Theoretical and experimental study of the infrared and Raman spectra of L-lysine acetylation

[Display omitted] •Experimental and theoretical Raman and infrared (IR) spectra of L-lysine Nε-Ace-Lys, Nα-Ace-Lys, and NαNε-Ace-Lys are studied.•Characteristic Raman and IR bands at 1500–1700 cm−1 and 3200–3400 cm−1 can be used to probe whether and how lysine is acetylated.•Potential energy distribution (PED) of vibrational modes of Nε-Ace-Lys, Nα-Ace-Lys, and NαNε-Ace-Lys are assigned.•Lysine acetylation in peptide can be distinguished by the Amide I, II and III bands in IR and Raman spectra. Acetylation is a common and extremely important protein modification in biology, referring to the covalent attachment of an acetyl group to the amino group. There are two forms of protein acetylation, which are lysine Nε-acetylation and N-terminal Nα-acetylation, respectively. Protein lysine Nε-acetylation is a globally important post-translational modification which plays a critical regulatory role in almost all aspects of cell metabolism. In addition, whether lysine on the N-terminal of protein can undergo Nα-acetylation is still a controversial viewpoint. Carrying out further molecular study of the role of acetylation is also the one of challenges. In order to investigate the protein acetylation more effectively, it is thus necessary to have a thorough and comprehensive understanding of lysine acetylation. In this work, both Raman and infrared (IR) spectra of L-lysine Nε-Ace-Lys, Nα-Ace-Lys, and NαNε-Ace-Lys were explored through both experimental experiment and theoretical computation based on density function theory (DFT). Vibration assignments and geometry structures of three acetylated lysines were therefore obtained for the first time in this work. The IR or Raman spectra of four molecules are very different from each other, which can be easily distinguished from the characteristic bands at 1500–1700 cm−1 and 3200–3400 cm−1 regions. Therefore, this work may provide the guide for probing the protein acetylation by Raman and IR spectroscopy.