Role of Phe‐D 5 isotopically labeled analogues of bradykinin on elucidation of its adsorption mode on Ag, Au, and Cu electrodes. Surface‐enhanced Raman spectroscopy studies

Raman (RS), surface‐enhanced Raman scattering (SERS), electrochemistry, and isotopic effect methods were used to characterize selective adsorption of two isotopically labeled bradykinin analogues, [(Phe‐D 5 ) 5 ]BK and [(Phe‐D 5 ) 8 ]BK, a hormone which is known to be involved in small‐cell and non‐small‐cell lung carcinoma and prostate cancer. The investigated analogues contain Phe residue, at position 5 or 8 in the amino acid sequence, substituted by Phe‐D 5 (five protons of L‐phenylalanine ring substituted by deuterium). [(Phe‐D 5 ) 5 ]BK and [(Phe‐D 5 ) 8 ]BK were immobilized onto electrochemically roughened Ag, Au, and Cu electrode surfaces under different applied electrode potentials (−1.000 V to 0.200 V) in an aqueous solution containing 0.01 M phosphate buffer (pH = 7.0) and 0.1 M Na 2 SO 4 . Based on the analyses of the spectral profiles in the 920 – 1050 cm −1 spectral range, specific conclusions were drawn with respect to the Phe⋅⋅⋅metal interactions and changes in the interaction that occurred when the adsorption conditions were varied. Copyright © 2013 John Wiley & Sons, Ltd.