Recent contributions of high resolution gas chromatography to the analysis of environmental hydrocarbons

Analyses of hydrocarbon fractions from different areas of the marine environment are described to illustrate the possibilities and limitations of high resolution gas chromatography (HRGC) in the analysis of environmental samples. Examples are given of dissolved, particulate, and sedimentary hydrocarbons and organochlorine compounds; the importance of an adequate sampling of the marine environment is stressed. HR chromatographic profiles obtained in two columns of low and high polarity (SE-52 and PEG 20M) permit the sources and transport pathways of both natural and anthropogenic hydrocarbons to be traced. Analysis of tissues of marine mammals, which metabolize or excrete many of the biogenic and petrogenic hydrocarbons present in other areas of the marine environment, may provide an opportunity to obtain relatively clean profiles of many anthropogenic compounds of interest. The plotting of mass chromatograms from data compiled by COM-GC-MS remains the most appropriate method for the conclusive indentification of these compounds.     

Electrochemical and structural investigations of oxide films anodically formed on ruthenium-plated titanium electrodes in sulfuric acid

The electrochemical characteristics of ruthenium oxides, formed on Ru-plated Ti electrodes in 0.5 M H₂SO₄ by potential cycling with different CV upper potential limits (E _SU), were systematically compared. The repeated potential cycling between 0.2 and 0.75 V activated the formation/reduction of surface Ru oxides with hysteretic behavior. This application of repeated CVs also modified the ability of Ru deposits for hydrogen adsorption/desorption. An irreducible Ru oxide accumulated on the electrode at potentials more positive than ca. 0.95 V, whose capacitive characteristics are applicable for electrochemical supercapacitors. This irreducible oxide was composed of an aggregate consisting of Ru in various oxidation states, bridged oxygen, OH and water in a 3D-like structure with a relatively ordered and compact nature, from the X-ray photoelectron spectroscopic and voltammetric results. The surface reconstruction of the Ru deposits induced by the repeated potential cycling with E _SU≥0.75 V was clearly observed from the SEM photographs. From the X-ray diffraction patterns, all the anodically formed Ru oxides showed an amorphous nature.     

Cyclic Conjugation Energy Effects in Polycyclic π-Electron Systems

Summary. The fact that cyclic arrangements of double bonds have a dramatic effect on the behavior of conjugated organic molecules is known since the 19th century. The fact that in monocyclic conjugated systems the size of the cycle and the number of -electrons involved is decisive for their stability (aromaticity) or lack of stability (antiaromaticity) is known since the 1930s. In polycyclic -electron systems several cyclic effects are present simultaneously and their separation became possible only recently. A molecular orbital method has been elaborated, by means of which the energy effects of individual cycles in polycyclic -electron systems can be estimated. This method is briefly outlined and illustrated by pertinent examples. An exhaustive bibliography of the topic considered is given.     

Chemical species produced in the reaction between ethanedial (glyoxal) and 5-amino-1,10-phenanthroline and their iron(II) complexes: electrochemical studies and analytical applications

The cyclic voltammetric behavior of carbon paste electrodes modified by direct admixing with the products of the reactions between ethanedial (glyoxal) and 5-amino-1,10-phenanthroline at 100°C and that of their iron(II) complexes is reported. The ligand(s) produced in absence of iron(II) are able to complex iron(II) and copper(II) ions reversibly, but other ions such as nickel(II), cobalt(II), cadmium(II) and manganese(II), if complexed, show no electrochemical activity. Admixing with the products of the reaction in the presence of excess of iron(II) ion, because of high insolubility and fast electron exchange, produces surfaces useful for amperometric detection in continuous-flow systems. The voltammetric and amperometric behavior in the presence of HSO^?₃ ions is reported in order to illustrate this application.     

Synthesis and electrochemistry of Group 6 tetracarbonyl (N,N′-bis(ferrocenylmethylene)ethylenediamine)metal(0) complexes

Thermal substitution reaction of Cr(CO)₄(η^2:2-1,5-cyclooctadiene), Mo(CO)₄(η^2:2-norbornadiene), and W(CO)₅(η²-bis(trimethylsilyl)ethyne) with N,N′-bis(ferrocenylmethylene)ethylenediamine (bfeda) yields M(CO)₄(bfeda) complexes which could be isolated from the reaction solution and characterized by elemental analysis, MS, IR, and NMR spectroscopy. In the case of tungsten, W(CO)₅(bfeda) is formed as intermediate and then undergoes the ring closure reaction yielding the ultimate product W(CO)₄(bfeda). The electrochemical behavior of the M(CO)₄(bfeda) complexes was studied by using cyclic voltammetry (CV) and differential pulse voltammetry (DPV) in dichloromethane with tetrabutylammonium tetrafluoroborate as electrolyte. Constant potential electrolysis of the complexes was performed successively at their peak potentials at 0 °C in their CH₂Cl₂ solution and the electrolysis was followed by in situ recording the electronic absorption spectra in every 5 mC. In the electrolysis of Cr(CO)₄(bfeda), the central Cr(0) is oxidized first and electrolysis continues with oxidations of two ferrocenyl groups until the end of totally three moles of electron passage per mole of complex. In the electrolysis of Mo(CO)₄(bfeda) and W(CO)₄(bfeda) the first oxidation occurs on the central atom forming a short-lived species which undergoes an intramolecular one-electron transfer and is reduced back to M(0) while one of the ferrocene units is oxidized to the ferrocenium cation at the same time. This indicates that the electron is transferred from iron to the central metal atom.     

Reactions of (η6-Arene)tricarbonylchromium Complexes: Hydrogenation,Nitration, and Bromination

In this study, we explore the reactions of coordinated arenes, e.g., hydrogenation, nitration, and bromination, to prepare compounds which are not accessible from conventional organic synthesis. The reaction products formed from reactions with the coordinated and the uncoordinated arenes are compared. The polycyclic aromatic hydrocarbons (PAHs) employed for this study include phenanthrene, methyl- and acetyl-phenanthrene, and benz[a]anthracene (BA), The tricarbonylchromium group demonstrated various characteristics which influence the reactions in this work, such as an electronic effect to deactivate hydrogenation, a steric effect to exhibit, highly positional selective nitration, and a free radical mechanism to direct bromine to attack at the ring coordinated to tricarbonylchromium.     

Synthesis and structure of the 1,2-isopropylidene-α-D-glucofuranose 3,5,6-bis-cyclophosphite complex with tungsten(0) pentacarbonyl

Metallocomplexes with optically active ligands are of considerable interest as catalysts of stereoselective processes. A complex of 1,2-isopropylidene-α-D-glucofuranose 3,5,6-bis-cyclophosphite with tungsten(0) pentacarbonyl has been synthesized for the first time and studied by X-ray crystallography.     

Synthesis of triphenylene derivatives by Pd-catalyzed Suzuki coupling/intramolecular CH activation between arylboronic acids and dibromobiphenyls

An efficient and regioselective synthesis of functionalized triphenylenes via palladium-catalyzed Suzuki-Miyaura coupling and subsequent intramolecular CH activation between arylboronic acids and dibromobiphenyls was developed. This methodology showed excellent atomic economy and regiospecificity as well as synthetic feasibility of unsymmetrical triphenylenes.     

Voltammetric determination of hafnium with calconcarboxylic acid

The interaction of Hf(IV) with calconcarboxylic acid (1-(2-hydroxy-4-sulfo-1-naphtylazo)-3-naphtolic acid) was investigated by cyclic voltammetry varying various factors (pH, ionic strength, contents of ethanol and scan rate). Optimal conditions of Hf(IV) determination in the presence of calconcarboxylic acid were found: acetic buffer solution pH 2.6, scan rate 0.5 Vs⁻¹. The detection limit of Hf(IV) concentration was 2.46 × 10⁻⁷ mol L⁻¹. The influence of foreign ions on the Hf(IV) determination was studied. It was established that some metals like cadmium, nickel, zinc, copper and titanium could be determined with Hf(IV) simultaneously. The method of voltammetric determination of hafnium was tested on model solutions and used in the determination of Hf(IV) in terbium-base alloy.     

Application of particles as pseudo-stationary phases in electrokinetic chromatography

Since the introduction of micelles by Terabe et al. (1984), many different species have been employed as carriers for electrokinetic chromatography. As it is not possible to separate uncharged solutes or ions with equal mobility in capillary electrophoresis, these phases are added to introduce or improve selectivity.

This review surveys the application of particles as pseudo-stationary phases. Up to now only very few applications exist based either on polymer particles for the separation of catechols and primary amines or silica-based material. With these particles separations are shown for phenols, polycyclic aromatic hydrocarbons and naphthalene derivatives. The characteristic properties of particles as pseudo-stationary phases and their benefits as well as their limitations are discussed.