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PubMed2004

Storage of substrate mixtures by activated sludges under dynamic conditions in anoxic or aerobic environments.

In spite of the fact that in most activated sludge plants substrate complex mixtures are removed under alternating anoxic and aerobic conditions, most studies on the dynamic response of biomass are limited to feeding a single substrate (acetate or glucose) under a single redox condition (aerobic or anoxic). In this study, the dynamic response of biomass in a sequencing batch reactor is described in terms of substrate removal and related storage as internal polymers, as functions of single or simultaneous feed of several substrates (acetate, glucose, glutamic acid and ethanol) and of anoxic vs. aerobic conditions. Under anoxic conditions, the four substrates were simultaneously removed at a significantly greater nitrate removal rate than when single substrates were present, so showing that the simultaneous removal was partially due to independent metabolic activities. On the other hand, the removal of every substrate was affected (positively or negatively) by the presence of the others, demonstrating that the substrates can be also used by the same metabolism. As an exception, acetate removal was not affected by the presence of other substrates. As for the comparison of aerobic and anoxic conditions, the acetate uptake rate almost doubled moving from anoxic to aerobic conditions, whereas other substrates were only slightly affected. This difference was probably due to the additional presence of aerobic denitrification, which was much more important for acetate. This also confirmed that acetate removal was independent from other substrates. In all cases, storage was the main mechanism of solids formation, so confirming the general importance of such phenomenon under dynamic conditions, independently from feed complexity and redox conditions.

Acetates↗
PubMed1996

Application of a self-modeling curve resolution approach to the study of solvent effects on the acid-base and copper (II)-complexing behavior of polyuridylic acid.

The solvent effect on the acid-base and complexation behavior of the homopolynucleotide polyuridylic acid (poly(U)) has been studied by means of potentiometric and spectrometric titrations (circular dichroism and UV-VIS) in water and in 30 and 50% (v/v) dioxane-water media. The potentiometric studies revealed the absence of polyelectrolytic effects in the acid-base equilibrium, and the spectrometric experiments detected only a random coil conformation associated with both the protonated and deprotonated species. The common behavior observed in the three media seems to indicate the weakness of both intramolecular interactions, i.e., base stacking, and solute/solvent interactions, i.e., hydrogen-bonding, and consequently their small effect during the protonation process. Differences regarding the solubility of the deprotonated species in the solvents used are due to the difficult stabilization of such a charged species in the low polar environment of the dioxane-water mixtures. Complexation has been exhaustively studied in aqueous media, and no conformational changes have been noticed in the only copper(II)-poly(U) complex detected. The inclusion of the copper(II) ion in the macromolecular skeleton of the polynucleotide does not contribute to an ordination of the structure, which remains as a random coil. No comparison between this equilibrium in aqueous solution and in the hydroorganic mixtures could be carried out since the limited pH range of the soluble complex in those solvent mixtures prevented a rigorous quantitative monitoring of such a chemical process.

Acids↗
PubMed1990

DNA adduct formation in human and mouse skin by mixtures of polycyclic aromatic hydrocarbons.

32P-Postlabelling analysis has been used to detect the formation in vivo of DNA adducts by components of complex mixtures of polycyclic aromatic hydrocarbons (PAHs) in coal-tar, creosote, bitumen, juniper tar, used engine oils and fuel exhaust condensates. The presence of DNA adducts derived from these agents has been investigated in mouse skin, in human skin explants maintained in short-term organ culture and in human skin in vivo, and the formation of many different PAH-DNA adducts was observed. Similar levels and patterns of adducts were found in DNA from human skin to those in mouse skin, which is known to be susceptible to the carcinogenic activity of PAH mixtures, thus demonstrating the potential hazard to man of epidermal contact with these materials.

Animals↗
PubMed1998

Electrospray ionization mass spectrometry of metalloporphyrins.

The magnesium, nickel, copper, zinc and vanadium metalloporphyrins from octaethylporphyrin, etioporphyrin I and tetraphenylporphyrin were characterized using electrospray ionization mass spectrometry (ESI-MS). The ion abundance of each of the porphyrins present in binary mixtures was monitored as a function of the porphyrin concentration and is dependent on the metalloporphyrin oxidation potential. It was found that, for binary mixtures of metalloporphyrins whose oxidation potentials differ by less than 0.1 V, the resulting ion abundance of each species is directly proportional to the concentration of each analyte in the mixture. For binary mixtures whose oxidation potentials differ by more than 0.1 V, relative abundances of the radical cations of each metalloporphyrin are determined by the oxidation potential and concentration of each metalloporphyrin with the analyte of lowest oxidation potential being ionized preferentially. The ability to ionize selectively one porphyrin over another in a binary mixture offers the potential to use ESI-MS for the qualitative analysis of porphyrins present in complex mixtures.

Electrochemistry↗
PubMed2000

Sequencing of peach latent mosaic viroid variants from nine North American peach cultivars shows that this RNA folds into a complex secondary structure.

We sequenced 34 new peach latent mosaic viroid (PLMVd) variants isolated from nine different peach cultivars. This study provides the widest view of PLMVd diversity reported to date and includes the original characterization of North American variants, which cannot be differentiated from European sequences. PLMVd appears as a species in which each isolate is a complex mixture of RNAs. Analysis of base-pair covariations supports the hypothesis that PLMVd folds into a complex branched structure with the potential of including three new pseudoknots. The resulting "globular-like" structure is in contrast to the rod-like one adopted by most other viroids.

Base Sequence↗
PubMed1997

Oxidation reactions of acetylenic fatty esters with selenium dioxide/tert-butyl hydroperoxide.

Reaction of methyl undec-10-ynoate (1) with selenium dioxide/tert-butyl hydroperoxide (TBHP) in aqueous dioxane gave methyl 9-oxo-undec-10-ynoate (2, 9%) and 9-hydroxy-undec-10-ynoate (3, 60%), while methyl octadec-9-ynoate (4) yielded mixtures of positional isomers of mono-keto (viz. methyl 8-oxo- and 11-oxo-octadec-9-ynoate, 5, 5%), hydroxy-keto (viz. methyl 8-hydroxy-11-oxo- and 11-hydroxy-8-oxo-octadec-9-ynoate, 6, 10%), and dihydroxy (viz. methyl 8,11-dihydroxy-octadec-9-ynoate, 7, 24%) derivatives. Similar treatment of a conjugated diacetylenic fatty ester (methyl octadeca-6,8-diynoate, 8) furnished a mixture of methyl 5-oxo- and 10-oxo-octadeca-6,8-diynoate (9, 12%) and a complex mixture of very polar products. Reaction of methyl octadec-11E-en-9-ynoate (methyl santalbate) (10) with selenium dioxide/TBHP in aqueous dioxane gave exclusively a mixture of regiospecific products, viz. methyl 8-oxo-octadec-11(E)Z-en-9-ynoate (11, 6%) and methyl 8-hydroxy-octadec-11E-en-9-ynoate (12, 70%). The structures of the various products were determined by a combination of spectroscopic and mass spectral analyses.

Fatty Acids↗
PubMed2006

Volumetric interpretation of protein adsorption: competition from mixtures and the Vroman effect.

A Vroman-like exchange of different proteins adsorbing from a concentrated mixture to the same hydrophobic adsorbent surface is shown to arise naturally from the selective pressure imposed by a fixed interfacial-concentration capacity (w/v, mg/mL) for which protein molecules compete. A size (molecular weight, MW) discrimination results because fewer large proteins are required to accumulate an interfacial w/v concentration equal to smaller proteins. Hence, the surface region becomes dominated by smaller proteins on a number-or-mole basis through a purely physical process that is essentially unrelated to protein biochemistry. Under certain conditions, this size discrimination can be amplified by the natural variation in protein-adsorption avidity (quantified by partition coefficients P) because smaller proteins (MW<50 kDa) have been found to exhibit characteristically higher P than larger proteins (MW<50 kDa). The standard depletion method is implemented to measure protein-adsorption competition between two different test proteins (i and j) for the same hydrophobic octyl sepharose adsorbent particles. SDS-gel electrophoresis is used as a multiplexing, separation-and-quantification tool for this purpose. Identical results obtained using sequential and simultaneous competition of human immunoglobulin G (IgG, protein j) with human serum albumin (HSA, protein i) demonstrates that HSA was not irreversibly adsorbed to octyl sepharose over a broad range of competing solution concentrations. A clearly observed exchange of HSA for IgG or fibrinogen (Fib) shows that adsorption of different proteins (i competing with j) to the same hydrophobic surface is coupled whereas adsorption among identical proteins (i or j adsorbing from purified solution) is not coupled. Interpretive theory shows that this adsorption coupling is due to competition for the fixed surface capacity. Theory is extended to hypothetical ternary mixtures using a computational experiment that illustrates the profound impact size-discrimination has on adsorption from complex mixtures such as blood.

Adsorption↗
PubMed2003

In situ biodegradation determined by carbon isotope fractionation of aromatic hydrocarbons in an anaerobic landfill leachate plume (Vejen, Denmark).

Concentrations and isotopic compositions (13C/12C) of aromatic hydrocarbons were determined in eight samples obtained from the strongly anoxic part of the leachate plume downgradient from the Vejen Landfill (Denmark), where methanogenic, sulfate-reducing and iron-reducing conditions were observed. Despite the heterogeneous distribution of the compounds in the plume, the isotope fractionation proved that ethylbenzene and m/p-xylene were subject to significant biodegradation within the strongly anoxic plume. The isotope fractionation factors (alphaC) for the degradation of the m/p-xylene (1.0015) and ethylbenzene (1.0021) obtained from the field observations were similar to factors previously determined for the anaerobic degradation of toluene and o-xylene in laboratory experiments, and suggest that in situ biodegradation is one major process controlling the fate of these contaminants in this aquifer. The isotope fractionation determined for 1,2,4-trimethylbenzene and 2-ethyltoluene suggested in situ biodegradation; however, the isotopic composition did not correlate well with the respective concentration as expressed by the Rayleigh equation. Some other compounds (1,2,3-trimethylbenzene, o-xylene, naphthalene and fenchone) did not show significant enrichments in delta13C values along the flow path. The compound concentrations were too low for accurate isotope analyses of benzene, toluene, 1- and 2-methylnaphthalene, while interferences in the chromatography made it impossible to evaluate the isotopic composition for 4-ethyltoluene, 1,3,5-trimethylbenzene and camphor. In addition to demonstrating the potential of assessing isotopic fractionation as a means for documenting the in situ biodegradation of complex mixtures of aromatic hydrocarbons in leachate plumes, this study also illustrates the difficulties for data interpretation in complex plumes and high analytical uncertainties for isotope analysis of organic compounds in low concentration ranges.

Bacteria, Anaerobic↗
PubMedDate not supplied

Strategies for toxicological evaluation of mixtures.

Different strategies for the toxicological evaluation of mixtures are presented. The purpose is to determine the effects of each component (variable) in the mixture, and possible interactions between variables. The examples presented have 3-5 predictor variables and 1-3 responses, and are based on statistical experimental design, multivariate data analysis and modelling. The following examples are presented: (1) inhalation experiments with synthetic vapour mixtures of hydrocarbons formulated by means of mixture design at different vapour concentrations (the experimental) region covers both partial and complete evaporation of the liquid mixtures); (2) combination of refinery streams for fuel blending by means of mixture design with constraints, followed by engine tests and determination of exhaust particles; (3) fractionation of organic extracts of diesel exhaust particles, and recombination of the extracts by means of mixture design, followed by mutagenicity testing of the recombined extracts in the Ames Salmonella assay; (4) spiking complex mixtures with individual compounds using factorial design, and subsequent mutagenicity testing. The data obtained from these four examples were analysed by means of Projections to Latent Structures (PLS). The effects of each variable and possible interactions, were quantified by means of PLS regression coefficients. Furthermore, the empirical models obtained were evaluated by means of correlation coefficients, cross validation and predictions.

Administration, Inhalation↗
PubMed2000

"IARC group 2A Carcinogens" reported in cigarette mainstream smoke.

As a follow-up to an earlier study on IARC Group I compounds, further efforts have been made to evaluate the international literature on cigarette mainstream smoke for reports on constituents classified as IARC "Group 2A: probably carcinogenic to humans" and IARC "Group 2B: possibly carcinogenic to humans." IARC classifies 59 agents, mixtures and exposures as Group 2A. Of the overall list of 59, 50 represent chemical entities or complex mixtures ( [IARC,] ). When only chemical entities which have their origin from cigarette components (tobacco and paper) are considered, further searching of the international literature has revealed that nine chemical compounds of the 50 Group 2A listings have been reported in cigarette mainstream smoke ( Table 1 ). In micrograms/cigarette (mug/cig), the ranges reported for each of the nine compounds are as follows: formaldehyde (3.4-283); benzo[a]pyrene (B[a]P) (0.004-0. 108); dibenz[a,h]anthracene (DB[a,h]A) (0.004-0.076); N-nitrosodiethylamine (DEN) (non-detectable-0.0076); benz[a]anthracene (B[a]A) (trace-0.08); N-nitrosodimethylamine (DMN) (non-detectable-0.7-1.62); acrylamide (1.1-2.34); 1,3-butadiene (16-77); and 2-amino-3-methyl-3H-imidazo[4,5-f]quinoline (IQ) (0. 00026-0.00049).

Animals↗
PubMed2004

Development of a physiologically based pharmacokinetic model for volatile fractions of gasoline using chemical lumping analysis.

Physiologically based pharmacokinetic (PBPK) models have often been used to describe the absorption, distribution, metabolism, and excretion of chemicals in animals but have been limited to single chemicals and simple mixtures due to the numerous parameters required in the models. To overcome the barrier to modeling more complex mixtures, we used a chemical lumping approach, used in the past in chemical engineering but not in pharmacokinetic modeling, in a rat PBPK model for gasoline hydrocarbons. Our previous gasoline model consisted of five individual components (benzene, toluene, ethylbenzene, xylene, and hexane) and a lumped chemical that included all remaining components of whole gasoline. Despite being comprised of hundreds of components, the lumped component could be described using a single set of chemical parameters that depended on the blend of gasoline. In the present study, we extend this approach to evaporative fractions of gasoline. The PBPK model described the pharmacokinetics of all of the volatility-weighted fractions of gasoline when differences in partitioning and metabolism between fractions were taken into account. Adjusting the ventilation rate parameter to account for respiratory depression at high exposures also allowed a much improved description of the data. At high exposure levels, gasoline components competitively inhibit each other's metabolism, and the model successfully accounted for binary interactions of this type, including between the lumped component and the five other chemicals. The model serves as a first example of how the engineering concept of chemical lumping can be used in pharmacokinetics.

Adsorption↗
PubMed2005

Bronchial hyperreactivity and other inhalation lung injuries in rescue/recovery workers after the World Trade Center collapse.

BACKGROUND: The collapse of the World Trade Center (WTC) on September 11, 2001 created a large-scale disaster site in a dense urban environment. In the days and months thereafter, thousands of rescue/recovery workers, volunteers, and residents were exposed to a complex mixture of airborne pollutants. METHODS: We review current knowledge of aerodigestive inhalation lung injuries resulting from this complex exposure and present new data on the persistence of nonspecific bronchial hyperreactivity (methacholine PC20 < or =8 mg/mL) in a representative sample of 179 Fire Department of the City of New York (FDNY) rescue workers stratified by exposure intensity (according to arrival time) who underwent challenge testing at 1, 3, 6, and 12 months post-collapse. RESULTS: Aerodigestive tract inflammatory injuries, such as declines in pulmonary function, reactive airways dysfunction syndrome (RADS), asthma, reactive upper airways dysfunction syndrome (RUDS), gastroesophageal reflux disease (GERD), and rare cases of inflammatory pulmonary parenchymal diseases, have been documented in WTC rescue/recovery workers and volunteers. In FDNY rescue workers, we found persistent hyperreactivity associated with exposure intensity, independent of airflow obstruction. One year post-collapse, 23% of highly exposed subjects were hyperreactive as compared with only 11% of moderately exposed and 4% of controls. At 1 yr, 16% met the criteria for RADS. CONCLUSIONS: While it is too early to ascertain all of the long-term effects of WTC exposures, continued medical monitoring and treatment is needed to help those exposed and to improve our prevention, diagnosis, and treatment protocols for future disasters.

Air Pollutants↗
PubMed1992

Alternative multimeric structures affect myogenin DNA binding activity.

The native molecular weight of the basic helix-loop-helix (bHLH) proteins myogenin, MyoD, and E12 was calculated from their mobilities on sucrose gradients and molecular sieve chromatography. The muscle bHLH proteins associate to form a variety of higher order complexes, most of which are larger than dimers. Homodimers bind to DNA sequences such as the MEF-1 site in the creatine kinase enhancer whereas homotetramers and larger forms do not recognize this DNA sequence. The ubiquitous bHLH protein E12 forms monomers or homodimers with little evidence for higher order complexes. Mixtures of myogenin and E12 show some heterodimeric structures, but most of the myogenin remains in large complexes. This result using purified proteins is also obtained in nuclear extracts from differentiated myotubes, in which most of the myogenin is present in large complexes that do not bind to the creatine kinase enhancer. A fusion protein containing only the myogenin HLH region forms large homomeric complexes. A model is presented in which each helix associates with a different subunit to form chains or ring structures to explain these observations. The partition of myogenin in nuclear extracts into dimers that recognize known DNA sequences and higher order complexes that do not raises important new issues concerning the regulation of skeletal muscle bHLH protein activity during myogenesis.

Animals↗
PubMed1990

Binding of recombinant interleukin-1 beta to the third complement component and alpha 2-macroglobulin after activation of serum by immune complexes.

Activation of human normal serum with tetanus/antitetanus immune complexes (TAT-IC) resulted in increased binding of 125I-labeled interleukin-1 beta (IL-1 beta) to serum factors, as opposed to untreated serum. Sodium dodecyl sulfate-polyacrylamide gel electrophoresis (SDS-PAGE) followed by autoradiography showed labeling of two large molecular mass factors of an apparent molecular weight (Mr) of 200,000 and 400,000, respectively. These complexes could be dissociated by reduction. No complexes were formed when reducing compounds were added to serum-TAT-IC-125I-IL-1 beta mixtures. Complex formation was largely prevented by alkylating compounds. Molecular sieve chromatography of TAT-IC-activated serum confirmed that 125I-IL-1 beta became bound to high Mr serum proteins. Fractions containing high molecular 125I-IL-1 serum protein complexes partially retained IL-1-like activity since they induced proliferation of an IL-1-dependent murine T helper (D10G4) cell lineage. The 125I-IL-1 beta binding factors could be immunoprecipitated from TAT-IC-activated serum 125I-IL-1 beta solutions by antisera to alpha 2-macroglobulin (alpha 2M) or to the third complement component (C3). SDS-PAGE of the immunoprecipitates showed radioactive bands corresponding to the expected Mr resulting from complex formation between 125I-IL-1 beta and these two proteins. Treatment of purified plasma alpha 2M and C3 with trypsin or activation with methylamine, which causes cleavage of the internal thiol ester and the appearance of free thiol groups in these proteins, mediated binding of 125I-IL-1 beta to alpha 2M and C3b. The results suggest that cleavage of the internal thiol ester in C3 and alpha 2M makes these plasma proteins susceptible to binding of 125I-IL-1 beta and that free thiol groups do play a role in the formation of 125I-IL-1 beta plasma protein complexes. Activated C3 and alpha 2M may function as IL-1 beta carrier proteins in biologic fluids, in addition to their other physiologic roles.

Antigen-Antibody Complex↗
PubMed1992

Comparative toxicity of four chlorinated dibenzo-p-dioxins (CDDs) and their mixture. Part I: Acute toxicity and toxic equivalency factors (TEFs).

There is presently no scientifically proven method to assess the toxicity of environmental samples containing complex mixtures of chlorinated dibenzo-p-dioxins (CDDs) of known composition. Their risk assessment is currently based on the interim concept of toxicity equivalency factors (TEFs), with the unproven assumption that all interactions of CDDs are additive. To address this problem we conducted acute toxicity studies with four different CDDs, viz 2,3,7,8-tetrachlorodibenzo-p-dioxin (tetra-CDD), 1,2,3,7,8-pentachlorodibenzo-p-dioxin (penta-CDD), 1,2,3,4,7,8-hexachlorodibenzo-p-dioxin (hexa-CDD) and 1,2,3,4,6,7,8-heptachlorodibenzo-p-dioxin (hepta-CDD), all containing chlorine substituents in the crucial 2,3,7,8-positions. The homologues, dissolved in corn oil/acetone, were administered to groups of five male Sprague Dawley rats at several doses (at least three) by gastric intubation. The obtained mortality data were employed to calculate the LD20,50 and 80 for each homologue. These data were subsequently used to prepare equipotent doses (expected mortality of 20, 50 and 80%) of a mixture containing all four homologues, each of them contributing one fourth of the toxicity, under the assumption of additive toxicity. The obtained LD50 value and (TEF) was for tetra-CDD 43 micrograms/kg (1), penta-CDD 206 micrograms/kg (0.2) hexa-CDD 887 micrograms/kg (0.05) and hepta-CDD 6325 micrograms/kg (0.007), respectively. The dose-response to the mixture confirmed the hypothesis of strict additivity in the acute toxicity of the four CDD homologues.

Animals↗
PubMed2003

Ozone-initiated reactions with mixtures of volatile organic compounds under simulated indoor conditions.

This study examines the primary and secondary products resulting from reactions initiated by adding ozone to complex mixtures of volatile organic compounds (VOC). The mixtures were representative of organic species typically found indoors, but the concentrations tended to be higher than normal indoor levels. Each 4-h experiment was conducted in a controlled environmental facility (CEF, 25 m3) ventilated at approximately 1.8 h(-1). The mixture investigated included 23 VOC (no O3), O3/23 VOC, O3/21 VOC (no d-limonene or alpha-pinene), and O3/terpene only (d-limonene and alpha-pinene). The net O3 concentration was approximately 40 ppb in each experiment, and the total organic concentration was 26 mg/m3 for the 23 VOC mixture, 25 mg/m3 for the 21 VOC mixture, and 1.7 mg/m3 for the d-limonene and alpha-pinene mixture. When the 23 VOC were added to the CEF containing no O3, no compounds other than those deliberately introduced were observed. When O3 was added to the CEF containing the 23 VOC mixture, both gas and condensed phase products were found, including aldehydes, organic acids, and submicron particles (140 microg/m3). When O3 was added to the CEF containing the 21 VOC without the two terpenes (O3/21 VOC condition), most of the products that were observed in the O3/23 VOC experiments were no longer present or present at much lower concentrations. Furthermore, the particle mass concentration was 2-7 microg/m3, indistinguishable from the background particle concentration level. When O3 was added to the CEF containing only two terpenes, the results were similar to those in the O3/23 VOC experiments, but the particle mass concentration (190 microg/m3) was higher. The results indicate that (i) O3 reacts with unsaturated alkenes under indoor conditions to generate submicron particles and other potentially irritating species, such as aldehydes and organic acids; (ii) the major chemical transformations that occurred under our experimental conditions were driven by O3/d-limonene and O3/alpha-pinene reactions; and (iii) the hydroxyl radicals (OH) that were generated from the O3/terpene reactions played an important role in the chemical transformations and were responsible for approximately 56-70% of the formaldehyde, almost all of the p-tolualdehyde, and 19-29% of the particle mass generated in these experiments.

Air Pollution, Indoor↗
PubMed2000

Minimal endocrine alterations in rodents after consumption of lake trout (Salvelinus namaycush).

Polychlorinated biphenyls (PCBs) and dioxins are known to cause disruptions in circulating hormone concentrations, which may influence fertility and normal fetal development. Structure activity relationships have been determined for individual congeners, but it is unclear what impacts occur due to exposure to complex mixtures of chemicals found in the environment. Most laboratory studies of PCB exposure have used commercial mixtures in high doses, which may not be representative of environmental concentrations of individual congeners, nor accurately represent complex interactions of multiple contaminants. The present study investigated endocrine alterations in rats associated with the consumption of lake trout collected from three specific locations in the Great Lakes. Composite fish samples were analyzed for PCBs, organochlorines, and mercury and ranged from 415 ppb to 1,275 ppb for individual contaminants. Fillet composites were fed to timed-pregnant Long-Evans rats as 30% of their diet. Concentrations of total thyroxine and estrogen were not significantly different in offspring of dosed dams from that of controls. However, aromatase activity was lowered in all dosed groups as compared with controls. This may represent a lowered expression of the CYP 19 gene in exposed rats or may be due to the presence of one or more substances in the contaminants that are capable of altering the affinity of the aromatase enzyme for its normal endogenous substrate. It is also possible that the number of maturing follicles in the lake trout-fed rats may be fewer than controls, which would result in an overall reduction in the enzyme activity. Data regarding the endocrine effects of environmental contaminant mixtures found in fish from the Great Lakes Basin are still controversial. Additionally, information is scarce with respect to the F1 generation of laboratory animals following environmental maternal exposures, therefore, we investigated the reproductive-endocrine alterations in rat offspring associated with the consumption of lake trout (Salvelinus namaycush) collected from three areas in the Great Lakes.

Animals↗
PubMed1989

Relative gas-liquid chromatographic retention factors of trimethylsilyl ethers of diradylglycerols on polar capillary columns.

Gas-liquid chromatography (GLC) on polar capillary columns provides a highly reproducible resolution and quantitation of molecular species of diradylglycerols when analyzed as the trimethylsilyl (TMS) ethers. In the absence of peak collection and determination of fatty acids or mass spectrometry, peak identification is obtained on the basis of relative retention times of reference standards or of relative retention times calculated from the additive contributions of component fatty chains. Unlike simple esters, complex mixtures of diradylglycerols present special problems in GLC peak identification, which must be attended to by auxiliary separations prior to GLC analysis. In the present study the positional sn-1,2(2,3)- and X-1,3-isomers were resolved by borate thin-layer chromatography (TLC) while the alkenylacyl-, alkylacyl- and diacylglycerols were separated as their TMS ethers by normal-phase high-performance liquid chromatography. The diradylglycerol nature of the sample was further verified by GLC determination of the carbon number distribution, which must be consistent with the composition of the fatty chains of the sample. Under these conditions the identification and quantitation of the molecular species on the polar capillary columns was always consistent with the total fatty acid composition of the sample, as well as with the fatty acid composition of any argentation TLC fractions isolated from some of the samples prior to the polar capillary GLC. Due to the great complexity of the natural diradylglycerol mixtures some peak overlaps occurred, which were reflected in their relative retention times. Nevertheless, a determination of diradylglycerol peak identity from relative retention times proved very satisfactory provided the above described procedures were employed.

Animals↗