Effect of chemical parameters on pyrene degradation in soil in a pulsed discharge plasma system

Degradation of pyrene in soil in a net-to-net pulsed discharge plasma (PDP) system was reviewed. Effect of main chemical parameters, including air flow rate, pyrene concentration, initial pH and soil moisture content on pyrene degradation was examined. The obtained results show that 87.9% of pyrene could be removed under the condition of 60 min reaction; increasing of air flow rate within 1 L min⁻¹ was favorable for degradation; pyrene removal was decreased with the increase of initial pyrene concentration; oxidation of pyrene was more evident in acidic soil; enhancement of soil moisture content has no benefit on pyrene degradation.     

Sensitive chemically amplified electrochemical detection of ruthenium tris-(2,2′-bipyridine) on tin-doped indium oxide electrode

Optimized combination of chemical agents was selected for sensitive electrochemical detection of dissolved ruthenium tris-(2,2′-bipyridine) (Ru-bipy). The detection was based on the chemical amplification mechanism, in which the anodic current of a redox-active analyte was amplified by a sacrificial electron donor in solution. On indium-doped tin oxide (ITO) electrodes, electrochemical reaction of the analyte was reversible, but that of the electron donor was greatly suppressed. Several transition metal complexes, such as ferrocene and tris-(2,2′-bipyridine) complexes of osmium, iron and ruthenium, were evaluated as model analyte. A correlation between the amplified current and the standard potential of the complex was observed, and Ru-bipy generated the largest current. A variety of organic bases, acids and zwitterions were assessed as potential electron donor. Sodium oxalate was found to produce the largest amplification factor. With Ru-bipy as the model analyte and oxalate as the electron donor, the analyte concentration curve was linear up to 50 μM, with a lower detection limit of approximately 50 nM. Preliminary work was presented in which a Ru-bipy derivative was attached to bovine serum albumin and detected electrochemically. Although the combination of Ru-bipy, oxalate and ITO electrode has been used before for electrochemiluminescent detection of Ru-bipy and oxalate, as well as electrochemical detection of oxalate, its utility in amplified voltammetric detection of Ru-bipy as a potential electrochemical label has not been reported previously.     

Thermal gradient induced sidebranching in directional solidification

The polycrystalline perovskitelike manganese oxides La_1-xA_xMnO (A = Na, and K, ) have been fabricated by sol-gel technique. For all the compositions explored in this work, the average manganese oxidation state is practically constant, at for A = Na, and for A = K, respectively. A close relationship is confirmed to hold between the Curie temperature (T_c) and the bond distance of Mn-O. Results of magnetic measurements show that these materials can be utilized as suitable candidates for magnetic refrigerants with wide applied temperature span, for their significant entropy change and the easily tuned Curie temperature. Received: 12 September 1997 / Revised: 18 December 1997 / Accepted: 21 January 1998     

A study of structural, compositional and optical properties of spray-deposited non-stoichiometric (Zn,Fe)S thin films

Non-stoichiometric ternary chalcogenides (Zn,Fe)S were prepared in the film form by pyrolytic spray deposition technique, using air/nitrogen as the carrier gas. The precursor solution comprised of ZnCl₂, FeCl₂ and thiourea. The depositions were carried out under optimum conditions of experimental parameters viz. carrier gas (air/nitrogen) flow rate, concentration of precursor constituents, nozzle substrate distance and temperature of quartz substrate. The deposited thin films were later sintered in argon at 1073 K for 120 min.The structural, compositional and optical properties of the sintered thin films were studied. X-ray diffraction studies of the thin films indicated the presence of (Zn,Fe)S solid solution with prominent cubic sphalerite phase while surface morphology as determined by scanning electron microscopy (SEM) revealed a granular structure.The chemical composition of the resulting thin films as analyzed by energy dispersive X-ray analysis (EDAX) reflected the composition of the precursor solutions from which the depositions were carried out with Fe at% values ranging from 0.4 up to 33.SEM micrographs of thin films reveal that the grain sizes of the thin films prepared using air as carrier gas and N₂ as carrier gas are in the vicinity of 300 and 150 nm, respectively.The diffuse transmittance measurements for thin films, as a function of wavelength reveal the dependence of direct optical band gap on Fe content and type of phase.     

Cosmic dust and our origins

The small solid particles in the space between the stars provide the surfaces for the production of many simple and complex molecules. Processes involving the effects of ultraviolet irradiation of the thin (hundredth micron) mantles are shown to produce a wide range of molecules and ions also seen in comets. Some of the more complex ones inferred from laboratory experiments are expected to play an important role in the origin of life. An outline of the chemical evolution of interstellar dust as observed and as studied in the laboratory is presented. Observations of comets are shown to provide substantial evidence for their being fluffy aggregates of interstellar dust as it was in the protosolar nebula, i.e. the interstellar cloud which collapsed to form the solar system. The theory that comets may have brought the progenitors of life to the earth is summarized.     

CONVERGENCE OF CASCADE ALGORITHMS AND SMOOTHNESS OF REFINABLE DISTRIBUTIONS

In this paper, the author at first develops a method to study convergence of the cascade algorithm in a Banach space without stable assumption on the initial (see Theorem 2.1), and then applies the previous result on the convergence to characterizing compactly supported refinable distributions in fractional Sobolev spaces and Holder continuous spaces (see Theorems 3.1, 3.3, and 3.4). Finally the author applies the above characterization to choosing appropriate initial to guarantee the convergence of the cascade algorithm (see Theorem 4.2).     

Temperature coefficient of NH chemical shifts of thioamides and amides in relation to structure

NH chemical shift temperature coefficients have been measured in a large series of N-substituted-3-piperidinethiopropionamides in which the NN distances are short but of varied length, as well as in a couple of the corresponding amides and in some simpler amides and thioamides. Geometries are calculated by means of ab initio DFT methods. The N-substituted-3-piperidinethiopropionamides show in most cases strong intramolecular N–HN hydrogen bonds according to IR spectra and ab initio calculations. For compounds with rather short NN distances the S=C–N–H moiety is non-planar. Dihedral angles as small as 160° are found. The NH chemical shift coefficients measured in non-polar solvents in all the N-substituted-3-piperidinethiopropionamides are more negative (−8 to −17 ppb/K) than in non-hydrogen bonded thioamides. For the latter in non-polar solvents like CDCl₃ and toluene the temperature coefficients are as small as −1 to −4 ppb/K. The large negative effects can be related not only to the non-planarity of the thioamide group in a way that the more pronounced the non-planarity the more negative the temperature coefficients, but also to strong hydrogen bonding and the fact that the acceptor is a nitrogen. For similar amides with non-planar amide groups and nitrogen acceptor large negative temperature coefficients are likewise seen. In polar solvents like DMF the effects in simple thioamides are uniform and close to −6 ppb/K, whereas in the more complex compound like 4p(t) the temperature coefficient is close to 0. An essential feature of measuring temperature coefficients of compounds without strong intramolecular hydrogen bonds in non-polar solvents and at low temperatures is to keep the concentration low enough to avoid dimerisation.     

NMR investigation of concentrated alumina and silica slurries

The longitudinal relaxation times (T₁) of water in concentrated silica and alumina slurries were measured as a function of solids content. It was shown that the results could be fit very well with a two-phase fast-exchange model between free and surface-bound water. As expected, values of T₁ for bound water were in the order of 20–2000 times lower than that for free water, indicating a higher effective viscosity of the surface-bound water. The strength of the interaction depended on the particular surface, and all of the aluminas examined interacted more strongly with water than the two silicas studied, which themselves differed considerably. The chemical mechanical polishing (CMP) removal rate of tantalum by silica slurries was shown to be directly correlated with the interaction parameters, derived from the NMR relation times rather than with total surface hydroxyl group concentration.     

Cl/HN3/I2全气相化学激光体系的化学动力学模拟计算

 对Cl/HN₃/I₂产生NCl(a)/I激光的过程进行了化学动力学计算，主要考察了Cl,HN₃和I₂的初始粒子数密度及其配比对小信号增益系数的影响。结果发现,当温度为400K, 初始Cl粒子数密度为1×10¹⁵，1×10¹⁶和1×10¹⁷cm^-3时,小信号增益系数分别达到1.6×10^-4,1.1×10^-3和1.1×10^-2cm^-1，获得最佳小信号增益系数的HN₃和I₂的初始粒子数密度分别为初始Cl粒子数密度的1～2倍和2%～4%。同时，对Cl，HN₃和I₂配比对小信号增益系数和增益持续时间的影响进行了讨论。     

采用空心阴极放电等离子体化学气相沉积方法制备a-CH薄膜

 研究了不同衬底-阴极距离、直流电压和H₂流量对a-CH薄膜沉积速率的影响。结果表明：衬底-阴极距离必须大于0.5cm，随着该距离的增加，薄膜的沉积速率减少；直流电压达550V时沉积速率最大；随着H2含量的增加，CH₄含量相对减少，沉积速率随之降低。用AFM观察了以该方法制得的448.4nm CH薄膜的表面形貌，表面粗糙度约为10nm。最后测出了不同条件下CH薄膜的UV-VIS谱，由此可以计算得到薄膜的禁带宽度及折射率。