Microbiological versus Chemical Reductive Sulfidation: An Experimental and Theoretical Study

Microbiological reductive sulfidation (RS) has rarely been documented, although it represents an efficient strategy for thiol formation. In this work, we reported on the sulfate-respiring bacterium Desulfovibrio sp.86 that previously demonstrated RS activity toward pesticide chlordecone. The purpose of study was to assess its substrate versatility using a set 28 carbonyls, compare with chemical and rationalize observed trends dual experimental theoretical approach. generally proceeds in two steps (S/O exchange sulfur donor like P4S10, reduction thione intermediate). Intriguingly, chlordecone found be converted into chlordecthiol following first step. Hence, designed protocol applied substrates their propensity directly thiols P4S10 treatment alone. Finally, performed density functional theory calculations these carbonyls thiocarbonyl derivatives build structural, electronic, thermodynamic parameters. results showed microbiological probably involved distinct mechanisms. Chemically, several possessing electron-withdrawing groups and/or aromatic rings, were transformed presence P4S10. correlation obtained electron affinity thiones led us conclude probable single-electron transfer occurred during We also variety aldehydes ketones, without ever detecting thiones. No significant calculated parameters, but relationship between aldehyde biotransformation bacterial growth observed. Differences selectivity open way further applications organic synthesis.