Feasibility of using solid sampling graphite furnace atomic absorption spectrometry for speciation analysis of volatile and non-volatile compounds of nickel and vanadium in crude oil

A method for the direct determination of volatile and non-volatile nickel and vanadium compounds in crude oil without previous treatment using direct solid sampling graphite furnace atomic absorption spectrometry is proposed. The crude oil samples were weighed directly onto solid sampling platforms using a microbalance and introduced into a transversely heated solid sampling graphite tube. In previous work of our group losses of volatile nickel and vanadium compounds have been detected, whereas other nickel and vanadium compounds were thermally stable up to 1300 and 1600 °C, respectively. In order to avoid this problem different chemical modifiers (conventional and permanent) have been investigated. With 400 μg of iridium as permanent modifier, the signal started to drop already after two atomization cycles, possibly because of an interaction of nickel (which is a catalyst poison) with iridium. Twenty micrograms of palladium applied in each determination was found to be optimum for both elements. The palladium was deposited on the platform and submitted to a drying step at 150 °C for 75 s. After that the sample was added onto the platform and submitted to the furnace program. The influence of sample mass on the linearity of the response and on potential measurement errors was also investigated using four samples with different nickel content. For the sample with the lowest nickel concentration the relationship between mass and integrated absorbance was found to be non-linear when a high sample mass was introduced. It was suspected that the modifier had not covered the entire platform surface, which resulted in analyte losses. This problem could be avoided by using 40 μL of 0.5 g L⁻¹ Pd with 0.05% Triton X-100. Calibration curves were established with and without modifier, with aqueous standards, oil-in-water emulsions and the certified reference material NIST SRM 1634c (trace metals in residual fuel oil). The sensitivity for aqueous standards and emulsions was close to that for SRM 1634c, making possible the use of aqueous standards for calibration. The limits of detection and quantification obtained for nickel and vanadium under this condition were found to be 0.02 and 0.06 μg g⁻¹, respectively, for both elements, based on 10 mg of sample. Nickel and vanadium were determined in the samples with (total Ni and V) and without the use of Pd (thermally stable compounds), and the concentration of volatile compounds was calculated by difference. The results were compared with those obtained by high-resolution continuum source graphite furnace atomic absorption spectrometry by emulsion technique; no significant differences were found for total Ni and V at the 95% confidence level according to a Student's t-test.     

Studies on mass production of transformed Panax ginseng hairy roots in bioreactor

The growth properties of Panax ginseng hairy roots transformed by Agrobacterium rhizogenes were compared between flask and aerated column or stirred bioreactor. In flask cultures, sucrose, initially 30 g/L, was nearly exhausted after 45 d of culture. The pH of the medium dropped from 5.5 to 4.96 after 10 d, but afterward it gradually increased to 6.4. After 45 d, hairy roots grew about 16-folds. The growth rate of hairy roots in air-bubble column or stirred bioreactor cultures was 1.13 (1.11) to 1.23 (1.20) g fresh wt (dry wt)/(g of cells·d), respectively. For both bioreactors, growth was about three times as high as in the flask cultivation.     

Direct separation of the enantiomers of cetirizine and related compounds by reversed-phase chiral HPLC

Summary Direct separations of the enantiomers of cetirizine and related compounds have been achieved by reversed-phase HPLC on the Chiralcel OD-R, a polysaccharide-derived chiral stationary phase; the mobile phase was usually perchlorate solution supplemented with acetonitrile. Resolution of the enantiomers of cetirizine and related compounds was good. The effect of the acetonitrile content of the mobile phase was investigated, and the effect of the structure of the chiral compounds on their behavior on the Chiralcel OD-R column is discussed.     

Determination of oxaliplatin in human plasma and plasma ultrafiltrate by graphite-furnace atomic-absorption spectrometry

A method for sensitive determination of the anti-cancer agent oxaliplatin in human plasma and human plasma ultrafiltrate (pUF) is presented. The method is based on the quantification of platinum by graphite-furnace atomic-absorption spectrometry, with Zeeman correction and an atomisation temperature of 2,700°C. Sample pretreatment involves dilution of the samples with a solution containing 0.15 mol L^–1 NaCl and 0.20 mol L^–1 HCl in water. Validation was performed in accordance with the most recent FDA guidelines for bioanalytical method validation. All results were within requirements. The validated ranges of quantification were 0.10–400 mol L^–1 for human pUF and 0.50–400 mol L^–1 for plasma. The assay is now successfully used to support pharmacokinetic studies of cancer patients treated with oxaliplatin.     

原油三维荧光分析中猝灭现象辨析

研究了原油的三维荧光猝灭现象，指出浓度过高是原油产生荧光猝灭的主要原因，将会造成三维荧光等值线图畸变，致使定量分析数据失真，谱图特征变异，难以获取原油特征三维指纹图。提出了避免荧光猝灭的预试方法，并列出了不同类型原油的最佳测试浓度。     

Exogenous donors of nitric oxide (a chemical aspect)

The review considers problems related to the formation, in the living organism, of nitric oxide, a versatile and vitally important regulator of cell metabolism. The pathways of formation of endogenous nitric oxide from L-arginine are discussed and the main approaches to increasing the NO concentration by introducing various types of exogenous nitric oxide donors into the organism and chemical and biological characteristics of these donors are considered. Primary attention is devoted to the known drugs that were shown to release NO under hydrolytic, oxidative, or reductive conditions. The solution of problems related to the elucidation of the mechanisms of drug action requires that the formation of nitric oxide be taken into account.     

Simultaneous determination of cobalt,copper, iron and vanadium in crude petroleum oils by HPLC

Summary A method has been developed for the simultaneous formation and solvent extraction of cobalt (II), copper (II), iron (II) and vanadium (IV) complexes of bis (acetylpivalylmethane)ethylenediamine (H₂APM₂en) in methyl isobutyl ketone. The complexes are eluted from a reversed phase HPLC column with a mixture of methanol:water:acetonitrile and detection was at 260 nm. The method has been applied to the simultaneous determination of cobalt, copper, iron and vanadium in crude petroleum oils at the ng level.     

生物降解原油研究的新方法

利用沥青质包裹烃和沥青质钌离子催化氧化（RICO）产物中的生标对生物降解原油进行了研究。研究表明，虽然原油中的生标受到了严重破坏，但利用这两种方法在沥青质中均可以获得较为完整的生标系列。与其它方法相比，这两种方法简单方便，结果较为可靠、准确，可能是生物降解原油研究的发展方向。     

原油溶胶-凝胶等温转变过程中的流变性研究

使用RS75流变仪，采用小振幅振荡剪切方法和稳态剪切方法对含蜡原油在溶胶 -凝胶等温转变过程中的流行了研究．结果表明，等温转变成的凝胶原油的结构在 很大程度上决定于预剪切速率，非牛顿含蜡原油在结构恢复过程中表现出不可逆的 触变特性．而凝胶原油在外力作用下向溶胶状态转变的过程中，要经历从线性粘弹 性变形，到非线性粘弹性变形，再到结构屈服的过程，且高剪切应力下的溶胶原油 结构与预剪切速率无关．     

High-performance liquid chromatography of ternary nickel dithiocarbamate complexes derived from some sympathomimetic drugs

Summary Nickel dithiocarbamate complexes derived from some sympathomimetic drugs are examined on silica Radial-Pak columns using binary solvents containing a small percentage of an organic polar modifier. Both the type and concentration of this modifier was found to influence the separation of the ternary from the parent binary complexes. When the two ligands in a ternary complex are racemic to each other, separation of the ternary complex is only possible when certain structural requirements of the molecule are fulfilled. Ternary complexes which contain structurally similar, but nonracemic ligands, are shown to be readily separated from binary complexes. When two such complexes differ only in that one of the ligands in one is enantiomeric to a ligand in the second complex, then it can be shown that the ternary complex with the (+) enantiomer ligand elutes faster from the silica column than the one with the (–) enantiomer ligand. An example of the use of ternary complexes for the identification of optical and structurally related impurities in pharmaceutical products is also given.