain reflectometer. The concentrations of 24 elements in the collected samples were analyzed by using instrumental neutron activation analysis, and its temporal trends and enrichment factors were investigated under different environmental conditions. Analytical control was carried out by using certified reference materials.     

Estimation of Ethyl Cellulose Layer Thickness of Coated Polyethylene Oxide Particles Using Differential Scanning Calorimetry

Particles of poly(ethylene oxide) (PEO) were coated using ethyl cellulose (EC). Equations and a method were proposed to estimate the EC layer thickness by using differential scanning calorimetry (DSC) based on melting or crystallization heat of phase-change materials. The result shows that EC layer thickness of polyethylene oxide particles determined using DSC is consistent with the result using an optical microscope.     

Synthesis and Cationic Polymerization of Open-Chain and Cyclic Enol Ethers

Abstract

Several new open-chain and cyclic enol ether monomers were prepared using simple, straightforward procedures. The reactivities of these monomers were compared using both differential scanning photocalorimetry and Fourier transform real-time infrared spectroscopy. In general, these new monomers were found to possess excellent reactivity in photoinitiated cationic polymerization using a diaryliodonium salt photoinitiator.     

Synthesis of Crosslinked Polymeric Particles and Their Application for the Superhydrophobic Surfaces Using Structured Polymeric Colloids

In this study, structured colloids such as self-organized supraparticles of polymeric lattices were used as coating materials for the fabrication of superhydrophobic surfaces. Crosslinked polystyrene (PS) nanospheres were synthesized using divinylbenzene as crosslinker to prevent the organic particles from being dissolved in toluene solvent. After evaporation-driven self-assembly of PS particles inside the toluene emulsions, supraparticles of PS lattices were fabricated and coated on glass substrate, followed by the plasma treatment using CHF₃ as gas source for fluorination process. After the fluorine treatment using plasma, superhydrophobicity was assessed by measuring water contact angle. The morphologies of supraparticles and the structure of coating film were observed using scanning electron microscope, and the elemental compositions of the coating films were detected by using X-ray photoemission spectroscopy (XPS) technique. We believe that the lotus effect from the supraparticles with different two length scales made crucial contribution to the generation of superhydrophobicity after plasma treatment for the formation of superhydrophobic surfaces.     

Single-cell protein analysis of a single mouse embryo by two-dimensional capillary electrophoresis

The characterization of protein expression from a single-cell mouse embryo using two-dimensional capillary electrophoresis (2D-CE) is described. These zygotes were obtained from Hsf1 gene knockout mice. Single zygotes were lysed off-column and proteins were fluorescently labeled using the fluorogenic dye 3-(2-furoyl)quinoline-2-carboxaldehyde (FQ). After injection, analytes were separated first according to molecular weight using capillary sieving electrophoresis (CSE) and then by micellar electrokinetic capillary chromatography (MEKC) to obtain protein expression fingerprints. Analytes were detected in a sheath flow cuvette using laser-induced fluorescence. In a 1-h 2D-CE separation, over 100 components were resolved with a spot capacity of 380.