title: Specific counterion repercussions on the thermal, pH-response, and electrochemical properties of side-chain leucine based chiral polyelectrolytes.
abstract: Effects of counterions of side chain amino acid based polyelectrolytes (PEs) on the solubility in aqueous medium, pH responsiveness, thermal properties, and ionic conductivities have been appraised. Deprotection of the tert-butyl carbamate (Boc) group from poly(Boc-l-leucine methacryloyloxyethyl ester) [P(Boc-l-Leu-HEMA)] was carried out to produce PE with trifluoroacetate as an associative counteranion (1a). PEs with bis(trifluoromethylsulfonyl)imide and hexafluorophosphate counteranion were prepared through anion exchange reactions of 1a. Protonation of the neutralized polymer (2) obtained from 1a, followed by anion exchange, leads to the production of miscellaneous PEs bearing different counteranions, such as tetrafluoroborate, trifluoromethanesulfonate, chloride, and nitrate. Differential scanning calorimetry traces of the PEs reveal that the comparatively larger and weakly coordinated counteranions require less thermal energy to dissociate, and thus, the glass transition temperature (Tg) of the PEs fall off with an increase in the size of the counteranion. A remarkable conductivity of 2.1 mS/cm was obtained in deionized water when Cl(-) acted as the counteranion. Steric and electronic factors of the counteranion induce a change of transition pH in different PEs, although the chiroptical nature was retained, as confirmed by circular dichroism spectroscopy.
authors.affiliation: Polymer Research Centre, Department of Chemical Sciences, Indian Institute of Science Education and Research Kolkata , Mohanpur-741246, Nadia, West Bengal, India.
authors.forename: Amal
authors.initials: A
authors.lastname: Narayanan
authors.forename: Kamal
authors.initials: K
authors.lastname: Bauri
authors.forename: Bhuban
authors.initials: B
authors.lastname: Ruidas
authors.forename: Goutam
authors.initials: G
authors.lastname: Pradhan
authors.forename: Sanjib
authors.initials: S
authors.lastname: Banerjee
authors.forename: Priyadarsi
authors.initials: P
authors.lastname: De