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Mechanisms of pentachlorophenol induced charge transport in lipid membranes

Pentachlorophenol (PCP) is one of the prominent environmental pollutant that has penetrated into food chain and is present in humans. Health concerns have been raised since daily intake of PCP by the US population is estimated to be 16-19 µg. PCP facilitates dissipation of electrochemical potential gradients of hydrogen ions across energy transducing membranes, which are the energy sources for the conversion of adenosine diphosphate into adenosine triphosphate. Closely linked to these dissipative effects is the development of electrical conductivity in lipid membranes, induced by the presence of PCP. Three modes of PCP - induced membrane electrical conductivity were theoretically analyzed and experimentally verifiable formulations of each models were developed. Experimental studies using the charge - pulse method involved characterization of the time dependent transmembrane voltage over a wide pH range, from 1.8 to 9.5, for 30 µM concentrations of PCP. Lipid membranes were prepared from dioleoyl phosphatidylcholine. It was shown that three PCP molecular species were determining the transmembrane transfer of hydrogen ions: electrically neutral PCP molecules (HA), negatively charged pentachlorophenolate ions (A⁻) and negatively charged heterodimers (AHA⁻). It was found that at pH>9 the membrane electrical conductivity was determined by the transmembrane movement of A⁻ ions, whenever pHAHA⁻ species. Two new membrane surface reactions were proposed as supplementary mechanisms for the generation of AHA⁻ in addition to the formation of AHA⁻ by the recombination of HA and A⁻, HA + A⁻→ AHA⁻. These new reactions are, (i) 2HA → H⁺ + AHA⁻, and (ii) H20 + 2A⁻ → OH' + AHA⁻. Reaction (i) provides formation of membrane permeable heterodimers AHA⁻ at pH < < 5.5 and reaction (ii) at pH> > 5.5. The maximum surface density of AHA" heterodimers was 0.09 pmol/cm² • The rate constant of formation of AHA' by recombination, HA + A⁻ → AHA' was estimated to be k[subscript f] = 2.6xl0⁹ cm² mol⁻¹ s⁻¹ and the dissociation rate constant for AHA⁻ Further, it was possible to determine the rate constants of transmembrane translocation for A' and AHA⁻ ions to be k[subscript a] = 6.6x10⁻⁵ s⁻¹ and k[subscript aha] = 1200 S⁻¹, respectively.

Identiferoai:union.ndltd.org:pdx.edu/oai:pdxscholar.library.pdx.edu:open_access_etds-2256
Date01 January 1996
CreatorsBrown, William Charles
PublisherPDXScholar
Source SetsPortland State University
Detected LanguageEnglish
Typetext
Formatapplication/pdf
SourceDissertations and Theses

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