| Norbadione a: kinetics and thermodynamics of cesium uptake in aqueous and alcoholic media. | |
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MedLine Citation:
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PMID: 20831226 Owner: NLM Status: MEDLINE |
Abstract/OtherAbstract:
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Norbadione A (NbA) is a mushroom pigment, which is assumed to be involved in (137)Cs accumulation all over Europe during the Chernobyl nuclear accident. NbA bears seven acid-base functional groups, among which are two enolic and two carboxylic acid moieties. This work deals with complex formation of Cs(+) and NbA in ethanol, ethanol/water (9:1) (M1), and water with, when required, the support of two Cs(+) ionophore probes, calix[4]arene-bis(crown-6-ether)dioxycoumarine (A1) and its tetrasuslfonated form (A2). In ethanol, two Cs(+) complexes are formed, with the affinity constants K(1EtOH) = (1.1 ± 0.25) × 10(5) and K(2EtOH) = (2.1 ± 0.4) × 10(3). In M1, a single Cs(+) complex occurs when only the enols are deprotonated, whereas a bicomplex is formed when both enols and carboxylic acids are deprotonated: K(1M1) = (1.5 ± 0.3) × 10(5) and K(2M1) = (4 ± 2) × 10(3). These data are confirmed by stopped-flow and T-jump kinetics. In ethanol, a fast Cs(+) exchange occurs between NbA and A1: direct rate constant, k(1) = (3.1 ± 0.1) × 10(7) M(-1) s(-1); reverse rate constant k(-1) = (2.8 ± 1) × 10(5) M(-1) s(-1); and Cs(+) exchange constant, K(1Exchange) = (9 ± 4) × 10(-3). In M1, the quenching of A2 fluorescence by NbA is used to determine the kinetics of complex formation with Cs(+): k(2) = (1.8 ± 0.4) × 10(9) M(-1) s(-1); k(-2) = (1.80 ± 0.15) × 10(4) s(-1); and K(1M1) = (1.5 ± 0.5) × 10(5). The affinity of NbA for Cs(+) is probably the result of the particular structure in which the two pulvinic acid arms adopt a conformation that forms two complexation sites composed of the two enolates and/or the two carboxylates. This renders the efficiency in Cs(+) uptake comparable to that of some calixarenes or crown ethers. |
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Authors:
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Alexandre Korovitch; Jean-Baptiste Mulon; Vincent Souchon; Isabelle Leray; Bernard Valeur; Aurélie Mallinger; Brice Nadal; Thierry Le Gall; Claude Lion; Nguyêt-Thanh Ha-Duong; Jean-Michel El Hage Chahine |
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Publication Detail:
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Type: Journal Article; Research Support, Non-U.S. Gov't |
Journal Detail:
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Title: The journal of physical chemistry. B Volume: 114 ISSN: 1520-5207 ISO Abbreviation: J Phys Chem B Publication Date: 2010 Oct |
Date Detail:
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Created Date: 2010-09-30 Completed Date: 2011-01-18 Revised Date: - |
Medline Journal Info:
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Nlm Unique ID: 101157530 Medline TA: J Phys Chem B Country: United States |
Other Details:
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Languages: eng Pagination: 12655-65 Citation Subset: IM |
Affiliation:
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Interfaces, Traitements, Organisation et Dynamique des Systèmes, Université Paris 7-CNRS UMR 7086, Bât. Lavoisier, 15 rue Jean Antoine de Baïf, 75205 Paris Cedex 13, France. |
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| MeSH Terms | |
Descriptor/Qualifier:
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4-Butyrolactone
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analogs & derivatives*,
chemistry Agaricales / chemistry Cesium / chemistry*, metabolism Cesium Radioisotopes / chemistry, metabolism Coordination Complexes / chemistry Ethanol / chemistry* Hydrogen-Ion Concentration Kinetics Phenylacetates / chemistry* Thermodynamics Water / chemistry* |
| Chemical | |
Reg. No./Substance:
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0/Cesium Radioisotopes; 0/Coordination Complexes; 0/Phenylacetates; 64-17-5/Ethanol; 7440-46-2/Cesium; 7732-18-5/Water; 90295-68-4/norbadione A; 96-48-0/4-Butyrolactone |
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