Retention prediction of polycyclic aromatic hydrocarbons in reversed phase liquid chromatography with various mobile phase compositions and column temperatures

Summary The relationship between the logarithmic capacity factor measured in reversed-phase liquid chromatography and the operating conditions including the mobile phase composition and the column temperature is investigated. The strategy described herein can offer the possibility to predict the retention of polycyclic aromatic hydrocarbons without any experiments and standard materials, by utilizing equations describing the relationships between retention, temperature, mobile phase composition and physicochemical properties of the solutes previously stored in the program of the microcomputer-assisted retention prediction system.This concept is one of the most promising techniques for the optimization of the separation conditions in reversed-phase liquid chromatography.     

The activation of tertiary amines by osmium cluster complexes: Further studies of the reaction of Os3(CO)10(NCMe)2 with triethylamine

The reactions of Os₃(CO)₁₂ and Os₃(CO)₁₀(NCMe)₂ with NEt₃ have been reinvestigated. Two new products, Os₃(CO)₁₀(μ-CH₂C(H)?NEt₂)(μ-H)) (2) and Os₃(CO)₁₀(syn-μ-η¹-CHCHNEt₂)(μ-H) (3) were obtained in low yields, 4% and 7%, in addition to the previously reported compound Os₃(CO)₁₀(anti-μ-η¹-CHCHNEt₂(μ-H) (1) (20% yield) when the reaction was conducted at 25°C using Os₃(CO)₁₀(NCMe)₂. Compounds 2 and 3 were characterized by IR, ¹H NMR and single-crystal X-ray diffraction analyses. Compound 2 contains a bridging methyl-metallated N-ethylimine ligand formed by the cleavage of one ethyl group from the NEt₃. Compound 3 is an isomer of 1 in which the bridging ligand has a syn conformation with respect to the cluster as compared with the anti conformation in 1. Compound 3 slowly isomerizes to 1. Compound 3 is de-carbonylated by exposure to UV radiation and is transformed to the new compound Os₃(CO)₉(μ₃-CC(H)?NEt₂)(μ-H)₂ (4) (58% yield) by an additional CH activation to form a triply bridging η¹-diethylaminovinylidene ligand. Compound 4 isomerizes to the compound Os₃(CO)₉(μ₃-HCCNEt₂)(μ-H)₂ (5) (70% yield) at 68°C. The latter contains a triply briding ynamine ligand which exhibits structural and reactivity features that are characteristic of a carbene ligand at the amine-substituted carbon atom. Crystal data: for 2, space group = P2₁/c, a = 9.236(2) Å, b = 12.469(2) Å, c = 18.107(3) Å, β = 104.67(1)°, Z = 4, 2518 reflections, R = 0.031; for 3, space group = P2₁/m, a = 7.644(1) Å, b = 12.706(2) Å, c = 11.912(2) Å, β = 108.02(1)°, Z = 2, 1295 reflections, R = 0.030; for 4, space group = P2₁/n, a = 10.233(2) Å, b = 14.834(4) Å, c = 14.538(2) Å, β = 99.88(2)°, Z = 4, 2403 reflections, R = 0.036.     

Fluorescence spectroscopy of polynuclear aromatic compounds in environmental monitoring

The occurrence of polynuclear aromatic compounds (PAC) in the environment and experimental techniques suitable for the detection of PAC in environmental compartments are briefly reviewed. The specific requirements for on-site andin situ environmental analysis are outlined. Particular emphasis is given to fluorescence spectroscopic techniques for the investigation of humic acid- and soil-containing samples. Some examples of studies in the literature on Shpol'skii and jet spectroscopy and on laser-induced fluorescence (OF) measurements of PAC and mineral oils are highlighted. Contaminants in the environment are usually encountered as multicomponent mixtures in very complex matrices. Total fluorescence analysis in combination with the chemometrical technique of rank annihilation factor analysis (RAFA) was employed for the evaluation of a six-component PAC mixture in toluene. It was shown that even in the presence of strong spectral overlap the qualitative identification of all compounds and the reliable quantification of five substances was possible. Results are presented from our stationary and time-resolved fluorescence investigations of the interactions between pyrene and humic acid in water. The Stern-Volmer analysis showed a significant effect of pH on the static quenching efficiency which can be explained by the pH-dependent macromolecular structure of humic acids. Preliminary results from studies of the deactivation of triplet PAC and quenching of delayed fluorescence by humic acid are reported. LIF measurements of mineral oils directly from soil surfaces and of a model oil in a soil column were performed with a fiber-optic coupled multichannel spectrometer. The fluorescence intensity/ concentration relationships were established for a crude and a fuel oil; the corresponding lower limits of detection (LOD) were determined to be 0.025 and 0.125% m/m (mass/mass percentages). These detection limits are compared with realistic oil contaminations of soils. In a soil column designed to mimic fixed-bed bioreactors the distributions of fluorescence signal intensities from a perylene-doped model oil before and after water flooding were determined. These results fromin situ measurements can provide a quantitative basis for the modelling of temporal and spatial contaminants' distributions in reactor design.     

FeCl3-catalyzed propargylation of aromatic compounds with propargylic acetates

A new method for the synthesis of propargylated aromatic compounds is developed. The reaction was carried out at room temperature in the presence of a catalytic amount of FeCl₃ in acetonitrile, high product yields were obtained with excellent regioselectivity and the reaction proceeded smoothly without exclusion of moisture or air.     

Retention characteristics of alkylated polycyclic aromatic hydrocarbons in normal phase liquid chromatography

Summary Retention characteristics of series of polymethyl and mono-n-alkyl derivatives of benzene and pyrene, and also of parent polycyclic aromatic hydrocarbons (PAH), were studied using silica and aminopropyl- and cyanopropyl-modified silica. Differences in the selectivities for the studied compound groups were found between the three phases. Deviations from linear behaviour in plots of log (k′)vs. carbon number were observed for the methyl series. These are explained in terms of differences in π-electron delocalisation within the aromatic ring systems. Further, the effect of methyl substitution on selectivity decreased with an increasing number of aromatic rings. Results were obtained which indicated that the primary adsorption site in a cyano column used in normal phase mode, at least for PAH molecules, is the cyano group.     

伯胺N1923负离子混合萃取稀土元素

本文测定了 N 1 9 2 3在p H6 的条件下对三价稀土离子的萃取,实验表 明 N 1 9 2 3作 为中性萃取剂配位于稀土原子,并且有较高的萃取率.分别选用三氯醋酸和硫氰酸根作为 阴离子,对 N 192 3作为萃取剂时两个体系的萃取行为、萃合物组成和配位数进行了测定和比较     

Convenient synthesis of 12H-benzo[a]xanthenes from 2-tetralone

Convenient and facile syntheses of 12H-benzo[a]xanthenes from 2-tetralone and 2-hydroxyaromatic aldehydes is described. 2-Tetralone reacted with 2-hydroxyarylaldehydes to yield 12H-benzo[a]xanthenes under acidic conditions.