Aquasonolysis of thiophene and its derivatives

The rate constants and products of the aquasonolysis of thiophene, tetrahydrothiophene, 2-methylthiophene, 2,5-dimethylthiophene, and 2-ethylthiophene have been investigated. The sonolysis of the selected compounds in aqueous solution follows pseudo-first-order kinetics. The aquasonolytical rate constants correlate very well with the water solubility and Henry's Law constants of thiophenes. Surprisingly, vapour pressures and heats of formation of thiophenes have little effect on their aquasonolytical rates. The pseudo-first-order rate constant for the decay of thiophene decreases as its initial concentration increases. These results indicate that the transfer process of organic solutes between cavitation bubbles and the bulk liquid can strongly affect the aquasonolysis. Furthermore, carbon disulfide, diacetylene, and dimers can be detected as common products during ultrasonic irradiations. Hence, the predominant pathway of the aquasonolysis of thiophenes is the pyrolysis during the collapse of cavities.     

Aquasonolysis of selected cyclic C(6)H(x) hydrocarbons

Aquasonolysis rates and products of selected cyclic C(6)H(x) hydrocarbons, benzene, 1,3-cyclohexadiene, 1,4-cyclohexadiene, cyclohexene, cyclohexane, and methylcyclopentane have been investigated. The sonolysis of selected compounds in aqueous solution follows first-order kinetics, and the aquasonolysis rate correlated well with the water solubility. The degradation rate decreased with the increase of initial concentration. The effect of initial concentration on the degradation of cyclohexene was more significant than that of benzene. The transfer process of organic solutes between cavitation bubbles and the bulk liquid affects the rates and products of their aquasonolysis.     

基于顶空及表面增强拉曼散射(SERS)结合的葱属植物挥发性物质研究

为了在常温下鉴定新鲜植物样品的挥发性物质,且避免繁杂前期样品的制备过程,将新鲜样品切细后置入顶空瓶中,用注射器抽取顶空瓶上方的挥发性物质注入用微波法制备的纳米银溶胶中,用R-3000便携式拉曼光谱仪进行SERS的测量。获得了葱属植物大蒜、韭菜、葱的挥发性物质的表面增强拉曼光谱(SERS)。大蒜的SERS谱中较强的峰出现在307,399,569,711,1 182,1 287,1 397,1 622 cm-1处。韭菜的SERS谱中最强的峰出现在672 cm-1,较弱的峰出现在274,412,575,1 185,1 289,1 396,1 618 cm-1处。葱的SERS谱中最强的峰出现在693 cm-1,次强峰出现在372,888,1 023 cm-1处,较弱的峰出现在1 088,1 211,1 322 cm-1。获得二烯丙基二硫(diallyl disulfide)、烯丙基甲基硫醚(allylmethyl sulfide)、1-丙硫醇(1-Propanethiol)的液态、气态的SERS谱。经对比研究得出：吸附在银表面的大蒜、韭菜、葱的主要挥发性物质分别是二烯丙基二硫(diallyl disulfide)、烯丙基甲基硫醚(allyl methyl sulfide)、1-丙硫醇(1-Propanethiol)。同是葱属植物但不同种大蒜、韭菜、葱其吸附在银表面的主要的挥发性物质不一样,吸附在银表面的各种葱的主要挥发性物质都是1-丙硫醇。该实验结果表明顶空与SERS结合,不需要复杂的提取过程,可直接用于新鲜植物的挥发性物质快速检测。     

Benzene formation during aquasonolysis of selected cyclic C6Hx hydrocarbons

Yield and selectivity of benzene produced from aquasonolysis of the selected cyclic C6Hx hydrocarbons, i.e., 1,4-cyclohexadiene, 1,3-cyclohexadiene, cyclohexene, cyclohexane, and methylcyclopentane, have been investigated in this work. Benzene cannot be detected during the aquasonolysis of cyclohexane and methylcyclopentane. The order of yield and selectivity of benzene was as follows: 1,4-cyclohexadiene>1,3-cyclohexadiene>cyclohexene. The initial concentrations of substrates can affect the yield of benzene. During the aquasonolysis of 1,3-cyclohexadiene and cyclohexene, other C6 species except benzene were also found. It was suggested that benzene could directly be generated by formal dehydrogenation of cyclic C6Hx hydrocarbons.     

Experimental and computational study of diethyl sulfide pyrolysis and mechanism

The pyrolysis of diethyl sulfide (C₂H₅SC₂H₅), a simulant for mustard chemical warfare agents, was studied in a turbulent flow reactor with extractive gas composition analysis by GC/MS and FTIR. Experiments were performed at approximately atmospheric pressure for four different temperatures between 630 and 740 °C with maximum residence times between 0.06 and 0.08 s. Temperature and species profiles were obtained on the centerline of the reactor. The mixing characteristics in the reactor were determined by using carbon monoxide as a tracer. 80% destruction of diethyl sulfide was observed for the experiment at the temperature of 740 °C and the residence time of 0.06 s. The following species were quantified: diethyl sulfide, ethylene, methane, ethane, acetylene, carbon disulfide, and thiophene. In addition, ethanethiol, methyl thiirane CH₃-(Cy-CH-CH₂-S), ethyl methyl disulfide, and diethyl disulfide were identified but not quantified. A light yellow solid containing sulfur condensed in sampling probes. Thermochemical properties for all species and a detailed mechanism were developed for modeling the reaction system. Thermodynamic and kinetic parameters were based on density functional theory and ab initio calculations using isodesmic work reactions for enthalpies. Kinetic parameters for chemical activation and unimolecular dissociation reactions were determined with multi frequency quantum RRK analysis for k(E) and master equation for fall-off. Important reactions were identified by sensitivity analysis and reaction pathway analysis of the mechanism. Model predictions show overall good agreement with experiment.     

Sulfur-containing components of supercritical garlic extracts and their synthetic analogs as potential biocides

We have shown that a specific component of supercritical (SC) garlic extract and some synthetic disulfide analogs are active as antimicrobials. In the course of this study, six compounds (diallyl disulfide, 1-propenylallyl disulfide, methylallyl disulfide, diallyl trisulfide, 2-vinyl-4H-1,3-dithiin, and 3-vinyl-4H-1,2-dithiin) were isolated from SC garlic extract and identified. Also, two novel sulfoxide-containing garlic analogs were synthesized. All isolated and synthetic substances were tested as potential antimicrobials against gram-positive bacteria Bacillus cereus, Mycobacterium smegmatis, and Micrococcus luteus and gram-negative bacteria Pseudomonas aurantiaca. Diallyl disulfide and diallyl trisulfide exhibited the best activity against both gram-positive and gram-negative bacteria.     

To the Kinetics of Nitrogen Incorporation during dc Magnetron Deposition

Investigations of nitrogen incorporation during film deposition by dc magnetron sputtering with a CrSiAl target in Ar/N₂ mixtures have been carried out in the range of the metallic mode. The rate of the nitrogen consumption is proportional to the nitrogen partial pressure during deposition and to the amperage. The corresponding rate constant decreases with the argon pressure. Furthermore, the condensation rate of the target species decreases with the nitrogen partial pressure and is determined by the rate constant of the nitrogen consumption. The experimental results are explained by a 4-stepped reaction sequence of nitrogen incorporation consisting in (1) ionization, (2) ion bombardment of the target and formation of a coverage by plating, (3) removal of the coverage by the sputter process, (4) condensation on the substrate.     

Application of supercritical fluid extraction to the development of new potential biocides on the basis of garlic (<Emphasis Type="Italic">Allium sativum</Emphasis> L.)

Garlic (Allium sativum L.) extracts were obtained using CO₂-supercritical extraction. The extracts were separated into individual components by the preparative HPLC and GC methods. Some of the isolated substances (allicin, ajoene, diallyl disulfide, and diallyl trisulfide), along with their two synthetic analogues with disulfide structure, were tested as potential biocides using a number of test objects (Candida utilis, Bacillus cereus, Pseudomonas aurantiaca, and Escherichia coli). Some of the tested substances exhibited a high efficiency as biocides, in particular, against gram-negative cultures. The results obtained are indicative of good prospects of using sulfur-containing garlic components and their synthetic analogues as potential antimicrobial agents.     

Photoluminescence Electron-Transfer Quenching of Rhenium(I) Complexes with Organic Sulfides

Electron-transfer(ET) from organic sulfides to excited state rhenium(I)-based heteroleptic tricarbonyl complexes [Re(bpy)(CO)₃(py)]⁺ (I) and [Re(bpy)(CO)₃(ind))]⁺ (II) in acetonitrile solution is facile and luminescence quenching constants, k_q, are in the range 10⁵–10⁸ M⁻¹s⁻¹. The detection of the sulfide radical cation in this system using time-resolved absorption spectroscopy is a direct evidence for the ET nature of the reaction. The k_q values for the quenching of Re(I)-complexes with organic sulfides are analyzed with a scheme involving rate controlling electron transfer process. The measured rate constants for the electron transfer (ET) reaction are close to the values calculated from Marcus theory.     

Kinetics of copper,nickel, cobalt and iron sulfidation by a modified “pellet” method. The effect of reaction at the metal/scale interface

This paper presents the results of studies on sulfidation of copper at temperature 600–700 K, nickel at 870–890 K, cobalt at 1060–1140 K and iron at 970–1170 K in sulfur vapor at 101 kPa with the use of a modified Wagner's pellet method. It has been stated that in the case of copper and nickel the initial heating of metal samples with a corresponding sulfide greatly influences the formation of hexagonal Cu₂S or Ni_{3 ± y}S₂ which are the thermodynamically stable phases under the reaction conditions. If these sulfides are lacking the scale morphology, the sulfidation rates are different. In the case of cobalt and iron the process of sulfure dissolution does not affect the sulfidation rate. The modified pellet method permits the measurement of the sulfidation kinetics of these metals which has not been possible with the use of the classical one.     

Oxidation of hydrogen sulfide and corrosion of stainless steel in gas mixtures containing H<Subscript>2</Subscript>S,O<Subscript>2</Subscript>, H<Subscript>2</Subscript>O,and CO<Subscript>2</Subscript>

The composition of volatile and solid products of oxidation of hydrogen sulfide and stainless steel in gas mixtures containing H₂S, O₂, H₂O, and CO₂ has been determined using mass spectrometry, x-ray diffraction analysis, and scanning electron microscopy. It has been shown that holding an H₂S–O₂ mixture at 301 K results in prevailing formation of elemental sulfur and iron sulfides in the form of porous hygroscopic crust on the reactor wall surface. Formation of gas-phase sulfur causes self-acceleration of the oxidation of hydrogen sulfide; the resulting water triggers corrosion of the reactor wall. Heating of the resulting sulfur-sulfide crust in O₂ medium is accompanied by formation of SO₂ and heat release at T > 508 K. After heating of the H₂S–CO₂ mixture to 615 K, H₂ and COS were found in the volatile reactants; no noticeable corrosion of the reactor wall has been detected. It has been established that addition of O₂ to the H₂S–CO₂ mixture and its heating to 673 K leads to formation of ferrous sulfates. The mechanisms of the observed processes are discussed.     

Reaction of hydrogen with chlorine during reactive ionic etching

The role of the chain mechanism of the interaction of chlorine with hydrogen in the gas phase during the reactive ionic etching (RIE) of GaAs in a CF₂Cl₂ plasma is discussed. In the presence of hydrogen, more volatile products are formed, and, as a result, the rate of etching becomes time-independent, while the boundary of etching becomes less diffuse and the etched surface appears to be smooth up to a depth of etching of >1 μm. The interaction of short-lived free radicals with the substrate is treated as heterogeneous chain termination.     

基于红外光谱研究沥青燃烧机理和有害气体成分分析

利用Rosemount气体分析仪和定碳炉搭建起固定床燃烧反应试验平台,通过红外光谱分析技术定量分析沥青及其胶浆在高升温速率条件下燃烧反应的有毒气态产物成分、及其释放规律。研究表明,在高升温速率、近等温条件下,沥青及胶浆的燃烧过程可近似分为活泼挥发组分析出燃烧、二次挥发析出结合残炭燃烧两个阶段,其主要气态产物为CO₂,CO,NO,NO₂及SO₂。沥青材料中活泼挥发组分含量是影响燃烧气态产物释放规律的关键因素之一,减少沥青材料中活泼挥发组分的含量可有效降低燃烧气态产物的生成、尤其是CO的产生。     

Modelling of the plasma-substrate interaction and prediction of substrate temperature during the plasma heating

Temperature of the substrate during plasma heating and spraying plays an important role on quality of the substrate and coating. In this study a three dimensional numerical model is developed to simulate the Ar-N₂ plasma jet and conjugate heat transfer between plasma and substrate. The influencing of operating parameters on thermal flux from the plasma to the substrate and substrate temperature are discussed. Transient simulations are carried out to predict the substrate temperature with heating time. The arc current, gas flow rate, stand-off distance, substrate material and environment around the substrate significantly affect the thermal flux to the substrate. Heat flux to the substrate cannot be neglected in the coating built-up models. Present model is validated by comparing the results of present model with previous predictions and measurements.     

纳米硫化铜近红外吸收材料

采用新型超声喷雾法技术,把摩尔分数都为0.5%的Cu(NO3)2和Na2S水溶液分别作为初始反应溶液,调节溶液体系的pH值在6～8,把经过超声雾化后的Cu(NO3)2溶液逐步加入到处于强力搅拌的Na2S水溶液中,经陈化过滤后获得纳米半导体硫化铜(CuxS,1≤x≤2)粉体。分析了不同热处理温度与原料配比对获得的硫化铜纳米颗粒化学成分的影响,用X射线粉末衍射仪表征了纳米硫化铜粒子的晶相与化学组成,并采用扫描电镜观察了相应化学组成的粒子晶相形貌,测定了不同化学组分纳米硫化铜粒子从可见到近红外胶体状的吸收和透射光谱。研究表明不同化学组成的纳米硫化铜对近红外光都具有显著的吸收效应,这是由于电子在硫化铜半导体纳米粒子能带中的跃迁所致,同时这些半导体粒子对可见光具有很高透过性,但其可见光透射率随着纳米粒子从Cu2S趋向CuS而略有下降。     

光谱探针猩红S与牛血清白蛋白结合的发光光谱

利用荧光光谱和紫外吸收光谱,详细研究了不同温度下猩红S(PS)与牛血清白蛋白(BSA)的结合反应,发现PS对BSA的内源性荧光具有较强的猝灭作用,其猝灭机理属于静态猝灭,由此求得PS与BSA间的结合常数、结合位点数及热力学参数等.结果表明:PS与BSA之间形成了1:1稳定复合物,它们之间的作用力主要是静电引力.根据Fo...     

Thio sol-gel synthesis of titanium disulfide thin films and nanoparticles using titanium(IV) alkoxide precursors

Titanium tetraisopropoxide reacts with hydrogen sulfide in butylamine solvent at room temperature to form an amorphous titanium alkoxy-sulfide which can be converted to crystalline titanium disulfide by heat treatment in a flowing hydrogen sulfide gas stream. The reaction has been studied using infrared and Raman spectroscopy, gas chromatography-mass spectrometry, X-ray diffractometry and energy-dispersive X-ray analysis measurements. Based on these studies, it is shown that a partially thiolysed alkoxide precursor forms through the replacement of a limited number of alkoxy groups by hydrosulfide moieties. This alkoxy-hydrosulfide is believed to form following a thiolysis-condensation mechanism similar to the hydrolysis-condensation process that occurs during the corresponding oxide sol-gel reaction. The alkoxy-hydrosulfide species can then be completely thiolysed at 800 °C in a stream of hydrogen sulfide to yield pure, hexagonal titanium disulfide in either film or particulate form.     

Numerical simulation of tissue freezing by liquid nitrogen based cryoprobe

A model is presented to simulate the cooling processes during tumor cryosurgery with different kinds of flows through the cryoprobe. The heat flux between the cryoprobe wall and the tumor, the heat transfer coefficient under different inflow conditions are obtained numerically. The impact of the inlet mass flow rate, gas volume fraction on these parameters is investigated. It is found that the heat transfer coefficient decreased significantly when inflow changed from two-phase annular flow to droplet flow, and to gas flow. The inlet gas volume fraction and flow velocity only significantly affect the freezing ability of the probe when the inflow is gas or in droplet phase. Simulation of the tumor temperature profiles under different flow conditions show that the heat transfer coefficient is a crucial parameter in temperature prediction during cryosurgery. Results indicate that when the cryoprobe wall is assumed at a constant temperature conventionally, the cooling effect could be overestimated. It would be more reasonable to use the constant wall heat transfer coefficient to simulate the cooling progress under a specific flow.     

Analysis of the Properties of Metal Sulfide Nanocrystals Synthesized by the Langmuir—Blodgett Technique

JETP Letters - Nanocrystals of metal sulfides (CdS, ZnS, CdZnS, CuS, and PbS) are formed upon the interaction of gaseous hydrogen sulfide with Langmuir—Blodgett films of metal behenates. To...     

Experimental Investigation of Taylor and Intermittent Slug-annular/Annular Flow in Microchannels

High-speed visualization of adiabatic flow and heat transfer rate determination for constant wall heat flux conditions were performed to study the flow and heat transfer behavior of non-boiling, gas–liquid two-phase vertical upward flow in a 2.00 mm-diameter tube. Liquids of different volatilities, including water, ethylene glycol, and hexadecane, were employed to investigate the roles of convective heat transfer and evaporation for a wide range of flow conditions encompassing Taylor, slug-annular, and annular flow regimes. The heat transfer rate is found to depend strongly on the flow regime. Significant evaporative cooling was observed for the volatile system at high gas flow rates. A heat transfer enhancement up to fivefold over that for the liquid-only flow was observed in the annular flow regime.