Preferential Binding of Lanthanides to Methanol Dehydrogenase Evaluated with Density Functional Theory.

Ran Friedman

doi:10.1021/acs.jpcb.0c11077

Abstract

Methanol dehydrogenase (MDH) is an enzyme used by certain bacteria for the oxidation of methanol to formaldehyde, which is a necessary metabolic reaction. The discovery of a lanthanide-dependent MDH reveals that lanthanide ions (Ln3+) have a role in biology. Two types of MDH exist in methane-utilizing bacteria: one that is Ca2+-dependent (MxaF) and another that is Ln3+-dependent. Given that the triply charged Ln3+ are strongly hydrated, it is not clear how preference for Ln3+ is manifested and if the Ca2+-dependent MxaF protein can also bind Ln3+ ions. A computational approach was used to estimate the Gibbs energy differences between the binding of Ln3+ and Ca2+ to MDH using density functional theory. The results show that both proteins bind La3+ with higher affinity than Ca2+, albeit with a more pronounced difference in the case of Ln3+-dependent MDH. Interestingly, the binding of heavier lanthanides is preferred over the binding of La3+, with Gd3+ showing the highest affinity for both proteins of all Ln3+ ions that were tested (La3+, Sm3+, Gd3+, Dy3+, and Lu3+). Energy decomposition analysis reveals that the higher affinity of La3+ than Ca2+ to MDH is due to stronger contributions of electrostatics and polarization, which overcome the high cost of desolvating the ion.

Highlights

Lanthanides are a group of metal elements with atomic numbers 57−71
They are often regarded as rare earth metals, lanthanides are quite abundant; even the rarest lanthanide, lutetium, is more abundant than silver and cadmium
Lanthanides are used in metallurgy, catalysis, and electronics; some lanthanide complexes have even medical uses

Summary

Introduction

Lanthanides are a group of metal elements with atomic numbers 57−71. they are often regarded as rare earth metals, lanthanides (except for the radioactive 61Pm, which is not considered further in this article) are quite abundant; even the rarest lanthanide, lutetium, is more abundant than silver and cadmium. The ions tend to have hard ligands such as O and F and can adopt a large variety of configurations, with coordination numbers (CNs) that range between 2 and 12. Their similar chemistry and the fact that many lanthanides are located together in the same ore make it difficult to separate them. A major difference between the lanthanides is their ionic radius, with the heavier lanthanides having smaller radii (a phenomenon that is termed “lanthanide contraction”). This has some impact on their chemical properties as well, which can be exemplified in their hydration properties.

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