RESUMEN
The use of a hyperthermal hydrogen induced cross-linking process to prepare laminates comprising polypropylene, poly(isobutylene-co-isoprene), and poly(vinyl acetate) is described. In this new, milder alternative to conventional plasma techniques, neutral molecular hydrogen projectiles were used to create carbon radicals on impacted surfaces by collision-induced dissociation of C-H bonds, and this process was used to cross-link polymers on a polypropylene surface. It was demonstrated that multiple layers of cross-linked materials could be added, creating polymer laminates with each layer introducing new functionalities and properties. In particular, the present work shows that the process is largely nondestructive toward ester functionalities. First, the esters were grafted to become nonleachable. Then, the esters were subsequently hydrolyzed to convert the surface from hydrophobic to hydrophilic. Afterward, the esters could be recovered by simple esterification demonstrating that further chemical transformations were possible.
Asunto(s)
Butadienos/química , Química Física , Ésteres/química , Hemiterpenos/química , Hidrógeno/química , Pentanos/química , Polienos/química , Polímeros/química , Polipropilenos/química , Polivinilos/química , Calor , Concentración de Iones de Hidrógeno , Interacciones Hidrofóbicas e Hidrofílicas , Microscopía de Fuerza Atómica , Espectroscopía de Fotoelectrones , Espectroscopía Infrarroja por Transformada de Fourier , Propiedades de SuperficieRESUMEN
The historical occurrence of Dechlorane Plus (DP) and detection of novel compounds structurally related to DP is described in a dated Lake Ontario sediment core. Our core was collected near the mouth of the Niagara River, which is known to be a major source of DP to the lake. Maximum DP concentrations (920 ng g(-1), dry weight) were observed between 1976 and 1980, the highest reported to date. Following that time, we observed a dramatic decrease in DP concentration which coincided with the enactment of United States federal and state laws to mitigate free release of chemicals into the Niagara River and installation of an industrial wastewater treatment facility. During the course of our research, four new substances structurally related to DP were also identified. These compounds were thought to arise from the Diels-Alder reactions resulting from impurities present in 1,5-cyclooctadiene, a feedstock used in production of DP. To confirm our hypothesis, Diels-Alder reactions were performed on the individual impurities. Using different stationary-phase capillary gas chromatography columns and high-resolution mass spectrometry, we were able to positively identify some of these novel compounds in the core. Interestingly, we also were able to identify a monoadduct compound, formed by addition of 1 mol of hexachlorocyclopentadiene to 2 mol of 1,3-cyclooctadiene, in lake trout. The concentration of this monoadduct was approximately 2 orders of magnitude greater than that of DP, suggesting that it is more bioaccumulative.
Asunto(s)
Retardadores de Llama/análisis , Agua Dulce/química , Sedimentos Geológicos/química , Hidrocarburos Clorados/química , Compuestos Policíclicos/química , Contaminantes Químicos del Agua/química , Animales , Canadá , Monitoreo del Ambiente , Great Lakes Region , Estructura Molecular , TruchaRESUMEN
Perfluorooctane sulfonate (PFOS) is a global contaminant and is currently among the most prominent contaminants in human blood and wildlife samples. Although "total PFOS" (SigmaPFOS) analytical methods continue to be the most commonly used for quantification, recent analytical method developments have made it possible to resolve the various isomers of PFOS by HPLC-MS/MS. Characterized technical PFOS standards (i.e., containing a mixture of PFOS isomers) are now available that enable isomer specific quantification of PFOS, however the advantages of such an analysis have notyet been examined systematically. Herein, PFOS isomers have been individually quantified for the first time in real samples and the results are compared to a traditional SigmaPFOS method; the influence of analytical standards and isomer specific electrospray and MS/ MS behavior were also investigated. The two human serum standard reference materials chosen for analysis contained dramaticallydifferent PFOS isomer profiles (approximately 30-50% total branched isomers) emphasizing that isomer patterns should not be ignored and may provide useful information on exposure sources (i.e., direct exposure to PFOS vs indirect exposure from PFOS-precursors). Depending on the sample and the particular MS/MS transition chosen for SigmaPFOS analysis (i.e., 499-->80 or 499-->99), SigmaPFOS concentrations may be over- or underestimated compared to the isomer specific analysis. Differences in the extent of in-source fragmentation and MS/MS dissociation contributed to the systematic analytical bias. It was also shown that SigmaPFOS data are prone to interlaboratory variation due to various choices of PFOS standards and instrumental conditions used. In the future, for either SigmaPFOS or isomer specific PFOS analyses, we suggest that accuracy can be maximized and interlaboratory discrepancies minimized by using a common chemically pure technical PFOS standard characterized by 19F NMR.
Asunto(s)
Ácidos Alcanesulfónicos/sangre , Fluorocarburos/sangre , Cromatografía Líquida de Alta Presión , Humanos , Isomerismo , Espectrometría de Masa por Ionización de ElectrosprayRESUMEN
Perfluorooctane sulfonate (PFOS) is the most prominent perfluoroalkyl substance found in the serum of humans and wildlife, yet the major routes by which exposure occurs are not clear. An important issue facing both the scientific and chemical regulatory communities is the extent to which PFOS concentrations in biota are attributable to direct exposure versus metabolism of PFOS-precursors (higher molecular weight derivatives that can be biotransformed to PFOS). Given that certain branched PFOS-precursors are chiral, we hypothesized that nonracemic proportions of PFOS isomers in biological samples could be used as a marker of significant exposure to PFOS-precursors. In this proof-of-principle study we examined the enantiomer-specific biotransformation of a high-purity model PFOS-precursor isomer: C(6)F(13)C*F(CF(3))SO(2)N(H)CH(2)(C(6)H(4))OCH(3) (named 1m-PreFOS hereafter, and whereby * indicates the chiral carbon center). A method for the enantiospecific separation of a compound with a long perfluoroalkyl chain and a chiral center was developed and applied to evaluate the enantioselectivity of 1m-PreFOS biotransformation in human liver microsomes. Gradient elution in reversed-phase mode on a Chiralpak IC column permitted the near-baseline separation of the two enantiomers (E1 and E2, nomenclature based on retention order) in 65 min. Microsome incubations demonstrated that E1 and E2 were metabolized at significantly different rates; k(E1) = 6.5(+/-0.3) x 10(-2) min(-1) (half-life = 10.6 min) and k(E2) = 5.2(+/-0.3) x 10(-2) min(-1) (half-life = 13.3 min), respectively. These results suggest that tracking of PFOS exposure sources by enantiomeric fractionation is feasible, and that new analytical methods for the enantioselective analysis of PFOS isomers in human and environmental samples should be developed.
Asunto(s)
Ácidos Alcanesulfónicos/química , Ácidos Alcanesulfónicos/metabolismo , Monitoreo del Ambiente/métodos , Fluorocarburos/química , Fluorocarburos/metabolismo , Ácidos Alcanesulfónicos/aislamiento & purificación , Biotransformación , Fluorocarburos/aislamiento & purificación , Humanos , Cinética , Microsomas Hepáticos/metabolismo , Reproducibilidad de los Resultados , Estereoisomerismo , Factores de TiempoRESUMEN
Fractions of methylated naphthenic acids (NAs) isolated from oil sands process-affected waterwere collected utilizing Kugelrohr distillation and analyzed by proton nuclear magnetic resonance (1H NMR) spectroscopy. 1H NMR analysis revealed that the ratio of methyl ester hydrogen atoms to remaining aliphatic hydrogen atoms increased from 0.130 to 0.214, from the lowest to the greatest molecular weight (MW) fractions, respectively, indicating that the carboxylic acid content increased with greater MW. Acute toxicity assays with exposure to monocarboxyl NA-like surrogates demonstrated that toxicity increased with increasing MW (D. magna LC50 values of 10 +/- 1.3 mM and 0.59 +/- 0.20 mM for the respective lowest and highest MW NA-like surrogates); however, with the addition of a second carboxylic acid moiety, the toxicity was significantly reduced (D. magna LC50 values of 10 +/- 1.3 mM and 27 +/- 2.2 mM forthe respective monocarboxyl and dicarboxyl NA-like surrogates of similar MW). Increased carboxylic acid content within NA structures of higher MW decreases hydrophobicity and, consequently, offers a plausible explanation as to why lower MW NAs in oil sands process-affected water are more toxic than the greater MW NAs.
Asunto(s)
Ácidos Carboxílicos/análisis , Aceites/química , Dióxido de Silicio/química , Pruebas de Toxicidad Aguda , Aliivibrio fischeri/efectos de los fármacos , Animales , Ácidos Carboxílicos/química , Ácidos Carboxílicos/toxicidad , Intervalos de Confianza , Daphnia/efectos de los fármacos , Ésteres , Mediciones Luminiscentes , Espectroscopía de Resonancia MagnéticaRESUMEN
The analytical conditions required to determine polybrominated diphenylethers (PBDEs) and a variety of other halogenated flame retardants (HFRs) by gas chromatography-high resolution mass spectrometry (HRMS) in environmental samples are reported. HRMS can be used to analyze brominated diphenylethers (BDEs), 2,2',4,4',5,5'-hexabromobiphenyl (BB-153) as well as for a number of other emerging HFRs like allyl 2,4,6-tribromophenyl ether (ATE), 2-bromoallyl 2,4,6-tribromophenyl ether (BATE), 2,3-dibromopropyl 2,4,6-tribromophenyl ether (DPTE), octabromotrimethylphenylindane (OBIND), pentabromoethylbenzene (PBEB), hexabromobenzene (HBB), 1,2-bis (2,4,6-tribromophenoxy) ethane (BTBPE), decabromodiphenylethane (DBDPE), Dechlorane Plus (DP), hexachlorocyclopentadienyl-dibromocyclooctane (HCDBCO), tetrabromoethylcyclohexane (TBECH), 1,2,5,6-tetrabromocylcooctane (TBCO), 2-ethylhexyl-2,3,4,5-tetrabromobenzoate (EHTeBB), and bis(2-ethly-1-hexyl)tetrabromophthalate (BEHTBP). The detection in environmental matrices and use of these non-BDE flame retardants is reviewed. A method for the analysis of PBDEs by isotope dilution HRMS and 16 other halogenated compounds primarily used as flame retardants is reported. A survey of selected environmental samples, which included Lake Ontario surface and tributary sediments, municipal wastewater effluent, sludge, and mussel tissues, detected PBDEs, DP, DBDPE, BTBPE, PBEB, BB-153, and HBB.
Asunto(s)
Monitoreo del Ambiente/métodos , Retardadores de Llama/análisis , Cromatografía de Gases y Espectrometría de Masas/métodos , Éteres Difenilos Halogenados/análisis , Bifenilos Polibrominados/análisis , Animales , Agua Dulce/química , Sedimentos Geológicos/química , Isótopos/química , Mytilus edulis/química , Ontario , Sensibilidad y Especificidad , Aguas del Alcantarillado/químicaRESUMEN
1,2,5,6-Tetrabromocyclooctane (TBCO) is a commercial brominated flame retardant that is employed mainly as an additive in textiles, paints and plastics. Very little is known about its presence or behavior in the environment or its analysis. TBCO can exist as two diastereomers, the stereochemistries of which have not been previously reported. We have named the first eluting isomer, under HPLC conditions, as alpha-TBCO (alpha-TBCO) and the later eluting isomer as beta-TBCO (beta-TBCO) when using an Acquity UPLC BEH C(18) column with methanol/acetonitrile/water as the mobile phase. The structural elucidation of these two isomers was accomplished by 1H NMR spectroscopy, GC/MS, LC/MS and X-ray structure determinations. alpha-TBCO is (1R,2R,5S,6S)-1,2,5,6-tetrabromocyclooctane and beta-TBCO is rac-(1R,2R,5R,6R)-1,2,5,6-tetrabromocyclooctane. As with some other brominated cycloaliphatic compounds, TBCO is thermally labile and the isomers easily interconvert. A thermal equilibrium mixture of alpha- and beta-TBCO consists of approximately 15% and 85% of these isomers, respectively. Separation of the two diastereomers, with minimal thermal interconversion between them, is achievable by careful selection of GC-capillary column length and injector temperature. LC/MS analyses of TBCO also presents an analytical challenge due to poor resolution of the isomers on chromatographic stationary phases, and weak intensity of molecular ions (or major fragment ions) when using LC-ESI/MS. Only bromide ions were seen in the mass spectra. APCI and APPI also failed to produce the molecular ion with sufficient intensity for identification.
Asunto(s)
Ciclooctanos/química , Retardadores de Llama/análisis , Hidrocarburos Bromados/química , Cromatografía Líquida de Alta Presión , Cristalografía por Rayos X , Ciclooctanos/análisis , Estabilidad de Medicamentos , Cromatografía de Gases y Espectrometría de Masas , Calor , Hidrocarburos Bromados/análisis , Isomerismo , Espectroscopía de Resonancia MagnéticaRESUMEN
BACKGROUND: Reported incidences of prostate cancer and masculinization of animals indicate a release of compounds with androgenic properties into the environment. Large numbers of environmental pollutants have been screened to identify such compounds; however, not until recently was 1,2-dibromo-4-(1,2-dibromoethyl)cyclohexane (TBECH) identified as the first potent activator of the human androgen receptor (hAR). TBECH has been found in beluga whales and bird eggs and has also been found to be maternally transferred in zebrafish. OBJECTIVES: In the present study we investigated interaction energies between TBECH diastereomers (alpha, beta, gamma, and delta) and the hAR, and their ability to activate the receptor and induce prostate-specific antigen (PSA) expression in vitro. METHODS: We performed computational modeling to determine interaction energies between the ligand and the AR ligand-binding site, and measured in vitro competitive binding assays for AR by polarization fluorometry analysis. We used enzyme-linked immunosorbent assays to determine PSA activity in LNCaP and HepG2 cells. RESULTS: We found the gamma and delta diastereomers to be more potent activators of hAR than the alpha and beta diastereomers, which was confirmed in receptor binding studies. All TBECH diastereomers induced PSA expression in LNCaP cells even though the AR present in these cells is mutated (T877A). Modeling studies of LNCaP AR revealed that TBECH diastereomers bound to the receptor with a closer distance to the key amino acids in the ligand-binding domain, indicating stronger binding to the mutated receptor. CONCLUSIONS: The present study demonstrates the ability of TBECH to activate the hAR, indicating that it is a potential endocrine disruptor.
Asunto(s)
Ciclohexanos/toxicidad , Disruptores Endocrinos/toxicidad , Retardadores de Llama/toxicidad , Receptores Androgénicos/efectos de los fármacos , Línea Celular Tumoral , Ensayo de Inmunoadsorción Enzimática , Células Hep G2 , Humanos , Masculino , Neoplasias de la Próstata/patología , Receptores Androgénicos/metabolismo , EstereoisomerismoRESUMEN
Perfluorinated acids (PFAs) and their precursors (PFA-precursors) exist in the environment as linear and multiple branched isomers. These isomers are hypothesized to have different biological properties, but no isomer-specific data are currently available. The present study is the first in a two-part project examining PFA isomer-specific uptake, tissue distribution, and elimination in a rodent model. Seven male Sprague-Dawley rats were administered a single gavage dose of approximately 500 microg/kg body weight perfluorooctane sulfonate (C(8)F(17)SO(3)(-), PFOS), perfluorooctanoic acid (C(7)F(15)CO(2)H, PFOA), and perfluorononanoic acid (C(8)F(17)CO(2)H, PFNA) and 30 microg/kg body weight perfluorohexane sulfonate (C(6)F(13)SO(3)(-), PFHxS). Over the subsequent 38 d, urine, feces, and tail-vein blood samples were collected intermittently, while larger blood volumes and tissues were collected on days 3 and 38 for isomer analysis by high-performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS). For all PFAs, branched isomers generally had lower blood depuration half-lives than the corresponding linear isomer. The most remarkable exception was for the PFOS isomer containing an alpha-perfluoromethyl branch (1m-PFOS), which was threefold more persistent than linear PFOS, possibly due to steric shielding of the hydrophilic sulfonate moiety. For perfluoromonomethyl-branched isomers of PFOS, a structure-property relationship was observed whereby branching toward the sulfonate end of the perfluoroalkyl chain resulted in increased half-lives. For PFHxS, PFOA, and PFOS, preferential elimination of branched isomers occurred primarily via urine, whereas for PFNA preferential elimination of the isopropyl isomer occurred via both urine and feces. Changes in the blood isomer profiles over time and their inverse correlation to isomer elimination patterns in urine, feces, or both provided unequivocal evidence of significant isomer-specific biological handling. Source assignment based on PFA isomer profiles in biota must therefore be conducted with caution, because isomer profiles are unlikely to be conserved in biological samples.
Asunto(s)
Contaminantes Ambientales/administración & dosificación , Contaminantes Ambientales/farmacocinética , Hidrocarburos Fluorados/administración & dosificación , Hidrocarburos Fluorados/farmacocinética , Animales , Contaminantes Ambientales/sangre , Contaminantes Ambientales/orina , Heces/química , Hidrocarburos Fluorados/sangre , Hidrocarburos Fluorados/orina , Isomerismo , Masculino , Ratas , Ratas Sprague-Dawley , Distribución TisularRESUMEN
Two major industrial synthetic pathways have been used to produce perfluorinated acids (PFAs) or their precursors: Telomerization and electrochemical fluorination (ECF). Products of telomer and ECF origin can be distinguished by structural isomer profiles. A mixture of linear and branched perfluoroalkyl isomers is associated with ECF. Telomer products characteristically consist of a single perfluoroalkyl geometry, typically linear. In biota, it is unclear if the isomer profile is conserved relative to the exposure medium and hence whether PFA isomer profiles in organisms are useful for distinguishing environmental PFA sources. A companion study suggested isomer-specific disposition following a single oral gavage exposure to rats. To confirm these findings under a more realistic subchronic feeding scenario, male and female rats were administered PFA isomers by diet for 12 weeks, followed by a 12-week depuration period. The diet contained 500 ng/g each of ECF perfluorooctanoate (PFOA, approximately 80% n-PFOA), ECF perfluorooctane sulfonate (PFOS, approximately 70% n-PFOS), and linear and isopropyl perfluorononanoate (n- and iso-PFNA). Blood sampling during the exposure phase revealed preferential accumulation of n-PFOA and n-PFNA compared to most branched isomers. Female rats depurated all isomers faster than males. Both sexes eliminated most branched perfluorocarboxylate isomers more rapidly than the n-isomer. Elimination rates of the major branched PFOS isomers were not statistically different from n-PFOS. Two minor isomers of ECF PFOA and one branched PFOS isomer had longer elimination half-lives than the n-isomers. Although extrapolation of these pharmacokinetics trends in rats to humans and wildlife requires careful consideration of dosage level and species-specific physiology, cumulative evidence suggests that perfluorocarboxylate isomer profiles in biota may not be suitable for quantifying the relative contributions of telomer and ECF sources.
Asunto(s)
Contaminantes Ambientales/administración & dosificación , Contaminantes Ambientales/farmacocinética , Hidrocarburos Fluorados/administración & dosificación , Hidrocarburos Fluorados/farmacocinética , Animales , Peso Corporal/efectos de los fármacos , Esquema de Medicación , Contaminantes Ambientales/sangre , Contaminantes Ambientales/orina , Heces/química , Conducta Alimentaria/efectos de los fármacos , Femenino , Hidrocarburos Fluorados/sangre , Hidrocarburos Fluorados/orina , Isomerismo , Masculino , Ratas , Ratas Sprague-Dawley , Distribución TisularRESUMEN
Juvenile rainbow trout (Oncorhynchus mykiss) were exposed in the laboratory to elevated doses of syn- and anti-isomers of Dechlorane Plus (DP) via their diet for 49 days (uptake phase), followed by 112 days of untreated food (depuration phase) to examine bioaccumulation parameters and possible metabolic products. Three groups of 60 fish were used in the study. Two groups were exposed separately to food fortified with known concentrations of syn- (0.79 +/- 0.03 microg/g, lipid weight) and anti-DP (1.17 +/- 0.12 microg/g, lipid weight) while a third control group was fed unfortified food. Neither isomer reached steady-state after 49 days of exposure. Only the syn-isomer accumulated linearly in the fish (whole-body minus liver) during the dosing phase with a calculated uptake rate constant of 0.045 +/- 0.005 (arithmetic mean +/- 1 x standard error) nmoles per day. A similar uptake rate was also observed for this isomer in the liver. The elimination of both isomers from the whole fish (minus liver) obeyed first order depuration kinetics (syn-: r2 = 0.6427, p < 0.001, anti-: r2 = 0.5350, p < 0.005) with calculated half-lives (t1/2) of 53.3 +/- 13.1 (syn-) and 30.4 +/- 5.7 (anti-) days. Elimination of the isomers from the liver was difficult to interpret because of suspected enterohepatic circulation and redistribution of the isomers in the liver during clearance from other tissues. The biomagnification factor (BMF, determined in whole fish minus liver) of the syn-isomer (5.2) was greater than the anti-isomer (1.9) suggesting that the former isomer is more bioavailable. A suite of metabolites were screened for in the liver including dechlorinated, hydroxylated, methoxylated and methyl sulfone degradates. Even with the purposely high dose used in the uptake phase, none of these degradates could be detected in the extracts. This suggests that if metabolites of DP are detected in fish from aquatic food webs their presence is likely not from in vivo biotransformation of the parent compound.
Asunto(s)
Monitoreo del Ambiente , Hidrocarburos Clorados/farmacocinética , Hígado/efectos de los fármacos , Oncorhynchus mykiss/metabolismo , Compuestos Policíclicos/farmacocinética , Contaminantes Químicos del Agua/farmacocinética , Animales , Biotransformación , Retardadores de Llama/farmacología , Agua Dulce , Hidrocarburos Clorados/química , Isomerismo , Hígado/metabolismo , Hígado/patología , Oncorhynchus mykiss/crecimiento & desarrollo , Compuestos Policíclicos/química , Factores de Tiempo , Contaminantes Químicos del Agua/químicaRESUMEN
Recent expansion within the oil sands industry of the Athabasca Basin of Alberta, Canada has led to increased concern regarding process-affected wastewaters produced during bitumen extraction. Naphthenic acids (NAs) have been identified as the primary toxic constituents of oil sands process-affected waters (OSPW) and studies have shown that with time, microbial degradation of lower molecular weight NAs has led to a decrease in observed toxicity. As earlier studies identified the need for an "unequivocal demonstration" of lower molecular weight NAs being the primary contributors to mixture toxicity, a study was initiated to fractionate an extracted NA mixture by molecular weight and to assess each fraction's toxicity. Successful molecular weight fractionation of a methylated NA mixture was achieved using a Kugelrohr distillation apparatus, in which fractions collected at higher boiling points contained NAs with greater total carbon content as well as greater degree of cyclicity. Assays with Vibrio fischeri bioluminescence (via Microtox assay) revealed that the lowest molecular weight NAs collected had higher potency (EC50: 41.9+/-2.8 mg l(-1)) than the highest molecular weight NAs collected (EC50: 64.9+/-7.4 mg l(-1)). Although these results support field observations of microbial degradation of low molecular weight NAs decreasing OSPW toxicity, it is not clear why larger NAs, given their greater hydrophobicity, would be less toxic.
Asunto(s)
Ácidos Carboxílicos/toxicidad , Alberta , Aliivibrio fischeri/efectos de los fármacos , Bioensayo , Ácidos Carboxílicos/química , Ácidos Carboxílicos/aislamiento & purificación , Fenómenos Químicos , Química Física , Diazometano/síntesis química , Diazometano/química , Industrias , Luminiscencia , Metilación , Peso Molecular , Petróleo , Espectrometría de Masa por Ionización de ElectrosprayRESUMEN
1,2-Dibromo-4-(1,2-dibromoethyl)cyclohexane (TBECH) is used primarily as an additive flame retardant. 1H NMR spectroscopy and an X-ray structure determination have revealed that a technical mixture consists largely of two (of the four possible) diastereomers, rac-(1R,2R)-1,2-dibromo-(4S)-4-((1S)-1,2-dibromoethyl)cyclohexane (alpha-TBECH) and rac-(1R,2R)-1,2-dibromo-(4S)-4-((1R)-1,2-dibromoethyl)cyclohexane (beta-TBECH), in a mole ratio of approximately 1:1. The two other possible isomers, gamma- and delta-TBECH, were not detected in a technical mixture. The TBECH isomers are thermally sensitive and can easily interconvert at temperatures of 125 degrees C. A thermal equilibrium mixture of alpha-, beta-, gamma- and delta-TBECH consists of approximately 33%, 33%, 17% and 17% of these isomers, respectively. Separation of all four TBECH diastereomers, with minimal thermal interconversion of the isomers, was achieved by careful selection of GC-capillary column length and injector temperature. Although technical TBECH does not contain the gamma- and delta-isomers, they may still be relevant environmental contaminants since manufacturing processes utilize thermal processes which may induce their formation.
Asunto(s)
Ciclohexanos/química , Retardadores de Llama/análisis , Bromo/química , Cromatografía de Gases y Espectrometría de Masas , Halogenación , Calor , Isomerismo , Espectroscopía de Resonancia Magnética , Estructura MolecularRESUMEN
The production of technical penta-BDE products such as Great Lakes DE-71 is not a clean process but, instead, gives complex mixtures of various BDE congeners. This study reports the verification of the structures of many of the BDE congeners in Great Lakes DE-71 using (1)H NMR and/or GC/MS. In total, 24 BDE congeners, including nine (tetra-BDEs 42, 48, 51, and 91; penta-BDEs 102, 104, and 119; hexa-BDEs 149 and 155) which had not been reported previously, were identified in this technical mix by (1)H NMR. The quantification of these congeners was realized by two independent methods: (1)H NMR spectroscopy in combination with HRGC/LRMS and isotopic dilution and HRGC/HRMS analysis. The values obtained compare well between methods, and with data produced in earlier studies.
Asunto(s)
Mezclas Complejas/análisis , Contaminantes Ambientales/análisis , Éteres Fenílicos/análisis , Bifenilos Polibrominados/análisis , Cromatografía de Gases , Cromatografía en Capa Delgada , Mezclas Complejas/química , Mezclas Complejas/aislamiento & purificación , Contaminantes Ambientales/química , Contaminantes Ambientales/aislamiento & purificación , Éteres Difenilos Halogenados , Espectroscopía de Resonancia Magnética , Espectrometría de Masas , Peso Molecular , Éteres Fenílicos/química , Éteres Fenílicos/aislamiento & purificación , Bifenilos Polibrominados/química , Bifenilos Polibrominados/aislamiento & purificaciónRESUMEN
The production of perfluoroalkylsulfonate (PFOS) derivatives from linear alkyl precursors using electrochemical fluorination is not a clean process but, instead, gives complex mixtures. This study reports the isolation and (19)F NMR characterization of eleven perfluorooctanesulfonate isomers from a commercial mixture. This allowed the quantification of the individual CF(3) branched isomers that predominate in technical PFOS.
Asunto(s)
Ácidos Alcanesulfónicos/química , Ácidos Alcanesulfónicos/aislamiento & purificación , Fluorocarburos/química , Fluorocarburos/aislamiento & purificación , Mezclas Complejas/química , Fluoruros/química , Isomerismo , Espectroscopía de Resonancia MagnéticaRESUMEN
1,2-dibromo-4-(1,2-dibromoethyl)cyclohexane (TBECH) is used primarily as an additive flame retardant. Technical grade TBECH consists of near equimolar amounts of two (of a possible four) diastereoisomers: rac-(1R,2R)-1,2-dibromo-(4S)-4-((1S)-1,2-dibromoethyl)cyclohexane ((alpha-TBECH) and rac-(1R,2R)-1,2-dibromo-(4S)-4-((1R)-1,2-dibromoethyl)cyclohexane (beta-TBECH). The two other possible isomers, gamma- and delta-TBECH, appear in the technical mixture when heated at temperatures above 120 degrees C. Careful selection of GC-capillary column length was critical in resolution of the two main diastereoisomers. Column lengths of 60 or 30 m (0.25 microm film thickness) resulted in incomplete separation of the alpha- and beta-isomers, while on a 10 m column, the isomers were baseline separated. The gamma- and delta-isomers could not be resolved on any column length in this study. Increased injector port temperature induced thermal conversion of the alpha- and beta-isomers to gamma- and delta-TBECH. Electron impact ionization (EI) was used to provide specificity because no characteristic ions in the electron capture negative ionization (ECNI) mass spectrum of TBECH were evident. In EI, the dominant ions in the mass spectrum corresponded to a concomitant loss of HBr and Br from the molecular ion; the biggest peak in this ion cluster (m/z 266.9208) was used for quantitation and the second biggest peak (m/z 264.9227) was used for confirmation. Beluga (Delphinapterus leucas) blubber extracts of animals from the Canadian Arctic (n=29) were analyzed using low resolution (LR) MS and high resolution (HR) MS run at a resolving power of 10,000. beta-TBECH was the only isomer observed in the samples and was detected in 17 samples. The LRMS technique appeared to overestimate beta-TBECH concentrations compared to HRMS, suggesting a small interference arose at the nominal mass monitored. This potential interference also led to some false positive and negative values (n=7) based on the expected ion ratio of the quantitation and confirmation ions. Observed concentrations of the beta-isomer as measured by HRMS ranged from 1.1 to 9.3 ng/g (lipid weight).
Asunto(s)
Ballena Beluga/metabolismo , Ciclohexanos/metabolismo , Retardadores de Llama/metabolismo , Contaminantes Químicos del Agua/metabolismo , Tejido Adiposo/metabolismo , Animales , Monitoreo del Ambiente , Femenino , Cromatografía de Gases y Espectrometría de Masas , MasculinoRESUMEN
Samples of potassium perfluorooctanesulfonate (PFOSK) from three suppliers were analyzed by LC-ESI-MS/MS for purity and by LC-ESI-MS for the percentage of linear isomer present. Our data indicated that the purity ranged from 80% to 98% and the percentages of linear isomer from 67% to 79%. The proportion of branched isomers present in the samples was also estimated using (19)F NMR. These results agreed quite closely with those found by LC-ESI-MS indicating that there is essentially no difference in overall SIM response factor for the branched isomers vs. that of the linear isomer. Several further observations relevant to the use of standards when analyzing for PFOS were encountered during this study. It appears unlikely that matrix effects attributable to the cation (sodium or potassium) present in PFOSNa or PFOSK internal standards is an issue. In seeking potential matrix effects, it was found that the chromatography was improved substantially when the standard was injected as a solution in 80:20 methanol/water rather than 100% methanol. Notably, in concert with the improvement in chromatography, an increase of about 10% in response was observed. In some closely related studies, when (18)O(2) mass-labeled perfluorohexanesulfonate was used as an internal standard, the actual and theoretical concentration ratios matched closely those for related native sulfonates as long as they did not co-elute. However, when they did co-elute, the peak intensities of the native species were enhanced by about 5%, while those of the labeled compound were suppressed by a similar amount. If this effect were not taken into account, the concentration of the native would be inflated by 10%.
Asunto(s)
Ácidos Alcanesulfónicos/análisis , Ácidos Alcanesulfónicos/química , Fluorocarburos/análisis , Fluorocarburos/química , Ácidos Alcanesulfónicos/normas , Calibración , Cromatografía Liquida/métodos , Fluorocarburos/normas , Isomerismo , Espectroscopía de Resonancia Magnética , Espectrometría de Masas/métodos , Estructura Molecular , Estándares de ReferenciaRESUMEN
The title compound (OctaInd), C(18)H(12)Br(8), is a commercial brominated flame retardant (BFR). In the mol-ecule, the five-membered ring has a slight envelope conformation, with a deviation of 0.317â (9)â Å for the flap C atom from four essentially planar C atoms. The dihedral angle between the two benzene rings is 74.00â (16)â Å.
RESUMEN
The title compound, C(18)H(14)Cl(10), is a decachlorinated commercial flame retardant. The structure determination confirms the relative stereochemistry. The central eight-membered ring is in a chair-type conformation. In the crystal structure, there are no significant inter-molecular inter-actions and mol-ecules are separated by normal van der Waals distances.
RESUMEN
The title compound, C(18)H(13)Cl(11), is an undecachlorinated commercial flame retardant. The asymmetric unit contains two independent half-mol-ecules. The complete mol-ecules are generated by crystallographic inversion symmetry, causing the terminal H atoms and one of the Cl atoms to be disordered equally over two sites in each mol-ecule. The central eight-membered rings are in chair-type conformations. In the crystal structure, there is a single weak inter-molecular C-Hâ¯Cl hydrogen bond.