title: X-ray absorption spectroscopy of cadmium phytochelatin and model systems.
abstract: Higher plants, algae and some yeasts respond to potentially toxic heavy metals such as cadmium by synthesizing phytochelatins and related cysteine-rich polypeptides. We have used X-ray absorption spectroscopy to study the nature of cadmium binding in such peptides isolated from maize (Zea mays) exposed to low levels of cadmium, and in two synthetic cadmium-peptide complexes, Cd-(gamma-Glu-Cys)3Gly and Cd-(alpha-Glu-Cys)3Gly. We have used the synthetic ions [Cd(SPh)4]2-, [Cd4(SPh)10]2- and [S4Cd10(SPh)16]4-as crystallographically defined models for the cadmium site. The Cd K-edge extended X-ray absorption fine structure (EXAFS) data, together with the Cd K, LI, LII and LIII near-edge spectra, reveal a predominantly tetrahedral coordination of cadmium by sulfur in both the phytochelatin and synthetic peptide complexes. In particular, the Cd LIII-edge lacks a peak at 3534.9 e V which was found to be prominent for oxygen- or nitrogen-coordinated species. The Cd-S distance in the phytochelatin complex is 2.54 A. The Cd K-edge EXAFS does not show any isolated, well-defined Cd-Cd interactions; however, contrary to the conclusion of previous work, their absence is not necessarily indicative of isolated cadmium-thiolate ligation. Evidence from other studies suggests that high static disorder, combined with a large vibrational component, serve to effectively wash out this contribution to the EXAFS. The sulfur K-edge, moreover, shows a low-energy feature both in the phytochelatin and in the synthetic cadmium-peptide complexes which is consistent with sulfide bound in a cluster with cadmium as found for [S4Cd10(SPh)16]4-. This feature strongly suggests the presence of a polynuclear cadmium cluster in maize phytochelatin.
authors.affiliation: Stanford Synchrotron Radiation Laboratory, Stanford University, CA 94309, USA. pickering@ssrl.slac.stanford.edu
authors.forename: I J
authors.initials: IJ
authors.lastname: Pickering
authors.forename: R C
authors.initials: RC
authors.lastname: Prince
authors.forename: G N
authors.initials: GN
authors.lastname: George
authors.forename: W E
authors.initials: WE
authors.lastname: Rauser
authors.forename: W A
authors.initials: WA
authors.lastname: Wickramasinghe
authors.forename: A A
authors.initials: AA
authors.lastname: Watson
authors.forename: C T
authors.initials: CT
authors.lastname: Dameron
authors.forename: I G
authors.initials: IG
authors.lastname: Dance
authors.forename: D P
authors.initials: DP
authors.lastname: Fairlie
authors.forename: D E
authors.initials: DE
authors.lastname: Salt
mesh_terms: D002104:Cadmium / Q000737:chemistry*; D005978:Glutathione; D008667:Metalloproteins / Q000737:chemistry* / Q000302:isolation & purification; D008958:Models, Molecular; D009942:Organometallic Compounds / Q000737:chemistry*; D054811:Phytochelatins; D010940:Plant Proteins / Q000737:chemistry* / Q000302:isolation & purification; D013052:Spectrometry, X-Ray Emission; D013438:Sulfhydryl Compounds / Q000737:chemistry; D013440:Sulfides / Q000737:chemistry; D003313:Zea mays