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Vibrational Frequency Shifts for Monitoring Noncovalent Interactions between Molecular Imprinted Polymers and Analgesics
Journal article   Peer reviewed

Vibrational Frequency Shifts for Monitoring Noncovalent Interactions between Molecular Imprinted Polymers and Analgesics

Wenjing Xi, Anna A Volkert, Michael C Boller and Amanda J Haes
Journal of physical chemistry. C, Vol.122(40), pp.23068-23077
10/11/2018
DOI: 10.1021/acs.jpcc.8b07771

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Abstract

The inherent sensitivity of molecular vibrational frequencies to their local chemical environment allows for the investigation of how small molecules interact within engineered cavities in molecular imprinted polymers (MIPs). These interactions arise via weak yet collective intermolecular interaction between the polymer and small molecule. Herein, intermolecular interactions between methacrylic acid-based MIPs and acetaminophen, aspirin, and caffeine are evaluated using shifts in the vibrational frequencies and changes in bandwidths of Raman-active modes. Recognition between these materials is measured experimentally and compared to modeled binding energies. Upon evaluation of Raman signals for the analgesics, intermolecular interactions such as hydrogen bonding and other weak interactions between the molecules and polymer backbone are quantified. Finally, dissociation constants and imprinting efficiencies are estimated for selectivity evaluation. This exploitation of the sensitivity of Raman-active vibrational band frequencies to collective intermolecular interactions for binding studies could facilitate the development and assessment of MIPs for small molecule recognition.

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