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Cadmium in Metallothioneins

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Cadmium: From Toxicity to Essentiality

Part of the book series: Metal Ions in Life Sciences ((MILS,volume 11))

Abstract

Metallothioneins (MTs) are low-molecular-mass cysteine-rich proteins with the ability to bind mono- and divalent metal ions with the electron configuration d 10 in form of metal-thiolate clusters. MTs are thought, among others, to play a role in the homeostasis of essential Zn(II) and Cu(I) ions. Besides these metal ions also Cd(II) can be bound to certain MTs in vivo, giving rise to the perception that another physiological role of MTs is in the detoxification of heavy metal ions. Substitution of the spectroscopically silent Zn(II) ions in metalloproteins by Cd(II) proved to be an indispensable tool to probe the Zn(II) sites in vitro. In this review, methods applied in the studies of structural and chemical properties of Cd-MTs are presented. The first section focuses on the physical basis of spectroscopic techniques such as electronic absorption, circular dichroism (CD), magnetic CD, X-ray absorption, and perturbed angular correlation of γ-rays spectroscopy, as well as mass spectrometry, and their applications to Cd-MTs from different organisms. The following is devoted to the discussion of metal binding affinities of Cd-MTs, cluster dynamics, the reactivity of bound Cd(II) ions with metal ion chelators and of thiolate ligands with alkylating and oxidizing agents. Finally, a brief summary of the known three-dimensional structures of Cd-MTs, determined almost exclusively by multinuclear NMR techniques, is presented. Besides Cd-MTs, the described methods can also be applied to the study of metal binding sites in other metalloproteins.

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Abbreviations

5F-BAPTA:

1,2 -bis-(2-amino-5-fluorophenoxy)ethane-N, N, N’,N’-tetraacetic acid

CD:

circular dichroism

COSY:

correlation spectroscopy

CTTS:

charge-transfer-to-solvent

Cys:

cysteine

DTNB:

5,5’-dithiobis-(2-nitrobenzoic acid)

EDTA:

ethylenediamine-N,N,N’,N’-tetraacetate

EPR:

electron spin resonance

ESI:

electrospray ionization

EXAFS:

extended X-ray absorption fine structure

FT-IR:

Fourier transform infrared (spectroscopy)

GIF:

growth inhibitory factor

GST:

glutathione-S-transferase

His:

histidine

HSQC:

heteronuclear single quantum coherence

LLCT:

ligand-to-ligand charge-transfer

LMCT:

ligand-to-metal charge-transfer

LUMO:

lowest unoccupied molecular orbital

MALDI:

matrix assisted laser desorption ionisation

MCD:

magnetic circular dichroism

MD:

molecular dynamics

MM:

molecular mechanics

MO:

molecular orbital

MS:

mass spectrometry

MT:

metallothionein

NMR:

nuclear magnetic resonance

NOE:

nuclear Overhauser effect

NQI:

nuclear quadrupole interaction

NTA:

nitrilotriacetate

PAC:

perturbed angular correlation

PDB:

Protein Data Bank

RMSD:

root-mean-square deviation

XANES:

X-ray absorption near-edge structure

XAS:

X-ray absorption spectroscopy

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Acknowledgment

Financial support by the Swiss National Science Foundation (SNSF Professorship PP002-119106/1 to E.F.) is gratefully acknowledged.

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  1. Institute of Inorganic Chemistry, University of Zürich, Winterthurerstrasse 190, CH-8057, Zürich, Switzerland

    Eva Freisinger & Milan Vašák

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  1. Eva Freisinger
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  2. Milan Vašák
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Correspondence to Eva Freisinger or Milan Vašák .

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  1. Inorganic Chemistry, Chemistry, Universität Basel, Spitalstr. 51, Basel, 4056, Basel Stadt, Switzerland

    Astrid Sigel

  2. Inst. Anorganische Chemie, Universität Basel, Spitalstr. 51, Basel, 4056, Switzerland

    Helmut Sigel

  3. Institute of Inorganic Chemistry, University of Zürich, Winterthurerstrasse 190, Zürich, 8057, Zürich, Switzerland

    Roland KO Sigel

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Freisinger, E., Vašák, M. (2013). Cadmium in Metallothioneins. In: Sigel, A., Sigel, H., Sigel, R. (eds) Cadmium: From Toxicity to Essentiality. Metal Ions in Life Sciences, vol 11. Springer, Dordrecht. https://doi.org/10.1007/978-94-007-5179-8_11

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