The potential of solid-phase microextraction on polyacrylate coated fibre, with sequential or simultaneous trimethylsilyl derivatisation followed by gas chromatographic–mass spectrometric analysis, was evaluated for a rapid determination of the distribution of the phytosterols in aqueous food matrixes. Influences of different parameters (bis(trimethylsilyl)trifluoro-acetamide and sterol exposure time, sterol concentration and experimental protocol) on the recovery of sterols were investigated to determine optimum conditions which were tested for sterol extraction and analysis from orange juice. Best selectivity, sterol recovery and derivatisation yields were obtained by extraction and simultaneous derivatisation through immersion of the SPME-PA fibre in the orange juice (10 min, 65 °C) after headspace absorption of BSTFA (30 min, 65 °C) on the fibre. Nevertheless the method developed cannot be used for quantitative analysis. But the possibility to effect rapid screen of phytosterol containing in complex media have been shown.

Analysis of aromatic compounds in the New Zealand manuka honey was carried out by solid phase microextraction followed by gas chromatography-mass spectrometry. A total of 38 compounds were detected. Seven of them such as; 1,4-bis(x-methoxyphenyl)-but-2-en-1-one, 1,5-bis(x-methoxyphenyl)-pent-3-en-1-one, 1,4-bis(x-methoxyphenyl)-1-pentanone, 1,6-bis(x-methoxyphenyl)-3-heptene, 1,6-bis(x-methoxyphenyl)-hex-2(3 or 4)-en-1-one and 2(3, 4 or 5)-hydroxy-1,6-bis(x-methoxyphenyl)-1-hexanone, had never before been identified as natural products. Their structures were deduced from the mass spectral data. Seven other compounds; 2,3-dimethoxynaphthalene, 4-(x-methoxyphenyl)-1-phenyl-1-butanone, desoxyanisoin, 2,6-dimethoxybenzoic acid benzyl ester, 4,4'-dimethoxystilbene, 3,3,4,5,5,8-hexamethyl-2,3,5,6-tetrahydro-s-indacene-1,7-dione and 1,5-bis(4-methoxyphenyl)-pentane-1,5-dione, were found in honey for the first time. Methyl syringate, ortho-methoxyacetophenone and 3-phenyllactic acid were the most abundant components.

A brief historical overview of physical chemistry at the University of Geneva as well as a description of the present research activities at the department of physical chemistry are presented.

Macrophage infectivity potentiator (MIP) was originally reported to be a chlamydial lipoprotein from experiments showing incorporation of radiolabeled palmitic acid into native and recombinant MIP; inhibition of posttranslational processing of recombinant MIP by globomycin, known to inhibit signal peptidase II; and solubility of native MIP in Triton X-114. However, the detailed structural characterization of the lipid moiety on MIP has never been fully elucidated. In this study, bioinformatics and mass spectrometry analysis, as well as radiolabeling and immunochemical experiments, were conducted to further characterize MIP structure and subcellular localization. In silico analysis showed that the amino acid sequence of MIP is conserved across chlamydial species. A potential signal sequence with a contained lipobox was identified, and a recombinant C20A variant was prepared by replacing the probable lipobox cysteine with an alanine. Both incorporation of U-¹⁴C-esterified glycerol and [U-¹⁴C]palmitic acid and posttranslational processing that was inhibitable by globomycin were observed for recombinant wild-type MIP but not for the recombinant C20A MIP variant. The fatty acid contents of native and recombinant MIP were analyzed by gas chromatography-mass spectrometry, and the presence of amide-linked fatty acids in recombinant MIP was investigated by alkaline methanolysis. These results demonstrated a lipid modification in MIP similar to that of other prokaryotic lipoproteins. In addition, MIP was detected in an outer membrane preparation of Chlamydia trachomatis elementary bodies and was shown to be present at the surfaces of elementary bodies by surface biotinylation and surface immunoprecipitation experiments.

Rearrangement of cholesta-2,4,6-triene in the presence of p-toluenesulfonic acid in acetic acid at 70 °C leads to 4-methyl-19-nor-cholesta-1,3,5(10)-triene and 1(10 → 6)-abeo-14β-cholesta-5,7,9(10)-triene in less than 2 h. Postulated mechanisms of formation of these products are supported by molecular mechanics calculations of the relative stabilities of reaction intermediates. The results suggest that Δ^5,7-sterols, the most common natural precursors of triunsaturated steroidal hydrocarbons in contemporary sediments, constitute another major source for monoaromatic A and B steroids in addition to Δ⁵-sterols.

The separation of different ring numbered polyaromatic hydrocarbons (PAHs) was accomplished by using cetyltrimethylammonium bromide (CTAB) in capillary electrokinetic chromatography. In order to increase the solubilities and selectivities of PAHs, acetonitrile (ACN) was used as an organic modifier. Under the optimised conditions, 11 aromatic compounds were separated within 14.5 min in a running electrolyte containing 10 mM phosphate, 30 mM CTAB, and 40% ACN at pH 6.0. The effects of CTAB and ACN concentrations, voltage and pH on the resolution were investigated. Reproducibilities of migration times range between 0.55 and 1.27 R.S.D.% and peak areas between 1.02 and 7.23 R.S.D.%. Limit of detections (LODs) range between 0.09 and 2.24 μg ml^−1. This new and fast separation method of PAHs was applied to cooked oil sample.

Separation and determination of some common metal ions was achieved with methyl 3-amino-3-(pyridin-3-yl)propanoate dihydrochloride (MAPP) as an ion-pairing reagent and pyridine as a detectable counter-ion for indirect UV detection at 254 nm. The effects of the complexing reagent and chromophore concentrations, applied voltage, and organic solvent content on the separation were investigated. The optimized separation was carried out in a running electrolyte containing 16 mM MAPP and 20 mM pyridine at pH 4.0 and was successfully applied to the qualitative and quantitative analysis of Li⁺, Na⁺, Mg²⁺, Ca²⁺, Ba²⁺, Ni²⁺, and Zn²⁺ in pharmaceutical vitamin preparations and various water samples.

A complex sedimentary sample from the Monterey Formation (CA, USA) has been submitted to GC–MS analysis followed by mass spectral deconvolution using Automated Mass Spectral Deconvolution and Identification System (AMDIS). Adjusting the parameters of the software allowed for the extraction of the spectrum of an unusual steroidal hydrocarbon coeluting with the major compound of the chromatogram. Following a careful interpretation of the “extracted� mass spectrum, the structure of the unknown has been postulated to be the 4,14-dimethylcholestane (DMC). Possible origins of this rare steroid are briefly discussed. Thus, application of AMDIS appears to be particularly suitable for the GC–MS analysis of natural complex mixtures characterized by a high number of analytes present in low amounts.

Polycyclic aromatic hydrocarbons (PAHs) including isomeric pairs were separated in capillary electrokinetic chromatography using a cationic surfactant cetylpyridinium bromide (CPBr) as additive. With addition of 2 mM CPBr into the running electrolyte, dynamic coating occurs in the capillary and EOF is reversed. Changes of electroosmotic and electrophoretic mobilities with increasing CPBr concentration were investigated. Under optimum separation conditions, running electrolyte contains 50% MeCN, 20 mM acetate, and 40 mM CPBr at pH = 4.0. Using high concentration of organic solvent, aggregation of surfactants into micelles is prevented. Significant retentions indicate solvophobic, n- and π-electron interactions between CPBr monomers and PAHs.

The 13²,17³-cyclopheophorbide a enol (CPP) is shown to convert mainly to a ~1:1 mixture of (13²R/S) chlorophyllones a (Chlone), when chromatographed over silica gel or alumina supports. 15¹-hydroxychlorophyllonelactone a and some other chlorophyll a related compounds are also tentatively identified as minor transformation products of CPP. This raises the possibility that the chlorophyllones reported in recent sediments may be analytical artifacts from CPP. However, data for the surface sediments from Lake Motte as well as literature data for other contemporary sediments show that, (i) they are not artifacts, (ii) considering that CPP is the intermediate compound in the formation of chlorophyllones from chlorophyll a, the hydroxylation of CPP in the sedimentary environment involves an enzymatic process leading preferentially to 13²S chlorophyllone a.

The characteristics of natural organic matter (NOM), which affect its interactions with and therefore the transport of colloids and particles, depend on the evolution of its individual components. Information on the temporal variations of the components of the organic matter of a well-studied eutrophic lake (Bret, VD, Switzerland) was extracted using pyrolysis/gas chromatography/mass spectrometry. The influence of aquagenic organic matter was found to be at a maximum in summer. The soil-derived organic matter, on the other hand, was found in larger proportions in winter and spring. The appearance of hydroxypropanone in the pyrolysis fragments in the summer months indicates that this portion of the organic matter is aquagenic and very fresh. The dominance of furaldehyde in pyrolysates during the rest of the year indicates the presence of polysac charides may be of either aquagenic or pedogenic origin. The absence of lignin fragments found in the NOM in this lake suggests that lignin-containing components of terrestrial organic matter are not leached out from the soil in significant quantities. A correlation was found between 3-day cumulative rainfall and the proportion of terrestrial components in the identified organic matter in the spring. This correlation disap peared in the summer, probably because of a higher vegetal cover and the masking effect of the high aquagenic productivity. These factors are also likely to be of importance in more complicated lacustrine systems.

Methane concentrations were measured in the water column of the northern basin of Lake Lugano in 1993 and 1994. Methane profiles show three distinct zones: (1) low concentrations generally below 0.1 mmol m−3 from the surface to 80–90-m depth; (2) a. sharp rise in concentration up to 50 mmol m−3 from 80–90- to not, vert, similar 150-m depth; and (3) from not, vert, similar 150-m depth to the bottom with a lower concentration gradient and with the highest methane concentrations in near-bottom water was not, vert, similar 80 mmol m−3. These profiles result from a combination of several factors such as fluxes from sediments, spatially variable vertical mixing, and aerobic and anaerobic bacterial oxidation in the water column. δ13C values indicate a biogenic origin for the methane. The methane inventory in the anoxic hypolimnion is not, vert, similar 2000 metric tonnes, yet its transfer to the surface water is almost completely cancelled by oxidation at the permanent redox interface situated at not, vert, similar 90-m water depth. Increased methane concentrations in near-surface water are not related to the deep-water methane reservoir but probably result from bacterial production of methane in the photic zone. Surface water is over saturated with methane in respect to the atmosphere. Anthropogenic eutrophication in temperate zone lakes has affected the carbon budget and methane production and storage. The potential impact of these changes on global emissions to the atmosphere should be evaluated.

Rearrangement of 5α- and 5β-cholesta-6,8(14)-dienes (13a and 13b, resp.) in the presence of anhydrous toluene-4-sulfonic acid in acetic acid leads to 5α- and 5β-12(13 → 14)-abeo-cholesta-8,13(17)-dienes (15a and 15b, resp.) via 5α- and 5β-cholesta-8,14-dienes (14a and 14b, resp.), respectively. Epimerization at C(20) of the spirosteradienes 15a and 15b occurs with increasing reaction time. Molecular-mechanics calculation of the relative stabilities of these compounds and of congeners thereof is in agreement with the observed reaction pathway.

To determine the limitations of electrospray mass spectrometry for the study of condensed-phase chemistry, it is important to understand the origin of cases for which the electrospray mass spectra, which are a measure of the relative abundances of gas-phase ions, do not reflect the equilibrium ion abundances in the solution electrosprayed. One such divergent case is that of free-base octaethylporphyrin. Under conditions for which this porphyrin is present in solution predominantly as the doubly charged, diprotonated molecule, the predominant ionic species observed in the electrospray mass spectrum is the singly charged, monoprotonated molecule. In this paper, direct optical spectroscopic measurements of the ions in solution (absorption spectra) and in the electrospray plume (fluorescence excitation spectra) are correlated with the ion distribution observed in the gas-phase (as reflected in the electrospray mass spectra) to determine at what point in the electrospray process and by what mechanism(s) the transformation from dication to monocation occurs. The data indicate that the major portion of the doubly protonated porphyrin species originally present in solution are converted to singly protonated species relatively late in the electrospray process, during the latter stages of droplet desolvation in the atmospheric/vacuum interface of the mass spectrometer, via the loss of a charged solvent molecule/cluster.