Investigation into mercury bound to biothiols: structural identification using ESI-ion-trap MS and introduction of a method for their HPLC separation with simultaneous detection by ICP-MS and ESI-MS.
Mercury in plants or animal tissue is supposed to occur in the form of complexes formed with biologically relevant thiols (biothiols), rather than as free cation. We describe a technique for the separation and molecular identification of mercury and methylmercury complexes derived from their reactions with cysteine (Cys) and glutathione (GS): Hg(Cys)(2), Hg(GS)(2), MeHgCys, MeHgGS. Complexes were characterised by electrospray mass spectrometry (MS) equipped with an ion trap and the fragmentation pattern of MeHgCys was explained by using MP2 and B3LYP calculations, showing the importance of mercury-amine interactions in the gas phase. Chromatographic baseline separation was performed within 10 min with formic acid as the mobile phase on a reversed-phase column. Detection was done by online simultaneous coupling of ES-MS and inductively coupled plasma MS. When the mercury complexes were spiked in real samples (plant extracts), no perturbation of the separation and detection conditions was observed, suggesting that this method is capable of detecting mercury biothiol complexes in plants.
Krupp
Eva M
EM
College of Physical Sciences, University of Aberdeen, Meston Walk, Aberdeen, AB24 3UE, UK. e.krupp@abdn.ac.uk
Milne
Bruce F
BF
Mestrot
Adrien
A
Meharg
Andrew A
AA
Feldmann
Jörg
J
D002851:Chromatography, High Pressure Liquid / Q000295:instrumentation / Q000379:methods; D013058:Mass Spectrometry / Q000295:instrumentation / Q000379:methods*; D008628:Mercury / Q000032:analysis*; D008956:Models, Chemical; D009941:Organomercury Compounds / Q000032:analysis*; D012275:Oryza / Q000737:chemistry; D011789:Quantum Theory; D015203:Reproducibility of Results; D012680:Sensitivity and Specificity; D021241:Spectrometry, Mass, Electrospray Ionization / Q000295:instrumentation / Q000379:methods*; D013438:Sulfhydryl Compounds / Q000032:analysis*; D013997:Time Factors
D009941:Organomercury Compounds; D013438:Sulfhydryl Compounds; D008628:Mercury