纳米Re2O7的萃取法制备及光催化特性研究

本工作从N235-正庚烷萃取体系中，以饱和萃取法制得前体物和纳米粉体Re₂O₇，平均粒径30 nm。以此纳米粉为光催化剂，研究了光降解甲基橙染料的最佳条件，并在相同条件下，与非纳米Re₂O₇及工业常用的纳米TiO₂进行比较，光降解甲基橙能力大小为：纳米Re₂O₇ > 锐钛矿型纳米TiO₂ > 非纳米Re₂O₇。     

Kinetic Determination of Microquantities of Rutin by Perturbation of the Bray-Liebhafsky Oscillatory Reaction in an Open System

A kinetic method is described for the microquantitative (microconcentration/microvolume) determination of rutin based on potentiometric monitoring of the concentration perturbations of the Bray-Liebhafsky (BL) oscillatory reaction being in a non-equilibrium stationary state close to a bifurcation point. The experiments are carried out in an open reactor. The response of the matrix system to perturbations by different concentrations of rutin ethanolic solutions is followed by a Pt-electrode. In the concentration range between 7.8×10^–8moldm^–3 and 9.1×10^–6mol dm^–3, we found a linear dependence of the maximal potential shift, E_m, on the logarithm of the rutin concentrations. The unknown concentrations can be determined from the calibration curve up to an accuracy of ±5%. The detection limit is 3.6×10^–8mol dm^–3. The amount of required sample can be as small as 10µL.     

生物体系中电子转移机理的研究Ⅱ: 分子间电子转移及 电子供、受体间不同基 团的影响

利用自编程序MOPAC-ET中AM1方法,及KT(Koopman'sTheorem)法,研究了二苯负离子体系的分子间电子转移现象,计算了其电子供、受体在不同距离下的V~A~B及它们之间的相关性,另外,还对两苯环间不同介入基团对电子转移的影响做了初步研究,发现不同的介入基团存在着较大的差异。     

比值光谱导数法同时测定铝合金中铁,铜,锌

用比值光谱－导数分光光度法，在ｐＨ５．５缓冲溶液中，利用金属－２－（５－溴－２－吡啶偶氮）－５－二乙氨基酚（５－Ｂｒ－ＰＡＤＡＰ）－ＯＰ三元络合物显色体系，对混合物中铁，铜，锌三组分进行了同时测定。合成试样５次测定回收率在９７．３％－１０４．４％之间。应用于铝合金中铁，铜，锌的测定，各６次测定的ＲＳＤ分别为３．６６％，１．３８％，２．０３％。     

Resolution of global signals using ratio differential pulse polarograms: Determination of p-nitroaniline and p-nitrotoluene in their mixture

Ratio differential pulse polarograms obtained by dividing the multianalyte and single analyte signals are proposed as a tool for resolution of global signals and quantification of the analytes from a qualitatively known mixture by differential pulse polarography (DPP) and related electroanalytical techniques. The influences of shape and position of the resolving function (DP polarograms of individual analyte) on the efficiency of resolution are discussed on simulated and experimental results. The method is applied for the determination of p-nitroaniline (NA) and p-nitrotoluene (NT) from their mixture in N,N′-dimethylformamide solutions with 0.1 M tetrabutylammonium iodide as supporting electrolyte, using an external calibration diagram and internal standard addition methods. NA and NT give one-electron DP polarographic peaks with 93 mV of peak separation and, therefore, show significant overlapping which depends on the concentration ratio of NA and NT in the mixture. The method is especially suitable for quantification of one analyte in the presence of a large excess of another analyte, because by division the component in excess is removed and the pseudo-ratio DPP of the minor component is clearly revealed in a way which is not possible by deconvolution using polynomial division or deconvolution by Fourier transforms.     

High temperature corrosion behaviour of M(Co,Ni)CrAIY-coatings on high temperature materials-microanalytical investigations

In our former investigations, the phenomenon high temperature corrosion (HTC) was described exemplarily on selected materialcoating combinations for blades of stationary gas turbines, mainly in the temperature region of up to 750° C. To answer the question, in which manner higher gas inlet and/or higher material surface temperature would influence the HTC behaviour, a special analytical technique—the integral layer profile analysis—was introduced to ameliorate concentration profile methods. By examining IN 738 LC specimens with CoCrAlY plasma spray coating, stressed by hot gas at 900° C, the limits of this system are shown by explaining the corrosion mechanism; the method is also used for other systems, e.g. U 520 with NiCrAlY coating at 750° C.     

Absolute configurations and circular dichroism of sesquiterpene-coumarin ethers

The absolute stereochemistry of 14 naturally occurring sesquiterpenecoumarin ethers is discussed. In 13 cases the coumarin moiety is isofraxidin (7-hydroxy-6,8-dimethoxycoumarin), in one case scopoletin (7-hydroxy-6-methoxycoumarin). The sesquiterpene moieties belong either to the bicyclic drimenole series or to its consecutive products (methyl migration, ring opening). The CD spectra of all compounds are given. The assignments of the absolute configurations are based on the method ofHoreau, chemical correlation by degradation reactions, extensive comparison of CD data, and biogenetic considerations.

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Absolute Konfigurationen und Circulardichroismus von Sesquiterpen-Cumarin-Ethern

Zusammenfassung Es wird die absolute Stereochemie von 14 natürlich vorkommenden Sesquiterpen-Cumarin-Ethern diskutiert. In 13 Fällen wird die Cumarineinheit von Isofraxidin (7-Hydroxy-6,8-dimethoxycumarin) repräsentiert, in einem Fall von Scopoletin (7-Hydroxy-6-methoxycumarin). Der Sesquiterpenteil ist entweder von Drimenol oder Folgeprodukten (Methylgruppenwanderung, Ringöffnung) abgeleitet. Die CD-Spektren aller Verbindungen sind angegeben. Die Zuordnung der absoluten Konfigurationen basiert auf der Methode vonHoreau, chemischer Korrelation über Abbaureaktionen, Vergleich der CD-Spektren und biogenetischen Überlegungen.

     

Comparison of the effective core potential and model potential methods in studies of electron correlation energy in molecules: Dihalides and halogen hydrides

Summary The effective core potential and model potential methods were used in post-SCF calculations on HC1, HBr, Cl₂, and Br₂ in order to gain insight into the effect of insufficient representation of inner nodes in the valence orbitals of the approximate methods. The results show that while the correlation energy may be slightly overestimated (by 1–7%), both the electric moment functions and the quantities depending on energy differences are consistently similar for the methods studied and close to the results from all-electron calculations.Dedicated to Prof. Klaus Ruedenberg     

Transient multi pulse method for the determination of N2O - interaction with ZSM-5 type zeolites

Summary Multipulse experiments reveal qualitative and quantitative, time-resolved information about the interaction of N₂O with ZSM-5 type zeolites under conditions of catalytic applications, like the mechanism of N₂O decomposition, amount and reactivity of an atomic surface oxygen species.