Electrospray tandem mass spectrometric analysis of zeaxanthin and its oxidation products

Carotenoids have been implicated in protection of the eye from light-mediated photo-toxicity caused by free radicals. Under conditions of normal oxidative stress the carotenoids serve as protective antioxidants; however, when the oxidative stress exceeds the antioxidant capacity, carotenoids can be oxidized into numerous cleavage products. The determination and identification of oxidized carotenoids in biological samples remains a major challenge due to the small sample size and low stability of these compounds. We investigated the reaction of various zeaxanthin cleavage products with O-ethyl hydroxylamine to evaluate their levels in a biological sample. For this, a sensitive and specific electrospray tandem mass spectrometry (ESI-MS/MS) was developed, avoiding the classical lower sensitive and specific HPLC-UV and fluorescence absorption methods. Protonated molecules [M + H](+) of carotenoids upon collision-induced dissociation produced a number of structurally characteristic product ions. A series of complicated clusters of product ions differing in 14 (CH(2))and 26 (C(2)H(2))Da was characteristic of the polyene chain of intact carotenoids. All carotenoid ethyl oximes of zeaxanthin cleavage products were characterized by the losses of 60 and 61 Da in their MS/MS spectra. Through the application of the LC/MS/MS method, we identified two oxime derivatives of 3-hydroxy-beta-ionone and 3-hydroxy-14'-apocarotenal with protonated molecules at m/z 252 and m/z 370 respectively, in a human eye sample.     

Preparative Separation and Analysis of Complex Mixtures of Leucomycins and Desmycarosyl Leucomycins Using HPLC and Mass Spectrometry

Composition and hydrolysis products of a biotechnical available complex of macrolides were analyzed by HPLC and ESI-CID-MSⁿ. Major components are leucomycin-type antibiotics (leucomycins A₁ (5), A₇ (3), A₉ (2), 9-desoxy-9-oxo-turimycin H₃ (4) and niddamycin B (6). Hydrolysis of the complex mixture yielded 9-, 13-isoforocidins (7, 8, 9, 11) and 9-oxo-forocidin (10). A preparative separation procedure was elaborated furnishing compounds 3 - 11 for semisynthetic experiments.Prof. Dr. Udo Gräfe deceased on 14.2.2003. For obituarity see: Schlegel B (2003) J Peptide Sci 9: 661–661.     

Computer interactive identification system for polycyclic aromatic hydrocarbons in reversed-phase microcolumn liquid chromatography

Summary A computer interactive identification system is proposed which is based on the relationship between retention and molecular properties such as the size and shape of polycyclic aromatic hydrocarbons (PAHs). This system offers an automatic analytical process for liquid chromatography, providing a reliable identification of the separated components. The identification can be further enhanced by the use of multiple detectors such as a multichannel UV detector. The system can be used for optimization procedures, resulting in a highly automatic complex analytical system.     

The synthesis and structure of potassium cyanotrimethylaluminate

The reaction of KCN with Al(CH₃)₃ to form K[Al(CH₃)₃CN] is greatly facilitated by the presence of an aromatic solvent: for p-xylene a solid complex, K[Al(CH₃)₃CN]·C₆H₄(CH₃)₂, has been isolated. The crystal structure of potassium cyanotrimethylaluminate has been determined from three-dimensional X-ray data measured by counter methods. K[Al(CH₃)₃CN] crystallizes in the monoclinic space group C2/c with cell dimensions a = 19.902(7), b = 9.211(4), c = 9.615(4) Å, β = 107.74(5)°, and p_calcd. = 1.09 g cm^?1 for Z = 8. Least squares refinement gave a conventional weighted R factor of 4.9% for 807 independent reflections. The monomeric [Al(CH₃)₃CN]^? units possess no crystallographic symmetry, and the packing in the unit cell is such that the nitrogen atoms on three such units approach the potassium atom to within 3.11 Å. The average aluminum-methyl carbon bond distance is 1.971 (7) Å, while the aluminum-cyano carbon distance is 2.047 (7) Å. This significant lengthening is attributed to partial electron deficiency in the aluminum-cyano carbon bond.     

Chiral separation of N-(trans-4-isopropylcyclohexylcarbonyl)-D,L-phenylalanine isomers by high performance liquid chromatography

Summary A high-performance liquid chromatographic method was developed for the chiral separation of a new anti-diabetic agent, N-(trans-4-isopropylcyclohexylcarbonyl)-D-phenylalanine, and its L-enantiomer. The separation was performed on a Sumichiral OA-3300 column. Optimized mobile phase was 0.025 mol.L⁻¹ ammonium acetate in methanol solution. UV detection was at 210 nm. Baseline chiral separation was obtained within 12 minutes. The detection limits are 80 pg for the D-enantiomer and 120 pg for the L-enantiomer. RSD of the method was below 1% (n=5).     

The identification of nitrated polycyclic aromatic hydrocarbons in diesel particulate extracts and their potential formation as artifacts during particulate collection

Summary The highly complex matrix of diesel particulate extracts was analyzed for nitrated polycyclic aromatic hydrocarbons (nitro-PAH) using fused-silica capillary-column gas chromatography along with a thermionic nitrogen-phosphorus detector (TID) and high-performance liquid chromatography followed by on-line catalytic reduction of the nitro-PAH to amino-PAH and subsequent fluorescence detection. Positive isomer identification and quantitation of nitro-PAH are from retention times of authentic standards and their mass spectra. The ease of nitro-PAH formation by nitration of PAH raises the question regarding the origin of these species, whether they are produced as “native” products during the engine combustion process and/or in the exhaust, or instead, formed as the result of chemical conversion to produce artifacts during the sampling procedure. This problem is assessed examing 1-nitropyrene-concentration in particulates of three light-duty diesel engines for different sampling times. 1-Nitropyrene concentrations show only a moderate increase with sampling time under average sampling conditions. Presented at the 15th International Symposium on Chromatography, Nürnberg, October 1984     

σ,π-acetylido complexes via P---C bond cleavage of phosphinoacetylenes: X-ray structure of Fe2(CO)6(CCPh)(PPh2)

Solutions of Co^II salts of organic acids in primary amines absorb molecular oxygen rapidly and irreversibly forming μ-dioxygen—cobalt complexes. Thermolysis leads to a homopolar cleavage of the OO bond with subsequent radical reactions involving ligand amine. After thermolysis the capacity of oxygen uptake is reestablished (catalysis).     

High-Temperature Proton Conductors Based on Strontium and Barium Cerates: The Interphase Exchange and Diffusion of Oxygen

Kinetic parameters of interphase exchange of oxygen in high-temperature proton conductors BaCe_0.95Nd_0.05O_3- and SrCe_0.95Y_0.05O_3- are determined using an isotope exchange method in the temperature range 630-820°C at oxygen pressures of 2.7-13.3 gPa and diffusion coefficients for oxygen are calculated. Effective energies of activation of oxygen exchange and diffusion coefficients for oxygen are calculated. Dependence of exchange characteristics and the diffusion coefficients on the oxygen pressure in the gas phase is investigated. The oxygen exchange on the surface of studied oxides is shown to proceed only with the participation of oxygen of the oxides, which causes high rates of interphase exchange of oxygen of studied cerates of barium and strontium. It is shown that the obtained data satisfactorily agree with those found in the relevant literature.     

A Robust and Efficient Method for the Computation of Equilibrium Composition in Gaseous Mixtures

This paper presents in detail a robust, efficient and accurate methodology for the computation of equilibrium composition in gaseous mixtures. The methodology is founded on the concept of the chemical basis, which is defined and formalized using a powerful matricial approach. The method is specially designed to be general, thus providing basic thermodynamic data in several areas, such as combustion, plasma chemistry and, more generally speaking, computational fluid dynamics. The performance of the method is given in terms of CPU usage and the computed results are compared with those in the published literature. The method is shown to yield results of very high quality in terms of accuracy and smoothness.