STRUCTURAL BASIS FOR ENGINEERED THERMOSTABILITY IN HALOALKANE DEHALOGENASES

Martin Marek1*, Klara Markova1,2, Klaudia Chmelova1,2, Sergio M. Marques1,2,
David Bednar1,2, Jiri Damborsky1,2

1Loschmidt Laboratories, Department of Experimental Biology and RECETOX, Masaryk University, Kamenice 5, 62500 Brno, Czech Republic

2International Clinical Research Center, St. Anne’s University Hospital Brno, Pekarska 53, 65691 Brno, Czech Republic
martin.marek@recetox.muni.cz


Enhancing protein robustness is crucial for fundamental research as well as for technological applications. Our previous computational protein design effort yielded an 11-point mutant haloalkane dehalogenase DhaA115 with outstanding thermostability (Tm = 73.5 °C,
DTm = 24 °C). Precise understanding of molecular basis for this thermostability remained sparse. Here we report 1.55 Å and 1.6 Å resolution structures of DhaA115 obtained by X-ray crystallography. We show that the placement of bulky aromatic amino acids on the protein surface triggered novel long-distance backbone changes, establishing a new double-lock system that: (i) closed access gates, (ii) reduced volumes of both main and slot access tunnels, and (iii) made the active site occluded. Despite of these extensive structural changes, experimental tracking of entry pathways by high-pressure krypton derivatization of DhaA115 crystals revealed transport of small ligands through enzyme’s tunnels. Experimental observations are in full agreement with the results from computer simulations. Our findings unravel a novel structural basis of enzyme thermostabilisation, which will pave the way for designing highly thermostable biocatalysts and therapeutics.

This work was supported by MSCA Marie Sklodowska-Curie Actions (792772) and GAMU (MUNI/H/1561/2018).