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Minor Isomer (minor + isomer)
Selected AbstractsToxicokinetics of perfluorocarboxylate isomers in rainbow troutENVIRONMENTAL TOXICOLOGY & CHEMISTRY, Issue 2 2009Amila O. De Silva Abstract Perfluorooctanoate (PFOA) and other perfluorocarboxylates (PFCAs) are widely dispersed in the environment. Current and/or historical production of PFOA and fluorochemical precursors was conducted by telomerization and electrochemical fluorination (ECF). Telomer products typically contain linear chains of perfluorocarbons, and ECF products are a mixture of linear and branched isomers. The objective of the present study was to examine the role of toxicokinetics on PFCA isomer profiles in fish since monitoring studies have revealed a predominance of n -isomers of PFCAs in biota. Using dietary exposure, rainbow trout were administered technical ECF PFOA isomers (6.9 ,g/kg/d), linear perfluorononanoate (1.4 ,g/kg/d n -PFNA), and isopropyl PFNA (1.1 ,g/kg/d iso -PFNA) for 36 d and then switched to a 40-d clean diet. Throughout exposure and depuration phases, blood and tissue sampling ensued. The accumulation ratio (AR) revealed similar accumulation propensity of n -PFOA and two minor branched PFOA isomers; however, the majority of branched isomers had lower AR values than n -PFOA. Enrichment of n -PFOA and n -PFNA relative to most branched isomers was consistent in all tissues. First-order elimination (kd) and half-life (t1/2) values were calculated. The largest t1/2 corresponded to n -PFNA followed by iso -PFNA. In ECF PFOA isomers, both n -PFOA and one minor branched isomer had the largest t1/2, suggesting that this minor isomer could be diagnostic of ECF exposure using environmental PFOA isomer patterns. Results of lower-dose ECF PFOA exposure showed similar results to the high-dose study; it is possible that both scenarios resulted in saturation of processes involved in PFCA transport. As such, the toxicokinetics of PFCA isomers at environmentally realistic levels may deviate from the results of the present study. [source] Structure Comparison of Early and Late Lanthanide(III) Homodinuclear Macrocyclic Complexes with the Polyamine Polycarboxylic Ligand H8OHECEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 19 2004Ulrike A. Böttger Abstract The solid-state structures of two new homodinuclear chelate complexes with the late lanthanide(III) ions Yb and Lu, [Na2(Yb2OHEC)].14.5H2O (1), and [Na2(Lu2OHEC)].14.5H2O (2) (H8OHEC = 1,4,7,10,14,17,20,23-octaazacyclohexacosane- 1,4,7,10,14,17,20,23-octaacetic acid), have been determined by X-ray crystal structure analysis. Each lanthanide(III) ion is coordinated by eight donor atoms of the ligand and the geometry of the coordination polyhedron approaches a bicapped trigonal prism. These structures are compared with those of the homodinuclear chelate complexes with the same ligand and the mid to early lanthanide(III) ions Gd, Eu, La and also Y. A distinctive structural change occurs across the lanthanide series. The centrosymmetric mid to early lanthanide(III) complexes are all ninefold-coordinated in a capped square antiprismatic arrangement with a water molecule coordinated in a prismatic position. This structure is maintained in aqueous solution, together with an asymmetric minor isomer. The late lanthanide(III) OHEC complexes not only lack the inner-sphere water, but the change of coordination sphere also results in a loss of symmetry of the whole complex molecule. The observed change of coordination mode and number of the lanthanide ion may offer a geometric model for the isomerization process in eight- and ninefold-coordinated complex species that are isomers in a possible coordination equilibrium observed by NMR in aqueous solution. This model may also explain the intramolecular rearrangements necessary during water exchange in the inner coordination sphere of the complex [(Gd2OHEC)(H2O)2]2, through a slow dissociative mechanism. Protonation constants of the H8OHEC ligand and complex formation constants of this ligand with GdIII, CaII, CuII and ZnII have been determined by solution thermodynamic studies. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004) [source] High specific activity tritium labeling of vitamin D derivative RO275646,JOURNAL OF LABELLED COMPOUNDS AND RADIOPHARMACEUTICALS, Issue 14 2005Steve A. de Keczer Abstract The octahydroindenone intermediate was tritium labeled using T2O isotope exchange labeling, and then elaborated to the vitamin D derivative RO275646. Though this method of labeling was expected to give the minor isomer, it was the shortest and most convenient route to the high specific activity metabolically stable labeled sites. A total of 34 mCi (from two separate runs) at 64 Ci/mmol of [3H]-RO275646 were prepared by this method. Copyright © 2005 John Wiley & Sons, Ltd. [source] gem -Dimethylcyclopropanation of dibenzylideneacetone using triisopropyl sulfoxonium tetrafluoroborateACTA CRYSTALLOGRAPHICA SECTION C, Issue 2 2009Michael G. Edwards The reaction between dibenzylideneacetone (dba) and triisopropyl sulfoxonium tetrafluoroborate has been reinvestigated. The stereochemistry of the major diasteromeric bis(gem -dimethylcyclopropane) adduct has now been assigned as [(1RS,3RS)-2,2-dimethyl-3-phenylcyclopropyl][(1SR,3SR)-2,2-dimethyl-3-phenylcyclopropyl]methanone, C23H26O, by X-ray crystallographic studies on a twinned crystal. The asymmetric unit contains two molecules of the adduct, the conformations of which differ in the orientation of the phenyl ring relative to the adjacent cyclopropanated double bond. The carbonyl groups of each adduct are aligned approximately along the a axis and in opposite directions to each other. The molecules pack to give a sinusoidal pattern along the b axis. This is the first acyclic bis(dimethylcyclopropyl) ketone for which an X-ray crystal structure determination has been reported, and is also the first bis-cyclopropanated dba analogue. The knowledge that the major diastereomer has the meso structure (and therefore the confirmation that the minor isomer is the racemate) will prove invaluable in future studies to utilize bis(dimethylcyclopropyl) ketones as reagents, in rearrangement processes, and as potential ligands and ligand precursors in organometallic chemistry. [source] Disposition of perfluorinated acid isomers in sprague-dawley rats; Part 2: Subchronic doseENVIRONMENTAL TOXICOLOGY & CHEMISTRY, Issue 3 2009Amila O. De Silva Abstract 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, ,80% n -PFOA), ECF perfluorooctane sulfonate (PFOS, ,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. [source] | ||||||||||