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Fig 1.

Three-dimensional model of HvADH2 active site in complex with different docked ligands.

A) Complex with (S)-1-PheOH. B) LigPlot analysis of the interactions between docked (S)-1-PheOH and HvADH2 model. The substrate is in purple. Hydrophobic contacts are shown as dark red arches. C) Complex with (S)-flurbiprofenol. D) Complex with (S)-flurbiprofenol, surface representation. The ligands are represented as white sticks or spheres. The NAD+ cofactor is in yellow and Zn2+ is represented as a pink sphere. Important residues are shown in green; the αC of G294 is shown as a sphere. The π-π staking interactions are shown by dotted lines and H-bonds by dashed lines.

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Fig 1 Expand

Fig 2.

Sequence alignment of HvADH2 with top 9 homologues.

3KRT: putative crotonyl CoA reductase from Streptomyces coelicolor. 1KOL: Formaldehyde dehydrogenase from Pseudomonas putida. 2DPH: Formaldehyde dismutase from Pseudomonas putida. 1HF3: liver alcohol dehydrogenase from Equus caballus. 1H2B alcohol dehydrogenase from Aeropyrum pernix. 4A10: 2-octenoyl-CoA carboxylase reductase from Streptomyces sp. JS360. 2CDB: glucose dehydrogenase from Sulfolobus solfataricus. 1F8F: benzyl alcohol dehydrogenase from Acinetobacter calcoaceticus. 1MAO: glutathione-dependent formaldehyde dehydrogenase from Homo sapiens.

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Fig 2 Expand

Fig 3.

F108L docked (F85 blue spheres and L108 purple spheres; NAD+, yellow sticks) with (S)-flurbiprofenol (white spheres), surface view.

The distance from the hydroxyl oxygen to the catalytic zinc (O-Zn) is 4.4 Å, and the distance from the substrate α-carbon to the C4 of the nicotinamide ring (αC-C4), is 5.9.

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Fig 3 Expand

Table 1.

Activity of purified wild-type and F108 variants of HvADH2 with rac-flurbiprofenol.

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Table 1 Expand

Fig 4.

Substrate specificity of purified F108G variant compared to WT HvADH2.

Buffer conditions: 4 M KCl, 50 mM Gly-KOH, pH 10.0.

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Fig 4 Expand

Fig 5.

Docking of (R)-1-PheOH (white spheres).

A) Catalytic site of the WT enzyme (F85 and F108 green spheres, NAD+, yellow sticks) shows stabilization of the substrate aromatic ring by F108. The distance from the hydroxyl oxygen to the catalytic zinc (O-Zn) is 4.6 Å, and the distance from the substrate α-carbon to the C4 of the nicotinamide ring (αC-C4), is 5.7 Å. B) Catalytic site of the F108G variant. The distance from the hydroxyl oxygen to the catalytic zinc (O-Zn) is 2.5 Å, and the distance from the substrate α-carbon to the C4 of the nicotinamide ring (αC-C4), is 4.0 Å.

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Fig 5 Expand