Self-Assembled Amphiphile Assisted Hydrolytic and C-C Bond Formation Reactions in Water

Mandal, Raki (2023) Self-Assembled Amphiphile Assisted Hydrolytic and C-C Bond Formation Reactions in Water. PhD thesis, Indian Institute of Science Education and Research Kolkata.

Text (PhD thesis of Raki Mandal (17RS040)) 17RS040.pdf - Submitted Version Restricted to Repository staff only Download (15MB)

Abstract

My thesis' objective is to investigate the catalytic or hydrolytic role of prebiotic amphiphiles and organic reactions in aqueous medium by mimicking nature. Even though there have been significant advances in research, many areas still need to be investigated. In chapter 2, we investigated the formation of amino-acid-based amphiphiles (N-acylated and O-acylated) and their catalytic/hydrolysis activity. Prebiotic amino-acid-based surfaces served as an efficient catalyst that exhibits regulation of catalytic function, substrate selectivity, and further adaptability to perform bio-catalysis. But this mixed amphiphilic system is not suitable to hydrolyse normal/stable ester. In chapter 3. inspired by natural membrane transport, we report that positively charged micro heterogeneous vehicles loaded with substrate could be trafficked suitably at the reaction site to promote the reactants' localization. The guided vehicular delivery coupled with electrolysis overcomes the entropic barrier related to the propinquity of the reactants and allows the hydrolysis of non-activated esters at physiological pH. In chapter 4, we applied the membrane transport inspired electrochemical method to hydrolyse stable plasticizer esters, key additives of many plastics at neutral pH. We designed choline-based amphiphiles N-lauryl choline (NLC), the mimic of serine protease like nucleophile and thiocholine-based nucleophilic amphiphiles N-lauryl thiocholine (NLTC), the mimic of cysteine protease like nucleophile to carry out the hydrolysis reactions at a bulk pH close to the physiological pH. These nucleophilic amphiphiles can tune the pKa of hydroxy or thiol group via self-assembly and thus useful to carry out hydrolysis of highly stable benzoate and phthalate esters. In chapter 5, We used this elegant approach for base promoted Aldol reaction. In chapter 6, we used membrane transport based elegant approach for electron transfer radical based benzoin type reactions via the guided delivery of the substrate close to the electrodes in the aqueous medium.

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