Journal of the American Chemical Society
Journal of the American Chemical Society
5 years ago

Infrared Determination of the Protonation State of a Key Histidine Residue in the Photosynthetic Water Oxidizing Center

Infrared Determination of the Protonation State of a Key Histidine Residue in the Photosynthetic Water Oxidizing Center
Takumi Noguchi, Shin Nakamura
Photosynthetic water oxidation is performed at the Mn4CaO5 cluster in photosystem II (PSII). The protonation structures of amino acid residues and water molecules around the Mn4CaO5 cluster are crucial in water oxidation reactions. In this study, we determined the protonation state of a key His residue in water oxidation, D1-H337, that is directly hydrogen-bonded with the oxygen atom of the Mn4CaO5 cluster, using polarized attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopy. Flash-induced polarized ATR-FTIR difference spectra upon the S1 → S2 transition of oriented PSII membranes showed broad negative and positive features at about 2600 and 2900 cm–1, respectively, with large dichroic ratios, accompanied by several minor peaks attributable to the Fermi resonance of a His NH vibration. Quantum mechanics/molecular mechanics (QM/MM) calculations well reproduced the characteristics of these features as the NτH stretching vibrations of D1-H337 in its protonated cation form. The spectral features were reversed in the S3 → S0 transition, indicating that this His remains protonated during the S-state cycle. The redox potential (Em) of the Mn4CaO5 cluster in the S1 → S2 transition, which was estimated from the QM/MM calculations, was found to be comparable to that of water oxidation when D1-H337 is protonated cation. It was thus concluded that the positive charge on the protonated D1-H337 plays an important role in retaining a high Em value of the Mn4CaO5 cluster throughout the reaction cycle to enable water oxidation.

Publisher URL: http://dx.doi.org/10.1021/jacs.7b04924

DOI: 10.1021/jacs.7b04924

You might also like
Discover & Discuss Important Research

Keeping up-to-date with research can feel impossible, with papers being published faster than you'll ever be able to read them. That's where Researcher comes in: we're simplifying discovery and making important discussions happen. With over 19,000 sources, including peer-reviewed journals, preprints, blogs, universities, podcasts and Live events across 10 research areas, you'll never miss what's important to you. It's like social media, but better. Oh, and we should mention - it's free.

  • Download from Google Play
  • Download from App Store
  • Download from AppInChina

Researcher displays publicly available abstracts and doesn’t host any full article content. If the content is open access, we will direct clicks from the abstracts to the publisher website and display the PDF copy on our platform. Clicks to view the full text will be directed to the publisher website, where only users with subscriptions or access through their institution are able to view the full article.