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Issue 38, 2011
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Coordination of uranium(VI) with functional groups of bacterial lipopolysaccharide studied by EXAFS and FT-IR spectroscopy

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Abstract

The complexation of uranyl ions with lipopolysaccharide (LPS), the main component of the cell wall of Gram-negative bacteria, was investigated on a molecular level with U LIII-edge extended X-ray absorption fine structure (EXAFS) and attenuated total reflection Fourier transform infrared (ATR-FT-IR) spectroscopy over a wide pH range (2.6 to 7.0). For the first time, structural determinations of uranyl complexes with cell wall compounds were extended from acidic up to neutral pH. The main functionalities responsible for uranyl binding are phosphoryl and carboxyl groups. At an excess of LPS, related to environmental conditions, the uranyl ion is mainly complexed by phosphoryl groups four-fold monodentately coordinated in the equatorial plane of the uranyl dioxo cation UO22+ showing great homologies to the uranyl mineral phase meta-autunite in the EXAFS spectra. At equimolar ratios of uranyl and functional groups of LPS, according to a slight deficit of phosphoryl groups, additional carboxyl coordination in a bidentate manner becomes important as it is shown by IR spectroscopy. From the vibrational spectra, a mixed coordination of UO22+ with both phosphoryl and carboxyl groups is derived. The coordination of uranyl ions to the LPS molecule is obviously mainly controlled by the U/LPS concentration ratio, and the influence of pH is only of minor significance at the investigated range.

Graphical abstract: Coordination of uranium(vi) with functional groups of bacterial lipopolysaccharide studied by EXAFS and FT-IR spectroscopy

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Publication details

The article was received on 31 Mar 2011, accepted on 18 Jul 2011 and first published on 30 Aug 2011


Article type: Paper
DOI: 10.1039/C1DT10546A
Citation: Dalton Trans., 2011,40, 9868-9876
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    Coordination of uranium(VI) with functional groups of bacterial lipopolysaccharide studied by EXAFS and FT-IR spectroscopy

    A. Barkleit, H. Foerstendorf, B. Li, A. Rossberg, H. Moll and G. Bernhard, Dalton Trans., 2011, 40, 9868
    DOI: 10.1039/C1DT10546A

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