Systematic Insights from Medicinal Chemistry To Discern the Nature of Polymer Hydrophobicity

Andrew J.D. Magenau, Jeffrey A. Richards, Melissa A. Pasquinelli, Daniel A. Savin, Robert T. Mathers

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Abstract

Predicting polymer hydrophobicity based on monomer structure is an ill-posed problem. Generally, the hydrophobicity of a polymer or a series of polymers has been determined through indirect methods (i.e., contact angle) after polymerization. This sequence presents a problem for the systematic design and rapid evaluation of specialty polymers synthesized via controlled polymerization methods. Here, we propose an approach inspired by medicinal chemistry to predict polymer hydrophobicity based on octanol-water partition coefficients (LogPoct) determined through simple computational approaches. We envisioned that LogPoct, analogous to what is used in drug design, could provide a rational methodology to translate molecular structures of monomers and oligomers into quantifiable hydrophobicity values for polymers. A combination of critical design criteria and the predictive power of LogPoct values, normalized by surface area (LogPoct/SA), accurately assess polymer hydrophobicity. Experimental corroboration with a polarity-sensitive dye (i.e., Nile Red), advancing water contact angles measurements, and swelling ratio experiments verify the method represents a dramatic improvement. A direct and quantitative correlation existed between spectral shifts of Nile Red and calculated LogPoct/SA values, confirming a quantifiable metric for predicting polymer hydrophobicity. Computationally predicted values also resulted in a first approximation of advancing contact angle measurements over a broad spectrum of common polymers providing a basis for estimating contact angles, a screening tool to enhanced monomer design a priori, and a criterion to understand polymer physical properties. Furthermore, swelling ratio measurements elucidated boundary limits for swelling of relatively hydrophobic and hydrophilic polymers in water and hexanes, in addition to alternative alcohol derivative solvents.

Original languageEnglish (US)
Pages (from-to)7230-7236
Number of pages7
JournalMacromolecules
Volume48
Issue number19
DOIs
Publication statusPublished - Sep 25 2015

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All Science Journal Classification (ASJC) codes

  • Organic Chemistry
  • Polymers and Plastics
  • Inorganic Chemistry
  • Materials Chemistry

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