大环二萜天然产物(±)-Mayol的全合成

西松烷型二萜类化合物是一大类广泛分布于松脂、烟草、陆地动物及海洋生物体中的具有十四元碳环骨架的化合物.其结构新颖复杂,且大多具有显著和广谱的生物活性.近几十年来,有关这类化合物的研究已引起了人们的极大兴趣.因此,开展这类天然产物及其类似物的全合成及构效关系的研究不仅具有重要的学术价值,而且具有潜在的应用前景.     

工业用水中总铁含量的快速测定

介绍了以菲咯嗪－醋酸钠－醋酸缓冲溶液为显色体系、用自制的铁含量比色测定仪快速测定工业用水中总铁含量的方法。总铁含量≤０５ｍｇ／Ｌ时，标准偏差≤００３ｍｇ／Ｌ；总铁含量＞０５ｍｇ／Ｌ时，相对标准偏差≤５％。单次测定时间（包括样品处理）为１０～１５ｍｉｎ。采用单色光源及微型流动比色池，由蠕动泵和电子线路实现自动进样，直接显示测定结果。     

Vibronisches Spektralverhalten von Molekülen: XX. Theoretische Untersuchung der S2←S0-Absorption des Pyrens im Rahmen der Herzberg-Teller-Näherung erster Ordnung

Summary On the basis of the completely-optimized S₀ and S₂ molecular geometries of pyrene the vibrational structure of the electronic S₂S₀ transition was calculated within both the Condon approach and the first-order Herzberg-Teller approach. The theoretical results demonstrate the significant influence of vibronic coupling. An analysis of the active vibrational modes is given. The theory-experiment comparison within the Herzberg-Teller approach is satisfactory.

     

meso-四(邻烷氧基苯基)卟啉合钴的合成、表征和性能研究

合成了meso-四(邻烷氧基苯基)卟啉合钴配合物10个,其中未见文献报道的新化合物8个，研究了其合成、分离、纯化方法,首次得到了该系列化合物的晶体或固体。用¹H NMR、MS、IR、UV、元素分析等表征确证了其结构,报道和解析了该类卟啉钴配合物的¹H NMR特殊波谱现象。用差示扫描量热法(DSC)和偏光显微镜(PM)研究了该系列配合物的液晶性能,发现6个配合物具有液晶性。研究了烷氧基链长、金属离子和分子空间结构对卟啉液晶性能的影响,烷氧基链长的增加、金属配合物的形成有利于液晶性能的改善。     

Rate processes on fractals: Theory,simulations, and experiments

Heterogeneous kinetics are shown to differ drastically from homogeneous kinetics. For the elementary reaction A + A products we show that the diffusion-limited reaction rate is proportional tot ^– h[A]² or to [A]^x, whereh=1- d _s/2, X=1+2/d _s =(h-2)(h-1), andd _s is the effective spectral dimension. We note that ford = d _s =1, h =1/2 andX = 3, for percolating clustersd _s = 4/3,h = 1/3 andX = 5/2, while for dust ds <1, 1 >h > 1/2 and >X > 3. Scaling arguments, supercomputer simulations and experiments give a consistent picture. The interplay of energetic and geometric heterogeneity results in fractal-like kinetics and is relevant to excitation fusion experiments in porous membranes, films, and polymeric glasses. However, in isotopic mixed crystals, the geometric fractal nature (percolation clusters) dominates.     

Photochemistry of molecules relevant to the atmosphere: photodissociation of nitric acid in the gas phase.

This Minireview gives an account of the photochemical decay of nitric acid HNO3 in the gas phase, which has been well investigated under bulk and molecular-beam conditions. Due to the importance of this molecule in atmospheric chemistry, attention was paid to the irradiation regions around 300 and 200 nm, where solar photolysis of HNO3 is expected to be particularly efficient. While the low-energy region is characterized by the products OH and NO2, the high-energy region gives rise to a variety of photochemical decay pathways, dominated by channels which lead to the products HONO + O in different electronic states.     

Filter Diagonalization with Finite Fourier Transform Eigenfunctions

Below, we briefly report on the progress in the development of the Filter Diagonalization technique when filtering is carried out with the aid of Finite Fourier Transform (FFT) eigenfunctions. During recent years interest in these functions, also known as ‘prolates’, or ‘slepians’, has increased among scientists doing research in the field of signal processing. The main explanation to this follows from the set of very special extremal and orthogonality properties exibited by the FFT eigenfunctions. Recent results of Walter and Shen on sampling with prolate spheroidal functions will necessary produce a new wave of interest. In the presented, Filter diagonalization machinery, we show that the sampling formula of Walter and Shen simplifies essentially the computation of matrix elements as certain 2D–integrals involving FFT eigenfunctions.     

Microwave and RF surface wave sustained discharges as plasma sources for plasma chemistry and plasma processing

The surface wave produced plasma belongs to a class of RF and microwave induced plasmas. It results from the propagation of an electromagnetic wave which uses the plasma column it sustains and the plasma tube as its sole propagating media. This type of plasma offers several advantages compared to the positive column plasma of dc discharges or to other RF and microwave produced plasmas. Surface wave plasmas require no internal electrodes, and they can be applied over an extremely broad range of wave frequencies (27 MHz to 10 GHz demonstrated) and gas pressures (about 10^–4 Torr to a few times the atmospheric pressures). Using the surface wave plasma technique, a large variety of plasma column diameters have been created (0.5–150 mm demonstrated) and no limitation on plasma column length (column up to 6 m long demonstrated) has been found. The surface wave produced plasma is used in elemental analysis and to sustain emission in lasing media. This article is intended as a guide for potential users of surface wave plasmas in the field of plasma processing and plasma chemistry.     

Photolytic oxidation of As species for determination of total As (including the ‘hidden’ As fraction) in coastal seawater by hydride generation-atomic fluorescence spectrometry

Ultraviolet irradiation (photolysis) in alkaline medium was applied for pretreatment of seawater samples so as to accurately determine total As by continuous-flow hydride generation-atomic fluorescence spectrometry. This sample pretreatment is meant to convert non-reducible As forms into inorganic As, which easily forms arsine. The optimised parameters were the treatment time and the pH of the medium. The behaviour of four hydride-reactive As species [As(III), As(V), MMA, DMA], and AsB, i.e. a typical non-hydride-reactive As species, when subjected to UV irradiation was studied. UV irradiation at pH 1 lead to conversion of all species into As(V) with the exception of AsB and DMA. Conversions of DMA and AsB into As(V) at pH 11 in less than 30 min were observed under UV irradiation. The limit of detection of As (measured as As(V)) by hydride generation-atomic fluorescence spectrometry was 0.1 μg/L and the repeatability of the oxidation procedure was about 10%. The method was applied to determination of total and directly reducible As at 11 sampling points of the Galician Coast (Atlantic Ocean, Spain). Total As concentrations were in the range 1.4-4.8 μg/L. A significant As fraction, between 20 and 44%, depending on the sampling point, corresponded to non-reducible As which was converted by UV irradiation into hydride-reactive As. This fraction should represent the sum of DMA, which yields a low sensitivity in the continuous flow-AFS system, and the hidden As fraction.