Related Experiment Video
Updated: May 31, 2026
09:58
Light-driven Enzymatic Decarboxylation
Published on: May 22, 2016
Employing AC and DC Electrolysis to Modulate Electroenzymatic Pathways for Efficient and Stereoselective H-D Exchange
Wassim El Housseini1, Rokas Gerulskis2, Nibedita Behera2
1Kummer Institute Center for Resource Sustainability, Missouri University of Science and Technology, Rolla, Missouri 65409, United States.
Journal of the American Chemical Society
|May 28, 2026
Summary
This study presents a new electroenzymatic platform for stereoselective hydrogen isotope exchange using electrode-controlled nicotinamide cofactors. The method achieves efficient deuterium labeling in chiral alcohols with high enantiopurity.
Area of Science:
- Biochemistry
- Organic Chemistry
- Electrochemistry
Background:
- Stereoselective hydrogen isotope exchange (HIE) is crucial for preparing labeled molecules.
- Efficient nicotinamide cofactor regeneration is essential for practical HIE implementation.
Purpose of the Study:
- To develop a redox-programmable electroenzymatic platform for stereoselective HIE.
- To enable electrode-controlled manipulation of nicotinamide cofactor states for HIE.
Main Methods:
- A wired ferredoxin-NADP+ reductase (FNR) electrode was used for reversible electrochemical interconversion of NADP+ and NADPD from D2O.
- Coupling cofactor cycling with enantioselective alcohol dehydrogenases (ADHs) created a reversible alcohol-ketone redox manifold.
- Direct-current and alternating-current electrolysis modes were employed to control stereochemical outcomes.
Main Results:
- The platform enabled efficient and stereoselective H-D exchange at chiral alcohols.
- Direct-current electrolysis allowed stereochemical editing using stereocomplementary ADHs.
- Alternating-current electrolysis facilitated stereoretentive labeling via rapid bidirectional cofactor cycling.
- Near-quantitative deuterium incorporation with high enantiopurity was achieved for various secondary alcohols.
Conclusions:
- The developed electroenzymatic platform offers a versatile strategy for stereoselective HIE.
- This approach provides precise control over stereochemical outcomes in deuterium labeling.
- The method is broadly applicable to a wide range of secondary alcohols, enhancing molecular labeling capabilities.
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