PubMed Health⌕ Search

Biomedical subjects

M P Yurawecz

Publications and source records attributed to M P Yurawecz.

31 records · Page 2Linked to original sources

Furan fatty acids determined as oxidation products of conjugated octadecadienoic acid.

The objective of this study was to identify oxidation products of conjugated linoleic acid (CLA), a series of octadecadienoic acids with conjugated double bonds, which have been reported to have antioxidant and anticarcinogenic properties. Reference materials of CLA were oxidized in different concentrations of water/methanol; for example, 0.5 g octadecadienoic acid was dissolved in 50 mL methanol, and 100 mL water was added; this suspension was heated at 50 degrees C and continuously aerated. Aliquots of 5 mL were taken over time, extracted with ether, treated with diazomethane and examined by gas chromatography/mass spectrometry and/or gas chromatography with flame-ionization detection. Products identified included the following furan fatty acids (FFAs): 8,11-epoxy-8,10-octadecadienoic; 9,12-epoxy-9,11-octadecadienoic; 10,13-epoxy-10,12-octadecadienoic; and 11,14-epoxy-11,13-octadecadienoic. Conjugated dienes should be considered as a possible source of FFAs, and CLA may have products common to furans in their overall oxidative scheme.

Anticarcinogenic Agents↗

Rapid determination of double bond configuration and position along the hydrocarbon chain in cyclic fatty acid monomers.

This study reports the structural elucidation of diunsaturated 5- or 6-membered ring cyclic fatty acid monomers (CFAM) isolated from heated flaxseed oil by complementary gas chromatography (GC)-mass spectrometry (MS) and GC-matrix isolation-Fourier transform infrared spectroscopy (MI-FTIR). Infrared measurements of CFAM were carried out on methyl ester derivatives as well-resolved chromatograms were obtained on a polar 100% cyanopropyl polysiloxane capillary GC column. By contrast, electron ionization MS of methyl ester derivatives was of limited value because of double bond migration during the ionization process in the mass spectrometer. This communication reports definitive MS fragmentation patterns that can confirm ring position and double bond position along the fatty acid chain in 1,2-disubstituted CFAM determined as 2-alkenyl-4,4-dimethyl-oxazoline derivatives. Double bond configuration (cis, trans, or conjugated cis,cis) in CFAM was confirmed by GC-MI-FTIR. The presence of CFAM, degradation products found in used frying oils, is a potential source of dietary toxicity.

Fatty Acids, Unsaturated↗

Identification of chlorinated nitrobenzene residues in Mississippi River fish.

Residues of lower chlorinated nitrobenzenes have been found at levels up to about 1 ppm in 8 samples of Mississippi River fish. Electron capture gas chromatography (EC/GC) was used for determination after extraction and cleanup using a procedure based on the AOAC multiresidue method for organochlorine and organophosphorus pesticides in nonfatty foods. The residues found included 2-, 3-, and 4-chloronitrobenzene and 2,3- and 3,4-dichloronitrobenzene; identity was confirmed by GC/mass spectrometry. GC retention times for 15 monochloro-through pentachloro-substituted nitrobenzene congeners were determined with OV-101 and mixed OV-101 + OV-210 columns at 130 degrees C. In studies of the nonfatty food extraction and cleanup procedures of the AOAC method, recoveries of 15 chlorinated nitrobenzenes from spiked fish samples ranged from 68 to 116%. GC of cleaned up fish extract aliquots equivalent to 20 mg sample allowed quantitation of individual congeners at levels of about 0.025 and 0.005 ppm with 3H and 63Ni EC detectors, respectively. The contamination of Mississippi River fish with chlorinated nitrobenzenes appears to be localized in a 150 mile section of the river extending from St. Louis, MO, to Cape Girardeau, MO; no chlorinated nitrobenzenes (less than 0.005 ppm) were detected in Mississippi River fish caught above or below this region of the river or in fish from the lower Missouri River, which joins the Mississippi River near St. Louis.

Animals↗

Gas-liquid chromatographic and mass spectrometric indentification of chlorinated trifluorotoluene residues in Niagara River fish.

Several unknown halogenated compounds were detected in Niagara River fish using a method similar to the AOAC multiresidue method for chlorinated pesticides in high-moisture foods. From gas-liquid chromatographic-mass spectrometric (GLC/MS) data and GLC retention times on 3 columns, 7 of the compounds were identified as 4-chloro-alpha,alpha,alpha-trifluorotoluene (0.17--2.0 ppm), 2-chloro-alpha,alpha,alpha-trifluorotoluene (0.002--0.1 ppm), 3,4-dichloro-alpha,alpha,alpha-trifluorotoluene (0.02--0.28 ppm), 2,4-dichloro-alpha,alpha-alpha-trifluorotoluene (0.02--0.17) ppm), 2,3-dichloro-alpha,alpha,alpha-trifluorotoluene (trace-0.005 ppm), 2,6-dichlorotoluene (not quantitated), and 2,4,5-trichlorotoluene (0.31 ppm was found in the only sample quantitated). Other isomers of tri- and tetrachloro-alpha,alpha,alpha-trifluorotoluene and di-,tri-, and tetrachlorotoluene were also present in these samples. Recoveries of the specific chlorinated trifluorotoluenes identified in these samples ranged from 86 to 108%.

Animals↗

Gas-liquid chromatographic determination of chlorinated norbornene derivatives in fish.

1,2,3,4,7,7-Hexachloro-2,5-norbornadiene (I), 1,2,3,4,5-endo,7,7-heptachloro-2-norbornene (II), and 1,2,3,4,7,7-hexachloro-5,6-endo-epoxy-2-norbornene (III) have been identified as contaminants in Mississippi River fish by combined gas-liquid chromatography (GLC)-mass spectrometry. The method used to determine residues of these compounds, which are associated with production of the pesticide endrin, is similar to the AOAC multiresidue method for chlorinated pesticides. The residues are extracted from the sample with acetonitrile, transferred to petroleum ether, and chromatographed on a Florisil column. Compounds I and II are eluted from the Florisil with petroleum ether and compound III is eluted with ethyl ether-petroleum ether (6 + 94). The concentrated eluates are analyzed by using electron capture GLC. The method provides adequate recoveries of all 3 chlorinated norbornene derivatives and allows quantitation at or below the 0.05 ppm level in fish with a 20 mg sample equivalent injection.

Animals↗

Determination of hexachloro-1,3-butadiene in spinach, eggs, fish, and milk by electron capture gas-liquid chromatography.

Hexachloro-1,3-butadiene (HCBD), a waste product formed in the manufacture of perchloroethylene and trichloroethylene, has been found in fish from the lower Mississippi River basin. The AOAC official method for organochlorine pesticide residues in fatty and nonfatty foods has been modified for the determination of HCBD residues in selected food commodities. Acetonitrile extracts of nonfatty foods, or the combined acetonitrile extracts obtained in acetonitrile-petroleum ether partitioning of fat isolated from fatty foods, are diluted with water and extracted with petroleum ether. The petroleum ether extracts are chromatographed on Florisil and HCBD is eluted with petroleum ether. The elute is analyzed by gas-liquid chromatography with an electron capture detector. Average recoveries of HCBD from fortified samples of fatty and nonfatty foods were greater than 90% in the interlaboratory trials of the method.

Animals↗

Fats and oils.

Explore the source record for details and available documents.

Animals↗

2-chloroethyl fatty acid esters as indicators of 2-chloroethanol in black walnuts, seasoning mixes, and spices.

Residues of 2-chloroethyl fatty acid esters (CEEs) and 2-chloroethanol (ECH), by-products of ethylene oxide fumigation, were determined in black walnuts, seasoning mixes, and spices. Extracts containing ECH and CEE were cleaned up by previously described procedures, and residue levels were quantitatively determined using a gas chromatograph equipped with a halogen-selective electrolytic conductivity detector. All food products that contained CEE residues also contained ECH. ECH residues ranged from less than 0.2 to 880 ppm and were less than 0.2-7 times the CEE levels found.

Chlorohydrins↗

Identification of O,O-dialkyl-S-methylphosphorodithioate residues in fish.

O,O-Dialkyl-S-methylphosphorodithioates were found in Mississippi River buffalo fish caught near several chemical plants and oil refineries in Hartford and Wood River, IL. These chemicals, which have not been previously recognized as environmental or food contaminants, were identified and quantitated by a procedure similar to the AOAC multiresidue method for organochlorine and organophosphorus pesticides, using gas chromatography (GC) with flame photometric detection (FPD). The key to their identification was a GC/FPD retention time pattern that was virtually the same as that for the diazomethane reaction products of a commercial zinc dialkyl dithiophosphate motor oil additive. GC/mass spectrometry (MS) showed that the compound producing the largest GC/FPD peak contained butoxy groups. The identification of this compound as O,O-di(2-methylpropyl)-S-methyl-phosphorodithioate (Compound C) was confirmed by GC/MS analysis by comparison with the authentic material. The buffalo fish contained 0.15 ppm Compound C and 0.5 ppm total O,O-dialkyl-S-methylphosphorodithioates. Subsequent analyses of fish from other areas showed that these contaminants were not limited to the Hartford-Wood River area. Lower residue levels of Compound C, ranging from 0.01 to 0.05 ppm, were found in fish from the Mississippi River at Sauget, IL, and from the Delaware River and Newark Bay in NJ.

Animals↗

Identification of cis- and trans-1,1,2,3,4-pentachloro-4-[1-methylethoxy]-1,3-butadiene residues in Mississippi River fish.

The cis- and trans-isomers of 1,1,2,3,4-pentachloro-4-[1-methylethoxy]-1,3-butadiene have been identified as contaminants in fish caught from the Mississippi River at St. Louis, MO, and as far as 150 miles south of that location. Up to 0.1 ppm of the cis-isomer and 0.8 ppm of the trans-isomer were determined by using a method based on the AOAC multiresidue method for detecting organochlorine and organophosphorus pesticides. In tests of the modified AOAC method on spiked fish, both isomers were quantitatively recovered (95-106%). A mixture of the cis- and trans-isomers was synthesized by reacting hexachlorobutadiene with sodium isopropoxide. Separation of the reaction products by Florisil column chromatography provided reference standards of the individual isomers for identification and quantitation of the residues. The stereospecificity of the synthesis reaction and the infrared and mass spectral data used to verify the structures of the products are discussed.

Animals↗

Gas chromatographic determination of electron capture sensitive volatile industrial chemical residues in foods, using AOAC pesticide multiresidue extraction and cleanup procedures.

Electron capture (EC) gas chromatographic (GC) parameters have been developed for determining some of the more volatile industrial chemicals that can be determined by the AOAC multiresidue method for organochlorine and organophosphorus pesticides with modified GC operating conditions. Retention times relative to pentachlorobenzene are reported for 143 industrial chemicals, pesticides, and related compounds on OV-101 GC columns at 130 degrees C. Also reported for most of the compounds are recoveries from fortified samples carried through the AOAC extraction and cleanup procedures for fatty and/or nonfatty foods, Florisil elution characteristics, and GC relative retention times on mixed OV-101 + OV-210 columns at 130 degrees C. Our laboratory has used the modified EC/GC parameters with the AOAC multiresidue extraction/cleanup procedures to determine many volatile halogenated industrial chemical contaminants in foods, chiefly in samples of fresh-water fish. Other modifications of the AOAC method are described to improve the tentative identification and quantitative measurement of these volatile residues.

Animals↗