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Electrochemical Ester Hydrolysis.pdf (820.52 kB)

Membrane Trafficking Inspired Hydrolysis of Non-Activated Esters at Physiological pH

preprint
submitted on 02.03.2020, 10:02 and posted on 03.03.2020, 07:47 by Pradip Kumar Tarafdar, Suman De Sarkar, Raki Mandal, Kingshuk Mahanty, Subhendu Mandal
Natural enzymes establish the proximity of the substrates to perform challenging reactions in aqueous medium, whereas most chemical catalysts typically follow stochastic way and are less efficient. Inspired by the membrane trafficking, a core biological process, herein we report that positively charged micro heterogeneous vehicles loaded with substrate could be trafficked suitably at the site of the reaction to promote the localization and proximity of the reactants. The guided vehicular delivery coupled with electrolysis overcomes the entropic barrier related to the proximity of the reactants and allows the hydrolysis of non-activated esters at physiological pH. Mechanistic investigations suggest that the reaction utilizes the electrochemical energy to generate hydroxide ion at the cathode and the positively charged micellar vehicles (loaded with substrates) trafficked selectively near cathode to promote the hydrolysis. The in situ modulation of surface charge was exploited to accelerate or inhibit the hydrolysis in a controlled manner akin to cofactors or zymogens of natural enzymes. We believe this elegant membrane trafficking inspired approach paves the way for the further applications of proximity controlled selective transformations in organic synthesis using green aqueous medium.

Funding

DST-Inspire (IFA13-CH-120, 2014)

Early Career Award (ECR/2016/001935)

History

Email Address of Submitting Author

srpradip@gmail.com

Institution

Indian Institute of Science Education and Research Kolkata

Country

India

ORCID For Submitting Author

0000-0002-1059-950X

Declaration of Conflict of Interest

No.

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ChemRxiv

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