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PubMed2003

Non-polar halogenated natural products bioaccumulated in marine samples. II. Brominated and mixed halogenated compounds.

Several identified and potential natural brominated bioaccumulative compounds were studied in this work. 4,6-dibromo-2-(2('),4(')-dibromo)phenoxyanisole (BC-2) previously detected in Australian marine mammals and isolated from sponges, was synthesized. Two byproducts (a tetrabromo isomer and a tribromo congener) were investigated as well. The byproducts of the synthesis were not identified in the environmental samples investigated. Previously described natural brominated compounds (BC-1, BC-2, BC-3, BC-10, BC-11, MHC-1) and anthropogenic brominated diphenyl ethers (BDE-47, BDE-99, BDE-100, BDE-154) were detected in a sample of human milk. The sample was from a woman from the Faeroe Islands who frequently consumed fish as well as whale blubber and meat. The most abundant compound originated from the natural tetrabromo phenoxyanisole BC-3 which may have a 3:1 distribution of bromine on the two phenyl units. This sample also accumulated a dibromochloroanisole, as well as a previously unknown mixed halogenated compound (MHC-X) and an unknown, most likely aromatic brominated compound. Co-elutions on a DB-5 column were found for BDE-99 and BC-11 as well as BDE-154 and the unknown brominated compound. This suggests that quantification of these two compounds has to be carried out carefully.Two samples of lower trophic level, namely Baltic cod liver and Mexican mussel tissue, were investigated as well. The cod liver samples contained BDE congeners but also abundant signals for the natural 2,3,3('),4,4('),5,5(')-heptachloro-1(')-methyl-1,2(')-bipyrrole Q1 and tribromoanisole (TBA). The mussel sample contained Q1, TBA, another halogenated anisole, BC-1, BC-2, and BC-3, as well as additional, potential natural brominated compounds in the elution range of tribromophenoxyanisoles.

Animals↗
PubMed1982

Acute inhalation toxicity of some halogenated and non-halogenated hydrocarbons.

1 The relative potency of effect of a wide range of halogenated and unsubstituted hydrocarbons on the central nervous system (CNS) and the heart of experimental animals have been determined. 2 The chemicals used caused either stimulation or depression of the rat CNS after 10 minutes' inhalation of concentrations ranging from 0.24% to greater than 80% (v/v), and cardiac sensitization in dogs after 5 minutes' inhalation of 0.12% to approximately 80% (v/v). 3 The toxicity could not be correlated with chemical structure, molecular weight, the presence or absence of various halogen atoms or the degree of saturation, but it was inversely related to the saturated vapour pressure. When the results were expressed on a thermodynamic scale the chemicals had similar potencies at relative saturations of 0.004 to 0.04 4 It is suggested that the effects of these chemicals on the CNS and the heart are probably structurally non-specific, and the chemicals may be regarded as physical toxicants whose effects are predictable from their physico-chemical properties.

Animals↗
PubMed2006

Isostructurality, polymorphism and mechanical properties of some hexahalogenated benzenes: the nature of halogen...halogen interactions.

The nature of intermolecular interactions between halogen atoms, X...X (X = Cl, Br, I), continues to be of topical interest because these interactions may be used as design elements in crystal engineering. Hexahalogenated benzenes (C6Cl(6-n)Br(n), C6Cl(6-n)I(n), C6Br(6-n)I(n)) crystallise in two main packing modes, which take the monoclinic space group P2(1)/n and the triclinic space group P1. The former, which is isostructural to C6Cl6, is more common. For molecules that lack inversion symmetry, adoption of this monoclinic structure would necessarily lead to crystallographic disorder. In C6Cl6, the planar molecules form Cl...Cl contacts and also pi...pi stacking interactions. When crystals of C6Cl6 are compressed mechanically along their needle length, that is, [010], a bending deformation takes place, because of the stronger interactions in the stacking direction. Further compression propagates consecutively in a snakelike motion through the crystal, similar to what has been suggested for the motion of dislocations. The bending of C6Cl6 crystals is related to the weakness of the Cl...Cl interactions compared with the stronger pi...pi stacking interactions. The triclinic packing is less common and is restricted to molecules that have a symmetrical (1,3,5- and 2,4,6-) halogen substitution pattern. This packing type is characterised by specific, polarisation-induced X...X interactions that result in threefold-symmetrical X3 synthons, especially when X = I; this leads to a layered pseudohexagonal structure in which successive planar layers are inversion related and stacked so that bumps in one layer fit into the hollows of the next in a space-filling manner. The triclinic crystals shear on application of a mechanical stress only along the plane of deformation. This shearing arises from the sliding of layers against one another. Nonspecificity of the weak interlayer interactions here is demonstrated by the structure of twinned crystals of these compounds. One of the compounds studied (1,3,5-tribromo-2,4,6-triiodobenzene) is dimorphic, adopting both the monoclinic and triclinic structures, and the reasons for polymorphism are suggested. To summarise, both chemical and geometrical models need to be considered for X...X interactions in hexahalogenated benzenes. The X...X interactions in the monoclinic group are nonspecific, whereas in the triclinic group some X...X interactions are anisotropic, chemically specific and crystal-structure directing.

Journal Article↗
PubMed1984

Mammary transfer and metabolism in the rat of halogenated fatty acids of halogenated olive oil.

To assess possible incorporation of halogenated fatty acids into the neonate via the milk, a 4-day study was carried out in which lactating Wistar rats were orally dosed with either brominated olive oil (BOO) (0.6 g/kg body wt/day) or chlorinated olive oil (COO) (0.4 g/kg body wt/day) for the first 4 days. On days 1-5 inclusive 2 pups per litter were sacrificed and the stomach curd and livers analyzed for halogenated fatty acids by gas liquid chromatography (GLC). On day 5 all dams also were sacrificed and their livers and adipose tissue similarly analyzed. With BOO, brominated fatty acids (bfa) accumulated in both the milk lipids and neonate liver lipids, and appeared to plateau on day 4 at levels of 2% and 5% respectively. In contrast to the BOO in which approximately 100% of the bfa was dibromostearic (DBS), the milk bfa comprised 79% (DBS), 9% dibromopalmitic (DBP) and 12% dibromomyristic (DBM) acids, suggesting maternal metabolism to the shorter chain brominated acids. In the neonate liver lipids the bfa composition was 47% (DBS), 12% (DBP) and 41% (DBM), suggesting either further metabolism in the neonate and/or preferential accumulation of the shorter chain brominated acids. The analysis of maternal tissue indicated very low bfa residues, contrary to previous studies in non-lactating rats. Similar results were obtained with COO.

Adipose Tissue↗
PubMed2006

Induced super-halogen behavior of metal moieties in halogen-doped clusters: LinI(-) and AlnI(-), n = 13, 1, 2, 3.

A comparative density functional theory (DFT) study of a series of neutral and negative-ionic lithium and aluminum clusters doped with iodine atom is presented. The I atom is found to preserve the same position at Li13 with and without the negative charge and Li13 to vary its shape from prolate to oblate with changing spin state of Li13I. Both the Mulliken and natural charges are considered, the natural-charge separation between the metal and halogen moieties being generally much larger (except for Al13I-). In LinI-, the additional electron is strongly localized on the metal moiety starting from n = 1, even though the electron affinity of Lin is much smaller than that of I. Such a super-halogen behavior of Lin is induced by highly electronegative iodine making the two components charged in LinI and leading to a charge-dipole interaction with the additional electron. In AlnI-, similar factors result in Aln being more negative than I already for n = 3, even though the electron affinity of I is higher, the effect escalating for n = 13.

Journal Article↗
PubMed2006

Absence of halogen...halogen interactions in chlorotrimethylsilane polymorphs.

The structures of in situ pressure-frozen chlorotrimethylsilane crystals, (CH3)3SiCl, have been determined at 0.23, 0.30 and 0.58 GPa. The molecular arrangements in the low-temperature and high-pressure phases are two-dimensionally isostructural, but different in the third perpendicular direction. Consequently, a striking similarity exists between the unit-cell dimensions of these polymorphs. The absence of short Cl...Cl contacts, both in the low-temperature or pressure-frozen phases of (CH3)3SiCl, has been rationalized in terms of the favoured packing patterns and comparable energies of halogen...halogen interactions and other van der Waals forces.

Journal Article↗
PubMed1992

In vivo studies on halogen compound interactions. IV. Interaction among different halogen derivatives with and without synergistic action on liver toxicity.

The liver toxicity of several halogen compound mixtures have been tested. The compounds were selected on the basis of their metabolic pathways: carbon tetrachloride (CT) and trichlorobromomethane (TCBM) undergo a dehalogenation via P450-dependent enzyme system, 1,2-dichloroethane (DCE) and 1,2-dibromoethane (DBE) are mainly conjugated with the cytosolic glutathione (GSH) by means of the GSH-S-transferase. The mixture TCBM+DBE shows a more than additive action on lipid peroxidation and liver necrosis. TCBM, like CT, reduces the hepatic level of GSH-S-transferase, increasing the amount of DBE available for cytochrome P450-dependent metabolism, with the production of toxic metabolites. Thus, the behavior of the mixture TCBM+DBE is very similar to that of the mixture CT+DBE, previously reported. Mixtures composed of CT+TCBM and DCE+DBE do not show any synergistic effect on liver toxicity. The results allow one to conclude that the toxicity of mixtures of halogen compounds can be partly predicted on the basis of their metabolic pathways. When the metabolism is quite different, a synergistic toxicity can occur if one pathway interferes with a detoxification mechanism of the other compound. If the two metabolisms are very similar they produce, at most, an additive toxicity.

Alanine Transaminase↗
PubMed1979

Potential halogenated industrial carcinogenic and mutagenic chemicals. I. Halogenated unsaturated hydrocarbons.

The halogenated aliphatic hydrocarbons represent one of the most important categories of industrial chemicals from a consideration of use categories, production volume, environmental and toxicological considerations, and hence most importantly, potential population risk. The major unsaturated hydrocarbons reviewed, primarily in terms of their synthesis, utility, stability, distribution and levels of exposure as well as their reactivity, carcinogenicity, mutagenicity and metabolism, include: vinyl chloride, vinylidene chloride, trichloroethylene, perchloroethylene, chloroprene, trans-1,4-dichlorobutene, hexachlorobutadiene and allyl chloride.

Adult↗
PubMed1979

Potential halogenated industrial carcinogenic and mutagenic chemicals. IV. Halogenated aryl derivatives.

A variety of halogenated aryl derivatives possess significant activity as solvents for pesticides, heat transfer agents, pesticide intermediates, additives for rubber products, intermediates in organic synthesis and as insect repellants and deodorants. Ortho- and para-dichlorobenzenes; 1,2,4-trichloro- and hexachlorobenzene, as well as bromobenzenes and benzylchloride were reviewed principally in terms of their synthesis, areas of utility, stability, distribution, reactivity, levels of exposure, populations at risk, metabolism, carcinogenicity and mutagenicity.

Animals↗
PubMed2005

Kinetic assessment of persistent halogenated xenobiotics in cell culture models: comparison of mono- and poly-halogenated compounds.

We evaluated the suitability of single and multiple cell type cultures as model systems to characterise cellular kinetics of highly lipophilic compounds with potential ecotoxicological impact. Confluent mono-layers of human skin fibroblasts, rat astrocytoma C6 cells, non-differentiated and differentiated mouse 3T3 cells were kept in culture medium supplemented with 10% foetal calf serum. For competitive uptake experiments up to four different cell types, grown on glass sectors, were exposed for 3h to (14)C-labelled model compounds, dissolved either in organic solvents or incorporated into unilamellar lecithin liposomes. Bromo-, or chloro-benzenes, decabromodiphenylether (DBP), and dichlorodiphenyl ethylene (DDE) were tested in rather high concentration of 20 microM. Cellular toxicity was low. Compound levels were related to protein, DNA, and triglyceride contents. Cellular uptake was fast and dependent on physico-chemical properties of the compounds (lipophilicity, molecular size), formulation, and cell type. Mono-halogenated benzenes showed low and similar uptake levels (=low accumulation compounds). DBP and DDE showed much higher cellular accumulations (=high accumulation compounds) except for DBP in 3T3 cells. Uptake from liposomal formulations was mostly higher than if compounds were dissolved in organic solvents. The extent of uptake correlated with the cellular content of triglycerides, except for DBP. Uptake competition between different cell types was studied in a sectorial multi-cell culture model. For low accumulation compounds negligible differences were found among C6 cells and fibroblasts. Uptake of DDE was slightly and that of DBP highly increased in fibroblasts. Well-defined cell culture systems, especially the sectorial model, are appropriate to screen for bioaccumulation and cytotoxicity of (unknown) chemical entities in vitro.

Animals↗
PubMed1996

Determination of biogenic halogenated methyl-phenyl ethers (halogenated anisoles) in the picogram m(-3) range in air.

Halogenated anisoles (methyl-phenyl ethers) appear to be ubiquitous organic trace compounds in the environment. An analytical method is presented for analyzing the altogether 134 congeners of chloro-, bromo- and mixed bromochloro-anisoles on an isomer-specific basis in air. High volume sampling (20 m(3) per hour) is carried out by adsorption, using a mixture of silica gel 60 and ENVI-Carb. The preseparation of the anisoles is achieved by NP-LC on Florisil (a magnesium silicate). The interference by volatile n-alkyl nitrates in the electron-capture detection can be avoided by a LC-preseparation on a carboneous phase. The isomer-specific separation and detection is performed by HRGC-ECD and HRGC-MS-SIM. A structure-specific systematic numbering of the 134 congeners of the chloro-, bromo- and bromochloro-anisoles is suggested. The retention data are given of 16 chloroanisoles, 10 bromoanisoles and 27 bromo-chloroanisoles on three stationary phases with different polarity.

Journal Article↗
PubMed2005

Platinum complexes of diazo ligands. Studies of regioselective aromatic ring amination, oxidative halogen addition and reductive halogen elimination reactions.

2-(Arylazo)pyridine ligands, L1a-1c react with the salt K2[PtCl4] to give the mononuclear complexes [PtCl2(L1)](1), which readily react with ArNH2 to yield the monochloro complexes of type [PtCl(L2)](HL2= 2-[(2-(arylamino)phenyl)azo]pyridine)(2) via regioselective ortho-amine fusion at the pendent aryl ring of coordinated L1. Oxidative addition of the electrophiles Y2(Y = Cl, Br, I) to the square-planar platinum(II) complex, has led to syntheses of the corresponding octahedral platinum(IV) complexes, [PtY3(L2)](3) in high yields. Ascorbate ion reductions of the platinum(IV) complexes, , resulted in reductive halogen elimination to revert to the platinum(II) complexes almost quantitatively. Isolation of products and X-ray structure determination of the representative complexes followed all these chemical reactions. In crystal packing, the compound [PtCl2(L1c)](1c) forms dimeric units with a Pt...Pt distance of 3.699(1) A. In contrast, the crystal packing of 2b revealed that the molecules are arranged in an antiparallel fashion to form a noncovalent 1D chain to accommodate pi(aryl)-pi(pyridyl) and Pt-pi(aryl) interactions. Notably, the oxidation of [Pt(II)Cl(L2a)](2a) by I2 produced a mixed halide complex [Pt(IV)ClI2(L2a)](5), which, in turn, is reduced by ascorbate ion to produce [Pt(II)I(L2a)] with the elimination of ClI. All the platinum(II) complexes are brown, the platinum(IV) complexes, on the other hand, are green. Low-energy visible range transitions in the complexes of the extended ligand [L2]- are ascribed to ligand basedpi-pi* transitions. Cyclic voltammetric behaviour of the complexes is reported.

Journal Article↗
PubMed2005

New route to 1-thia-closo-dodecaborane(11), closo-1-SB11H11, and its halogenation reactions. The effect of the halogen on the dipole moments and the NMR spectra and the importance of spin-orbit coupling for the 11B chemical shifts.

Reaction between nido-B10H14 (1) and elemental sulfur in CHCl3 in the presence of Et3N at room temperature, followed by treatment with Et3N.BH3 at 170-190 degrees C, resulted in the isolation of closo-1-SB11H11 (2) in 50% yield. Selected electrophilic halogenation reactions of compound led to the isolation of a series of monohalogenated derivatives of general constitution 12-X-closo-1-SB11H10 (12-X-, where X = Cl, Br, and I). The structures of 12-Cl- and 12-I- were determined by an X-ray diffraction analysis and the structures of all compounds were geometry optimised at the RMP2(fc)/6-31G* level. The constitution of all compounds is consistent with the results of mass spectrometry and multinuclear (1H and 11B) spectroscopy complemented by two-dimensional [11B-11B]-COSY and 1H{11B(selective)} NMR measurements. Experimental 11B chemical shifts generally show acceptable agreement with theoretical values calculated by GIAO methods, but spin-orbit coupling must be included for nuclei bearing heavy-atom substituents such as Br or I. The dipole moments determined for the B12-X bonds show similarities to those of aliphatic C-X bonds and confirm unambiguously the B12 --> S dipole moment orientation in the SB11 cage.

Journal Article↗
PubMed1995

Effects of halogenated and non-halogenated anesthetics on diaspirin cross-linked hemoglobin induced contractions of porcine pulmonary veins.

Diaspirin crosslinked hemoglobin (DCLHb) is a resuscitative fluid presently undergoing clinical trials. Administration of DCLHb is associated with an elevation of mean arterial pressure in vivo and contraction of isolated blood vessels in vitro. The mechanisms for the vascular actions are unknown but may be due to inhibition of nitric oxide (NO). Halothane has been reported to inhibit NO induced relaxation. We examined the effect of anesthetics on DCLHb induced contraction of blood vessels. Porcine pulmonary veins were excised, cut into rings and placed in organ chambers filled with 25 ml Krebs-Ringer solution (37 degrees C). Following equilibration at their optimal length the rings were exposed to increasing concentrations of serotonin(10(-8)M-10(-5)M). Endothelial activity was confirmed by relaxation greater than 80% with ACh (10(-6)M). DCLHb (1.5 x 10(-8)M to 6 x 10(-7)M) contracted porcine pulmonary veins (1.04 +/- 0.17g to 3.45 +/- 0.22g), and halothane (0.5% and 1%) significantly inhibited these DCLHb induced contractions in a dose-related manner (-41.6 +/- 8.1% and -73.3 +/- 8.2%, respectively). At equi-molar concentrations, isoflurane had no inhibitory activity. The relative effect of these volatile anesthetics is consistent with their inhibitory actions on other heme containing proteins. Propofol (10(-5)M) only has inhibitory effects on lower concentrations of DCLHb. Fentanyl did not have inhibitory effects. These results suggest that halogenated anesthetics may interact with the heme iron of DCLHb and inhibit its binding with NO.

Anesthetics, Inhalation↗
PubMed1988

Studies on contamination of vegetable drugs with halogen derivative pesticides. Part 2: Concentrations of halogen derivative pesticides in vegetable blends and herbal granulated products produced in Poland in 1980-1984.

Changes in concentration levels of halogen derivative pesticides (p,p'-DDT and its metabolites p,p'-DD and p,p'-DDE, as well as HCH, DMDT, aldrin, dieldrin) in vegetable blends and granulated products produced in Poland were studied in the period 1980-1984. By means of GLC and TLC methods it has been found, that as in the case of raw materials, contamination levels of these materials increased from 1980 up to the maximum values for vegetable blends in 1982 and in granulated products in 1983. Generally, concentration levels in vegetable blends and in raw material were similar over the same periods of time, whereas concentrations in granulated products were considerable lower.

Chromatography, Gas↗
PubMed1988

Studies on contamination of vegetable drugs with halogen derivative pesticides. Part 1: Changes of concentrations of halogen derivatives in herbal raw materials within the period of 1980-1984.

Levels of concentration of halogen derivatives (p,p'-DDT with metabolites p,p'-DDD and p,p'-DDE, HCH, DMDT, aldrin, dieldrin) and their changes in herbal raw materials commercially manufactured in Poland within the period of 1980-1984 have been analyzed (qualitative analyses by TLC, quantitation by GLC). Higher levels of these compounds in 1982 as compared with the periods of 1980-1981 and 1983-1984 has been noticed.

Chromatography, Gas↗