Rhodococcus erythropolis is a promising Gram-positive bacterium capable of numerous bioconversions including those involving alcohol dehydrogenases (ADHs). In this work, we compared and optimized the redox biocatalytic performances of 1-butanol-grown R. erythropolis NCIMB 13064 cells in aqueous and in non-conventional gas phase using the 1-butanol–hexanal oxidation–reduction as model reaction. Oxidation of 1-butanol to butanal is tightly coupled to the reduction of hexanal to 1-hexanol at the level of a nicotinoprotein–ADH-like enzyme. Cell viability is dispensable for reaction. In aqueous batch conditions, fresh and lyophilized cells are efficient redox catalysts (oxidation–reduction rate = 76 micromol min−1 g cell dry mass−1) being also reactive towards benzyl alcohol, (S)-2-pentanol, and geraniol as reductants. However, butanol hexanal oxidation–reduction is strongly limited by product accumulation and by hexanal toxicity that is amajor factor influencing cell behavior and performance. Reaction rate is maximal at 40 ◦C pH 7.0 in aqueous phase and at 60 ◦C- pH 7.0–9.0 in gas phase. Importantly, lyophilized cells also showed to be promising redox catalysts in the gas phase (at least 65 micromol min−1 g cell dry mass−1). The system is notably stable for several days at moderate thermodynamic activities of hexanal (0.06–0.12), 1-butanol (0.12) and water (0.7)
