偏最小二乘法在原子吸收光谱分析中的应用——钴和铟的同时测定

本文用偏最小二乘法（ＰＬＳ）校正了火焰原子吸收分析Ｉｎ２５２．１３７ｎｍ对Ｃｏ２５２．１３６ｎｍ的吸收线重叠干扰,对混合样中Ｃｏ和Ｉｎ的含量进行了测定,结果令人满意。     

Determination of heavy metal concentration in feed and permeate streams of polymer enhanced ultrafiltration process

Polymer enhanced ultrafiltration (PEUF) is a newly developed method for the removal of heavy metals from aqueous solutions. This method was applied for the removal of mercury and cadmium with the presence of polyethyleneimine (PEI) as a water soluble polymer. After ultrafiltration experiments for metal–polymer mixtures, two separate streams, namely, retentate and permeate, former of which contains mainly metal–polymer complex and free polymer molecules while latter of which mainly contains free metal ions, were obtained. At the end of PEUF experiments, performance of operation was determined by concentration analyses which was achieved by atomic absorption spectroscopy (AAS) applied in a different way for permeate and retentate streams considering the effect of presence of polymer. For mercury analysis, cold vapor AAS was applied. It was observed that the presence of PEI did not affect the atomic absorption signal when 10% HCl was added to the sample solutions. For calcium and cadmium, flame AAS was used. It was observed that change in PEI concentration results in change in measured concentration of calcium and cadmium. Therefore, two new approaches were developed for accurate measurement of concentrations of calcium and cadmium. It was also observed that presence of other metals did not affect the accuracy of the measurement of a particular metal in the concentration range studied.     

Dimer asymmetry in superoxide dismutase studied by molecular dynamics simulation

Summary Molecular dynamics (MD) simulations of 100 ps have been carried out to study the active-site behaviour of the Cu,Zn superoxide dismutase dimer (SOD) in water. The active site of each subunit was monitored during the whole simulation by calculating the distances between functional residues and the catalytic copper. The results indicate that charge orientation is maintained at each active site but the solvent accessibility varies. Analysis of the MD simulation, carried out by using the atomic displacement covariance matrix, has shown a different intra-subunit correlation pattern for the two monomers and the presence of inter-subunit correlations. The MD simulation presented here indicates an asymmetry in the two active sites and different dynamic behaviour of the two SOD subunits.     

Structural aspects and electronic absorption of the hydroxyphenanthroperylene quinones fringelit D,hypericin, and stentorin

Summary PPP type semiempirical quantum chemical calculations of absorption spectra were performed for hypericin, fringelit D, stentorin, and their respective conformers, tautomers, and deprotonated species. The results agree with the experimental absorption spectra of hypericin, stentorin, and fringelit D, their deprotonated species, and the polarized absorption spectra of an ,-long chain appended hypericin derivative embedded in stretched polyethylene.

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Strukturelle Aspekte und elektronische Absorptionseigenschaften der Hydroxyphenanthroperylenchinone Fringelit D, Hypericin und Stentorin

Zusammenfassung Semiempirische quantenchemische Rechnungen (PPP-Typ) der Absorptions-spektren von Hypericin, Fringelit D, Stentorin und ihrer Konformeren, Tautomeren und deren Deprotonierungsprodukten wurden durchgeführt. Die Resultate stehen in Einklang mit den experimentellen Absorptionsspektren von Hypericin, Fringelit D, Stentorin, ihrer Deprotonierungsprodukte und dem polarisierten Absorptionsspektrum eines in gestrecktem Polyethylen eingebetteten ,-substituierten Hypericinderivates.

     

Determination of trace elements in human serum by inductively coupled plasma atomic emission spectrometry with flow injection

An analytical method for the simultaneous determination of some trace elements (Au, Fe, Mg, Li, Sr, Zn) in human serum by inductively coupled plasma atomic emission spectrometry (ICP-AES) with flow injection is described. Physical interference caused by the change of sample viscosity is discussed. When 100 μl of serum was injected, the relevant recoveries of > 99% for Li, > 98% for Cu and Mg, > 95% for Fe were obtained for an NIST SRM with R.S.D. > 1.3% using optimized flow injection parameters. The prepared lyophilized control serum for routine analysis in clinical laboratories was analyzed and verified for the validity of the technique employed in this experiment using NIST SRM 909 as a primary reference material.     

Evaluation of a magnetically coupled microcavity hollow cathode discharge for atomic emission spectroscopy

A magnetically coupled microcavity hollow cathode discharge device was evaluated for its analytical potential as a boosted atomic emission source. A magnetic field using an electromagnet was applied perpendicular to the axis of the microcavity hollow cathode. The intensity of the atomic emission of copper, aluminum and the ionic emission of magnesium increased with increasing magnetic field until it reached a maximum. A further increase in the field strength did not lead to an enhancement of these emissions. The attainment of the maxima was attributed to the increase in the electron temperature and radial diffusion of the electrons from the center of the microcavity axis. Electron temperatures in the presence of the magnetic field calculated based on the semicorona model were shown to be proportional to the square of the reduced field strength. Further, these maxima were correlated to the energies of the upper levels of the transition studied.     

气相二茂铁双电荷离子的动能谱研究

The unimolecular charge separation reactions of the doubly charged ions FeC_(10)H_(10)~(2+)、FeC_(10)H_9~(2+)、FeC_(10)H_8~(2+) produced in the ion source by electron impact from ferrocene have been studied using Mass analyzed Ion Kinetic Energy Spectrometry (MIKES) technique. From the values of the kinetic energy releases (T), the intercharge distances (R) of the exploding doubly charged ions in their transition structures have been estimated and some structural informations about the transition states can be obtained. The collision induced reactions of the FeC_(10)H_(10)~(2+) ion with Ar have been studied using MIKES, we postulate a new type of continuing reaction which may be "collisional charge separation induced dissociation".     

Metal furnace heated by flame as a hydride atomizer for atomic absorption spectrometry: Sb determination in environmental and pharmaceutical samples

The present work describes a metallic hydride atomizer for atomic absorption spectrometry, by evaluating the performance of the Inconel 600^® tube. For this purpose, stibine was used as the model volatile compound and antimony determination in river and lake sediments and in pharmaceutical samples was carried out to assess the metal furnace performance. Some parameters are evaluated such as those referring to the generation and transport of the hydride (such as KBH₄ and acid concentrations, carrier gas flow rate, injected volume, etc.), as well as those referring to the metal furnace (such as tube hole area, flame composition, long-term stability, etc.). The method presents linear Sb concentration from 2 to 80 μg L⁻¹ range (r > 0.998; n = 3) and the analytical frequency of ca. 140 h⁻¹. The limit of detection (LOD) is 0.23 μg L⁻¹ and the precision, expressed as R.S.D., is less than 5% (40 μg L⁻¹; n = 10). The accuracy is evaluated through the reference materials, and the results are similar at 95% confidence level according to the t-test.     

RECENT PROGRESS OF NANO-MECHANICAL MAPPING

 Nano-mechanical mapping by atomic force microscopy has been developed as an useful application to measure mechanical properties of soft materials at nanometer scale. To date, the Hertzian theory was used for analyzing force-distance curves as the simplest model among several contact mechanics between elastic bodies. However, the preexisting methods based on this theory do not consider the adhesive interaction in principle, which cannot be neglected in the ambient condition. A new analytical method was introduced to estimate the elasticity and the adhesive energy simultaneously by means of the JKR theory, describing adhesive contact between elastic materials. Poly(dimethylsiloxane) (PDMS) and isobutylene-co-isoprene rubber (IIR) were analyzed to verify the applicable limit of the JKR analysis. For elastic samples such as PDMS, the force-deformation plots obtained experimentally were consistent with JKR theoretical curves. Meanwhile, for viscoelastic samples, especially for IIR, the experimental plots revealed large deviations from JKR curves depending on scanning velocity and maximum loading force. Some nano-rheological arguments were employed based on the difference between these specimens.     

火焰原子吸收法测定铅锌矿中微量镓

将样品中的硫化物用HNO3氧化为硫酸盐后，再用HNO3、HF、H2SO4进一步溶解，在6mol/LHCl介质中用乙酸丁酯萃取镓，水反萃取后，用火焰析子吸收法测定Ga，该法检出限为0．80μg/mL，相对标准偏差为2．1％，用该法测得国家一级标准品的结果均与推荐值相符。