Publication detail
Catalytic mechanism for Renilla-type luciferases
Schenkmayerova, A. Toul, M. Pluskal, D. Baatallah, R. Gagnot, G. Pinto, GP. Santana, VT. Stuchla, M. Neugebauer, P. Chaiyen, P. Damborsky, J. Bednar, D. Janin, YL. Prokop, Z. Marek, M.
Original Title
Catalytic mechanism for Renilla-type luciferases
Type
journal article in Web of Science
Language
English
Original Abstract
The widely used coelenterazine-powered Renilla luciferase was discovered over 40 years ago, but the oxidative mechanism by which it generates blue photons remains unclear. Here we decipher Renilla-type catalysis through crystallographic, spectroscopic and computational experiments. Structures of ancestral and extant luciferases complexed with the substrate-like analogue azacoelenterazine or a reaction product were obtained, providing molecular snapshots of coelenterazine-to-coelenteramide oxidation. Bound coelenterazine adopts a Y-shaped conformation, enabling the deprotonated imidazopyrazinone component to attack O-2 via a radical charge-transfer mechanism. A high emission intensity is secured by an aspartate from a conserved proton-relay system, which protonates the excited coelenteramide product. Another aspartate on the rim of the catalytic pocket fine-tunes the electronic state of coelenteramide and promotes the formation of the blue light-emitting phenolate anion. The results obtained also reveal structural features distinguishing flash-type from glow-type bioluminescence, providing insights that will guide the engineering of next-generation luciferase-luciferin pairs for ultrasensitive optical bioassays.
Keywords
CYPRIDINA LUCIFERIN; PROTEIN CRYSTALLIZATION; BIOLUMINESCENCE; RENIFORMIS; LIGHT; CHEMILUMINESCENCE; COELENTERAZINE; STABILITY; LUMINESCENCE; SPECIFICITY
Authors
Schenkmayerova, A.; Toul, M.; Pluskal, D.; Baatallah, R.; Gagnot, G.; Pinto, GP.; Santana, VT.; Stuchla, M.; Neugebauer, P.; Chaiyen, P.; Damborsky, J.; Bednar, D.; Janin, YL.; Prokop, Z.; Marek, M.
Released
1. 1. 2023
Publisher
NATURE PORTFOLIO
Location
BERLIN
ISBN
2520-1158
Periodical
Nature Catalysis
Year of study
6
Number
1
State
United Kingdom of Great Britain and Northern Ireland
Pages from
23
Pages to
38
Pages count
16
URL
BibTex
@article{BUT183685,
author="Schenkmayerova, A. and Toul, M. and Pluskal, D. and Baatallah, R. and Gagnot, G. and Pinto, GP. and Santana, VT. and Stuchla, M. and Neugebauer, P. and Chaiyen, P. and Damborsky, J. and Bednar, D. and Janin, YL. and Prokop, Z. and Marek, M.",
title="Catalytic mechanism for Renilla-type luciferases",
journal="Nature Catalysis",
year="2023",
volume="6",
number="1",
pages="23--38",
doi="10.1038/s41929-022-00895-z",
issn="2520-1158",
url="https://www.nature.com/articles/s41929-022-00895-z"
}