Microsolvation of phthalocyanines in superfluid helium droplets.

Experimental and theoretical investigations of the spectroscopy of molecules in superfluid helium droplets provide evidence for the key role of the first helium layer surrounding the dopant molecule in determining the molecule's spectroscopic features. Recent investigations of emission spectra of phthalocyanine in helium droplets revealed a doubling of all transitions. Herein, we present the emission spectra of Mg-phthalocyanine and of phthalocyanine-argon clusters in helium droplets, which confirm the splitting as a general effect of the helium environment. A scheme of levels is deduced from the emission spectra and attributed to quantized states of the first helium layer surrounding the dopant molecule.     

Study of adsorption of oxygen on β-Al2O3 + Au and β-Al2O3 + Pt: Work function measurements—proposition of a model

To improve the understanding of the electrochemical effects observed on an original potentiometric gas sensor, interactions of oxygen with the device were investigated. This gas sensor is made of a solid electrolyte (treated Na-β-alumina) associated with two metallic electrodes (gold and platinum) located in the same gas mixture. Adsorption of charged oxygen species, considered responsible for the electrical response developed by the sensor, was investigated by work function measurements. Results showed that charged oxygen species only form on partially gold or platinum covered solid electrolyte. Comparison of these results with those obtained in a previous calorimetric study of interactions between oxygen and the same materials suggests the existence of at least two different oxygen species adsorbed on the surface of the sensitive element. The first one, located on the solid electrolyte surface, is neutral and characterized by an endothermal reaction of formation. The second one is charged and probably produced at the gas/solid electrolyte/metallic electrode interface. A mechanism based on the concept of “three phase boundary” and similar to the “reverse spillover” phenomenon is proposed to account for the adsorption of these oxygen species.     

新型AFM探针的制备及应用

采用熔拉 -腐蚀复合方法 ,将普通单模石英光纤制成直锥形光纤探针。利用自制工具将探针打弯 ,制成悬臂式光纤探针 ,在AFM上取得了较理想的测试结果。将自制光纤探针和商用硅材料探针获得的两种扫描图像进行了对比 ,分析了悬臂式光纤探针的特点     

Time-resolved fluorescence study of the single tryptophan in thiocyanate and azide derivatives of horseradish peroxidase: Implication for a p H-induced conformational change in the heme cavity

Detailed pH-dependent steady state and picosecond time-resolved tryptophan fluorescence studies on thiocyanate and azide complexes of horseradish peroxidase have been carried out. The fluorescence decay of the single tryptophan in these species was fitted to a discrete three exponential model. Maximum entropy method analysis also gave three distinct regions of lifetime distributions. The fast subnanosecond lifetime component was found to have > 97% amplitude contribution while other two longer lifetime components have small contributions. Small contributions from the nanosecond lifetime components possibly arise from apoprotein impurity or some small amount of disordered heme conformer of the protein. pH dependence of the fast picosecond lifetime components was found to show a systematic behavior which has been interpreted in the light of obligatory conformation change associated with activation of the enzyme at low pH.     

Fluorescence line narrowed spectra of Zn and metal-free cytochrome c

Fluorescence line narrowing (FLN) spectroscopy was used to study the role of the polypeptide chain in influencing the spectrum of Zn-substituted cytochrome c (Zn cyt c) and metal-free cyt c (porphyrin cyt c). For both derivatives the spectra show characteristics of relaxed fluorescence from an inhomogeneously broadened sample. Zero phonon lines and phonon wings can be clearly distinguished, and vibrational frequencies of the ground and excited states were identified. The inhomogeneous distribution width for porphyrin cyt c is slightly wider than that of Zn cyt c and a second population of molecules was apparent in the porphyrin cyt c. The phonon coupling was greater for Zn cyt c than for porphyrin cyt c, which may be due to the extra coupling to the polypeptide chain by metal ligation.This work has been done in partial fulfillment of the requirements for the Doctor of Philosophy degree.     

元素在石墨炉内石墨探针表面上的原子化机理研究：Ⅶ.锗的原子化机理

本文应用Ｘ－射线衍射，Ｘ－射线光电子能谱，俄歇电子能谱和其它一些实验，考察石墨炉升温过程中氟化锗，锗酸钠在石墨探针表面上的形态变化，阐明了它们的原子化机理：ＧｅＦ２与Ｎａ２ＧｅＯ３首先分解为ＧｅＯ２，ＧｅＯ２还原为ＧｅＯ，后者在＞２４００Ｋ热分解产生自由态的锗原子，ＧｅＦ２和Ｎａ２ＧｅＯ３的原子化均源于ＧｅＯ（ｇ）的气相分解。原子化的升温过程中，在１４００－２４００Ｋ ＧｅＦ２和Ｎａ２ＧｅＯ３都产     

Modeling of RF plasma torch with a metallic tube inserted for reactant injection

Flow, temperature, and electromagnetic (EM) fields in a radio-frequency thermal plasma torch designed for the preparation of superconducting powders or films have been analysed by using a new two-dimensional modeling approach with the electric field intensity as the fundamental EM field variable. The insertion of a stainless steel injection tube into the torch leads to large induction currents in this tube. Although such large induction currents cause pronounced changes of the EM fields near the injection tube, flow and temperature fields are little affected. There exists only one large toroidal vortex in the upper part of the present torch, while the maximum temperature appears at an off-axis location within the coil region.     

Fluorescent humic substances–arsenic complex in well water in areas where blackfoot disease is endemic in Taiwan

The relationship between the four components, (1) fluorescence intensity, (2) arsenic concentration, (3) pH and (4) total dissolved solids, (TDS) measured in well waters from areas in Taiwan where blackfoot disease (BFD) is endemic was studied, as well as the relationships between the four degrees of BFD and each of the above four symptomatic components, in order to evaluate the etiological factors of BFD more progressively. The following 95% confidence intervals were obtained in well water samples (n = 1189): fluorescence intensity, 26.837–32.570; arsenic concentration, 0.103–0.127 mg dm^?3; pH, 7.466–7.519; and TDS 733.063–801.647 mg dm^?3. Fluorescence intensities of the four degrees of BFD were not all the same (F = 64.54, P < 0.001), and nor were arsenic concentrations (F = 72.03, P < 0.001), pH values (F = 7.30, P < 0.001), nor TDS values (F = 10.76, P < 0.001). In addition, multiple comparisons indicate that the higher the epidemical degree, the higher the fluorescence intensities, arsenic concentrations and pH values become; however, such a relationship is not found for TDS values. Moreover, the fluorescence intensities have positive linear correlations with arsenic concentrations (r = 0.49, P < 0.001), pH (r = 0.25, P < 0.001), and TDS (r = 0.18, P < 0.001), as do the arsenic concentrations with pH (r = 0.22, P < 0.001). Of the four epidemical degree groups, pairs are not significantly different from one another in correlation coefficients between fluorescence intensity and arsenic concentration, which implies a steady relationship between fluorescent compounds and arsenic. We conclude that fluorescent compounds in well water, as possible etiological factors of BFD, are closely related to arsenic along with pH and TDS values in the areas where BFD is endemic. In addition, we infer that a complex is formed by fluorescent compounds, arsenic and other metals.     

高频单线圈双调谐NMR单晶探头的研制

本文报道了一种测角单晶NMR探头。该探头采用单线圃双调谐电路,工作频率在90MHz-110 MHz连续可调,可进行交叉极化大功率去耦实验。文中提出了一种简单而有效的测角装置,可使单晶绕三个互相垂直轴转动实现单晶的NMR测量。作为典型的应用例子,本文利用该探头实现了单晶DGO(2NH₂CH₂COOH·H₂C₂O₄)屏蔽张量的测量。