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Biomedical subjects

J A Sphon

Publications and source records attributed to J A Sphon.

At least 19 recordsLinked to original sources

Effects of fumonisin B1 on lipid peroxidation in membranes.

Electron spin resonance (ESR)1 spin-label oximetry and spin trapping techniques have been used to study the effect of fumonisin B1 (FB1), an amphipathic mycotoxin on lipid peroxidation in egg yolk phosphatidylcholine (EYPC) bilayers. In the study of the interaction between FB1 and lipid bilayers our results show that fumonisin disturbs the ordering of membranes, enhances oxygen transport in membranes, and also increases membrane permeability. In our model system, lipid peroxidations were initiated by extended incubation of the liposomes, or by inducing Fe2+ ions, UV illumination of H2O2 or ultrasound irradiation. As an indication of the rates of lipid oxidation in EYPC, the consumption of molecular oxygen was studied by monitoring the oxygen concentration in the aqueous phases of the liposomes. Lipid-derived free radicals generated during the oxidation process were measured by a spin trapping method. The incorporation of FB1 in the test samples made the membranes highly susceptible to oxidation. Our results provide the first evidence that the fumonisins appear to increase the rate of oxidation, promote the free radical intermediate production and accelerate the chain reactions associated with lipid peroxidation. The disruption of membrane structure, the enlargement of the relative oxygen diffusion-concentration products, as well as the enhancement effects on membrane permeability, thus provide additional insights into potential mechanisms by which the fumonisins could enhance oxidative stress and cell damage.

Carboxylic Acids↗

Effects of fumonisin B1 and (hydrolyzed) fumonisin backbone AP1 on membranes: a spin-label study.

Electron spin resonance (ESR) spectroscopy and spin label techniques have been used to study the effects of fumonisin B1 (FB1) and hydrolyzed fumonisin backbone (AP1) on the structural and dynamic properties of phosphatidylcholine membranes at the molecular level. Multilamellar liposomes consisting of dimyristoylphosphatidylcholine (DMPC) and egg yolk phosphatidylcholine (EYPC) were used. Six different nitroxide spin labels were used to determine what effects FB1 may impart on the ordering and mobility of lipids in membranes. The experimental results disclose the following: (1) In the fluid phase membrane, FB1 significantly increases the fluidities of n-doxylstearic acid (SA) spin labels (SL) attached to carbons 5 and 7, which disorders the alkyl chains and perturbs the surface region of the bilayer; by comparison, minimal effects were detected near the center of the bilayer. (2) In the gel phase, FB1 and AP1 imparts marked rigidifying effects on membrane fluidity, which enlarges the change in ordering on the phase transition even further. (3) FB1 also restricts the mobility of the (rigid) cholestane spin label. (4) A reduction in mobility of the tempo-stearate spin label suggests that the tricarballylic acid (TCA) moieties of FB1 might mimic the structure of polar headgroups in phospholipids. The present results may provide additional mechanisms to elucidate the toxicological activities of the fumonisins.

Dimyristoylphosphatidylcholine↗

Effects of fumonisin B1 on oxygen transport in membranes.

Electron spin resonance (ESR) spin-label oximetry has been used to study the effects of fumonisin B1 (FB1), a sphingoid-like mycotoxin, on oxygen transport in phosphatidylcholine (PC) bilayers. Moreover, the use of spin labels attached to different carbons of fatty acids makes it possible to do structural and oximetric determinations with the same test sample. Specifically, the incorporation of 10 mol% FB1 increased the oxygen transport properties of both saturated and unsaturated membranes at 37 degrees C by ca. 30% and decreased the ordering of the hydrocarbon chains near the surface of the membranes; concomitantly, oxygen transport near the center of bilayers was diminished slightly, and the relative oxygen diffusion-concentration product profile curves were markedly flattened.

Carcinogens, Environmental↗

Capillary supercritical fluid chromatography/negative ion chemical ionization mass spectrometry of trichothecenes.

A capillary supercritical fluid chromatography/mass spectrometry interface incorporating a heated frit restrictor is described. The trichothecene mycotoxins T-2 toxin, deoxynivalenol and roridin A were used to evaluate the effect of restrictor temperature and carbon dioxide mobile phase on the negative ion chemical ionization (CI) spectra of these compounds under electron capture, proton abstraction and chloride attachment conditions. Restrictor temperatures less than 100 degrees C above the melting point of the samples retarded sample transfer into the mass spectrometer, but neither restrictor temperature nor carbon dioxide mobile phase significantly affected negative ion CI conditions.

Anti-Bacterial Agents↗

Electron impact mass spectrometry of BHT and its alteration products.

The electron impact (EI) mass spectra of 2,6-di-tert-butyl-4-methylphenol (BHT) and certain of its alteration products are described in detail. Accurate mass measurements confirm the elemental compositions of important fragment ions in the EI spectra. Collisionally activated mass spectra are also used to study fragmentation and suggest common ion structures. The reference spectra provide the basis for identifying various alteration products of BHT by capillary gas chromatography/mass spectrometry (GC/MS) without the necessity of isolating individual components. Application of GC/MS is made to three studies: (i) pyrolysis of hydroperoxy-BHT as a potential pathway to alteration products in food; (ii) GC/MS pyrolysis of hydroperoxy-BHT as a model study; and (iii) alteration of BHT in ethanol/water as a food-simulating solvent.

Butylated Hydroxytoluene↗

Collisional activation mass spectra of M-. ions of azo dyes containing 2-naphthol.

Collisionally activated decomposition mass spectra of M-. ions of azo dyes are presented. The compounds are of general structure Ar(1)--N = N--Ar(2), where Ar(1) is substituted phenyl and Ar(2) is 2-naphthol. Characteristic fragment ions observed include m/z 157, which corresponds to the 2-naphthol substituent with cleavage of the--N = N--bond represented as [Ar(2)--N]-.. Ion of general structure [Ar(1)--NH]- are also observed. Parent ion scans of m/z 157 provide a potential screening technique for 2-naphthol-containing axo dyes. Specific results are reported for the chloroform extract of FD&C Red #8, and capillary gas chromatographic introduction is compared with direct exposure probe introduction for the identification of dyes.

Azo Compounds↗

Field desorption mass spectrometry of cyanogenic glycosides.

The field desorption mass spectra of several underivatized cyanogenic glycosides exhibit molecular ions or ions derived from the parent compound by protonation and alkali metal cationization. Abundant fragment ions are present and can be readily related to structure. Significant deviations from established fragmentation pathways are observed due to the nature of the aglycone. The ability to successfully determine the presence of cyanogenic glycosides by field desorption is demonstrated in crude extracts isolated from Vicia sativa, a food-contaminating plant material.

Crystallization↗

Headspace sampling and gas-solid chromatographic determination and confirmation of greater than or equal to 1 ppb vinyl chloride residues in polyvinyl chloride food packaging.

The determination and confirmation of residual vinyl chloride (VC) in polyvinyl chloride (PVC) food packaging materials are described. PVC packaging materials are dissolved in dimethylacetamide (DMAC). VC is sparged from solution with helium gas and collected in sealed vials of ethanol. VC is detected and quantitated by using a headspace sampling technique and standard gas-solid chromatography (GSC) with flame ionization detection. GSC peak heights of about 5% full scale deflection are obtained for samples of PVC containing 1 ppb VC. Polymer samples taken from tubing, blood bags, food packaging films, bottles, and unprocessed resin were analyzed. Residual VC levels ranged from 0.3 to 913 ppb. VC was confirmed by GSC-mass spectrometry, using selected ion recording of m/z 62 and 64 in conjunction with full mass scans to identify components eluting near VC.

Chromatography, Gas↗

Use of mass spectrometry for confirmation of animal drug residues.

Mass spectrometry is a technique capable of providing unambiguous confirmation of drug residues in edible tissues at trace levels. This has led to an increase in the number of new animal drug applications containing a mass spectrometry procedure as the confirmatory test. Written guidelines do not exist to cover the requirements to be met for acceptance of these procedures. The legal, analytical, and practical requirements to be considered in developing and submitting these procedures will be presented on current requirements and past experiences.

Animals↗

Field desorption mass spectrometry of mycotoxins and mycotoxin mixtures, and its application as a screening technique for foodstuffs.

The field desorption mass spectra of a variety of mycotoxins have been studied. These include the 4 aflatoxins B1, B2, G1, and G2, rubratoxin B, T-2 toxin, and zearalenone, as well as mixtures of these mycotoxins. The spectra of all of the mycotoxins exhibited molecular ions [M]+. Under the conditions employed, only rubratoxin B exhibited major fragmentation. The field desorption technique has been applied to the analysis of both spiked and naturally contaminated extracts of foodstuffs. The potential of the method as an analytical screening technique for the presence of mycotoxins has been evaluated.

Aflatoxins↗

Determination of vinylidene chloride in Saran films by electron capture gas-solid chromatography and confirmation by mass spectrometry.

A method is presented for determining vinylidene chloride (VdC) in Saran food packaging films by using electron capture gas-solid chromatography. The VdC present was confirmed by combined gas-solid chromatography-mass spectrometry, employing selected ion recording. The method is capable of detecting larger than or equal to 5 ppm VdC in films. Production lots of Saran film were analyzed and found to contain 6-30 ppm VdC.

Chromatography, Gas↗