Wide-dynamic-range Kinetic Investigations of Deep Proton Tunnelling in Proteins

Overview

Journal Nat Chem

Specialty Chemistry

Date 2016 Aug 25

PMID 27554414

Citations 11

Authors

Bridget Salna

Abdelkrim Benabbas

J Timothy Sage

Jasper van Thor

Paul M Champion

Affiliations

Soon will be listed here.

Abstract

Directional proton transport along 'wires' that feed biochemical reactions in proteins is poorly understood. Amino-acid residues with high pKa are seldom considered as active transport elements in such wires because of their large classical barrier for proton dissociation. Here, we use the light-triggered proton wire of the green fluorescent protein to study its ground-electronic-state proton-transport kinetics, revealing a large temperature-dependent kinetic isotope effect. We show that 'deep' proton tunnelling between hydrogen-bonded oxygen atoms with a typical donor-acceptor distance of 2.7-2.8 Å fully accounts for the rates at all temperatures, including the unexpectedly large value (2.5 × 10(9) s(-1)) found at room temperature. The rate-limiting step in green fluorescent protein is assigned to tunnelling of the ionization-resistant serine hydroxyl proton. This suggests how high-pKa residues within a proton wire can act as a 'tunnel diode' to kinetically trap protons and control the direction of proton flow.

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