Related Experiment Video
Updated: Apr 28, 2026

An Anaerobic Biosensor Assay for the Detection of Mercury and Cadmium
Published on: December 17, 2018
What factors influence the metal-proton spin-spin coupling constants in mercury- and cadmium-substutited rubredoxin?
Małgorzata Kauch1, Magdalena Pecul
1Faculty of Chemistry, University of Warsaw , Pasteura 1, 02-093 Warszawa, Poland.
Abstract:
The indirect metal-proton spin-spin coupling constants between protons in cysteine groups and the mercury or cadmium nucleus have been calculated for a small model of Me-rubredoxin complex (Me = Cd, Hg) by means of density functional theory with zeroth-order regular approximation Hamiltonian (DFT-ZORA). The calculated spin-spin coupling constants, in spite of the moderate size of the model system, are in good agreement with the values measured in NMR experiment, which are in the 0.29-0.56 Hz range for the Cd complex and in the 0.57-2.20 Hz range for the Hg complex. The robustness of the chosen method has been verified by calculations with a number of different exchange-correlation functionals and basis sets. Additionally, it has been shown that the short- and long-distance metal-proton coupling constants are affected mainly by the values of the metal-proton distance and the H-N-C-C dihedral angle.
Related Concept Videos
Colors and Magnetism
When atoms or molecules absorb light at the proper frequency, their electrons are excited to higher-energy orbitals. For many main group atoms and molecules, the absorbed photons are in the ultraviolet range of the electromagnetic spectrum, which cannot be detected by the human eye. For coordination compounds, the energy difference between the d orbitals often allows photons in the visible range to be absorbed and emitted, which is seen as colors by the human...
Spin–Spin Coupling Constant: Overview
Qualitatively, any spin plus-half nucleus polarizes the spins of its electrons to the minus-half state. Consequently, the paired electron in the hydrogen–carbon bond must...
Spin–Spin Coupling: Three-Bond Coupling (Vicinal Coupling)
The extent of coupling depends on the C‑C bond length, the two H‑C‑C angles, any electron-withdrawing substituents, and the dihedral angle between the...
NMR Spectroscopy: Spin–Spin Coupling
Spin–Spin Coupling: One-Bond Coupling
Spin–Spin Coupling: Two-Bond Coupling (Geminal Coupling)
The central atom need not be NMR-active because its electrons are affected by the electron polarization of the spin-active atoms. However, spin information is transmitted less effectively than in one-bond coupling, and 2J values are usually weaker than 1J values. The energy of...

