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Measuring the Micro-Polarity and Hydrogen-Bond Donor/Acceptor Ability of Thermoresponsive N-Isopropylacrylamide/N-tert-Butylacrylamide Copolymer Films Using Solvatochromic Indicators

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Abstract:

Thin polymer films are important in many areas of biomaterials research, biomedical devices, and biological sensors. The accurate in situ measurement of multiple physicochemical properties of thin polymer films is critical in understanding biocompatibility, polymer function, and performance. In this work we demonstrate a facile spectroscopic methodology for accurately measuring the micro-polarity and hydrogen-bond donor/acceptor ability for a series of relatively hydrophilic thermoresponsive copolymers. The micro-polarity of the N-isopropylacrylamide (NIPAM) and N-tert-butylacrylamide (NtBA) co-polymers was evaluated by means of the E T(30), α, β, and π* empirical solvatochromic polarity parameters. The data shows that increasing the NtBA fraction in the dry copolymer film reduces polarity and hydrogen-bonding ability. Within the Kamlet–Taft polarity framework, the NIPAM/NtBA copolymer films are strong hydrogen-bond acceptors, strongly dipolar/polarizable, and rather moderate hydrogen-bond donors. This characterization provides a more comprehensive physicochemical description of polymers, which aids the interpretation of film performance. Comparison of the measured E T(30) values with literature data for other water-soluble polymers show that dry NIPAM/NtBA copolymers are slightly more polar than poly(ethylene oxide), less polar than polyvinylalcohol, and approximately the same polarity as poly(N-vinyl-2-pyrrolidone). These findings indicate that this spectroscopic method is a facile, rapid, and nondestructive methodology for measuring polymer properties in situ, suitable for most biomaterials research laboratories.

Keywords: N-ISOPROPYLACRYLAMIDE; N-TERT-BUTYLACRYLAMIDE; POLARITY; SOLVATOCHROMISM; THERMO-RESPONSIVE COPOLYMER FILMS; THIN POLYMER FILMS

Document Type: Research Article

DOI: http://dx.doi.org/10.1366/000370209787944343

Affiliations: 1: Nanoscale Biophotonics Laboratory, School of Chemistry, National University of Ireland, Galway, Galway, Ireland; School of Physics, National University of Ireland, Galway, Galway, Ireland 2: Nanoscale Biophotonics Laboratory, School of Chemistry, National University of Ireland, Galway, Galway, Ireland; National Centre for Biomedical Engineering Sciences, National University of Ireland, Galway, Galway, Ireland 3: National Centre for Biomedical Engineering Sciences, National University of Ireland, Galway, Galway, Ireland 4: School of Chemistry & Chemical Biology, University College Dublin, Ireland 5: School of Physics, National University of Ireland, Galway, Galway, Ireland

Publication date: April 1, 2009

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