Abstract
Abstract— Fourier transform infrared (FTIR) difference spectroscopy of the electrochemically generated anion radical of bacteriochlorophyll a was used to follow the molecular changes upon one‐electron reduction. An IR spectroelectrochemical cell was constructed, allowing in situ electrolysis in connection with spectroscopic investigations from 200 to 10 000 nm. FTIR difference spectra of the BChl a anion formation in THF d8 at U=+0.9 V (as determined by ferrocene calibration) were obtained. After complete formation of the radical, the reverse process was followed. Comparison of visible and IR spectra of the reduction and re‐oxidation processes indicates that more than 90% of the BChl a anion could be formed with 90% of it being reversible. The main IR absorbance changes are observed for the conjugated and even for the non‐conjugated C=O groups of BChl a. These results demonstrate the use of the combination of FTIR spectroscopy and electrochemistry for the characterization of radicals of the isolated pigments and of their in vivo bonding to the protein environment.
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