Dual Mode Chip Enantioselective Express Discrimination of Chiral Amines via Wettability-Based Mobile Application and Portable Surface-Enhanced Raman Spectroscopy Measurements

A dual-mode functional chip for chiral sensing based on mobile phone wettability measurements and portable surface-enhanced Raman spectroscopy (SERS) is reported. The plasmon-active regular gold grating surface was covalently grafted with chiral recognition moieties, L- or D-enantiomers of tartaric acid, making stereoselective discrimination of chiral amines possible. Chiral sensing of amines includes two modes of analysis, performed subsequently on the one chip surface with portable instruments (mobile phone equipped with a camera and developed application (app) Dropangle and a portable Raman spectrometer). First, the wettability changes, caused by enantioselective entrapping of chiral amines, are monitored and analyzed via our mobile phone app, allowing detection of the optical configuration and concentration of enantiomers with 1 order of magnitude accuracy. Second, SERS measurement on the same chip provides information about the chemical structure of entrapped amines and allows calculation of the enantiomeric excess with great accuracy. The applicability of the developed chip is demonstrated on a variety of chiral amines, including tyrosine, cysteine, dopamine (DOPA), and dextromethorphan in analytical solutions and in commercially available DOPA-containing drug. Moreover, we demonstrate that the chips could be regenerated and used repeatedly for at least five cycles.