pH titration monitored by quantum cascade laser-based vibrational circular dichroism

J Phys Chem B. 2014 Apr 10;118(14):3941-9. doi: 10.1021/jp4122886. Epub 2014 Apr 2.

Abstract

Vibrational circular dichroism (VCD) spectra of aqueous solutions of proline were recorded in the course of titrations from basic to acidic pH using a spectrometer equipped with a quantum cascade laser (QCL) as an infrared light source in the spectral range from 1320 to 1220 cm(-1). The pH-dependent spectra were analyzed by singular value decomposition and global fitting of a two-pK Henderson-Hasselbalch model. The analysis delivered relative fractions of the three different protonation species. Their agreement with the relative fractions obtained from performing the same analysis on pH-dependent Fourier transform infrared (FT-IR) and QCL-IR spectra validates the quantitative results from QCL-VCD. Global fitting of the pH-dependent VCD spectra of L-proline allowed for extraction of pure spectra corresponding to anionic, zwitterionic, and cationic L-proline. From a static experiment, only pure spectra of the zwitterion would be accessible in a straightforward way. A comparison to VCD spectra calculated for all three species led to assignment of vibrational modes that are characteristic for the respective protonation states. The study demonstrates the applicability of QCL-VCD both for quantitative evaluation and for qualitative interpretation of dynamic processes in aqueous solutions.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Anions / chemistry
  • Cations / chemistry
  • Circular Dichroism*
  • Hydrogen-Ion Concentration
  • Lasers, Semiconductor*
  • Proline / chemistry*
  • Spectroscopy, Fourier Transform Infrared
  • Water / chemistry

Substances

  • Anions
  • Cations
  • Water
  • Proline