Molecule-specific vibration-based chiral differentiation of Raman spectra using cysteine modified gold nanoparticles: the cases of tyrosine and phenylalanine

Abstract

The chirality of amino acids plays a key role in many biochemical processes, with the development of spectroscopic analysis methods for the chiral differentiation of amino acids being significant. Normal Raman spectroscopy is blind to chirality; however, chiral discrimination of tyrosine (Tyr) (or phenylalanine, Phe) enantiomers using Raman spectra can be achieved assisted by the construction of a simple chiral selector (i.e., cysteine (Cys)-modified Au nanoparticles (NPs)). Due to the synergetic effect between Cys and the Au NPs, the characteristic Raman scattering intensities of the Tyr (or Phe) enantiomer with the same chirality of Cys are enantioselectively boosted by over four-fold compared with those of the counter enantiomer of Tyr (or Phe). The large differences in the Raman signals allow for the determination of enantiomeric excess. Interestingly, such enantiomeric discrimination is not revealed by the common chiral analysis method of circular dichroism spectroscopy. Consequently, it is anticipated that Raman spectroscopy based on molecular vibrations will find broad applications in chirality-related detection with high sensitivity and species specificity.