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A computational study of the ground and excited state acidities of synthetic analogs of red wine pyranoanthocyanins

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Abstract

The color of mature red wines is due in large part to the chemical transformation of grape anthocyanins into pyranoanthocyanins. Given the difficulties of isolation and purification of pyranoanthocyanins from wines, experimental investigations have focused on pyranoflavylium cations, synthetic analogs that contain the basic chromophoric moiety of pyranoanthocyanins. Quantum chemical methodologies have been extensively employed to predict the physical, spectroscopic and photophysical properties of anthocyanins and, more recently, pyranoflavylium cations. In the present work, we employ TD-DFT with the B3-LYP functional and the def2-TZVP basis set, combined with estimation of solvation free energies via COSMO, to estimate a priori the pKa values of the ground state and the lowest excited singlet and triplet states of a series of seven substituted hydroxypyranoflavylium cations. For the ground state and the first excited singlet state, the quantum chemical results compare favorably to experimental values for most of these compounds. Although there are currently no experimental data for the lowest excited triplet state, the acidity is predicted to be more similar to that of the ground state than to the excited singlet state, as is generally found experimentally for photoacids.

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Acknowledgements

We are grateful for generous support by the School of Pharmaceutical Science and Technology, Tianjin University, China, including computer time on the SPST computer cluster Arran, and for computer time at the Vienna Scientific Cluster (VSC), Project No. 70376. F. H. Q and G. T. M. S. thank the CNPq and CAPES (Finance code 001), Brazil, for fellowships and NAP-PhotoTech, INCT-Catálise (CNPq 465454/2014-3 and 444061/2018-5), and CNPq (FHQ Universal Grant 408181/2016-3) for funding. A.A.F. thanks the FCT, Portugal (SFRH/BPD/94299/2013), for fellowship support.

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Authors and Affiliations

  1. School of Pharmaceutical Science and Technology, Tianjin University, Tianjin, 300072, People’s Republic of China

    Jing Wang, Farhan Siddique, Hans Lischka & Adelia J. A. Aquino

  2. Instituto Superior Técnico, Universidade de Lisboa, 1049001, Lisbon, Portugal

    Adilson A. Freitas

  3. Instituto de Química, Universidade de São Paulo, Av. Lineu Prestes 748, São Paulo, SP, 05508-030, Brazil

    Cassio P. Silva, Gustavo T. M. Silva & Frank H. Quina

  4. Department of Chemistry and Biochemistry, Texas Tech University, Lubbock, TX, 79409-1061, USA

    Hans Lischka

  5. Department of Mechanical Engineering, Texas Tech University, Lubbock, TX, 79409, USA

    Adelia J. A. Aquino

  6. Institute for Soil Research, University of Natural Resources and Life Sciences Vienna, Peter-Jordan-Strasse 82, 1190, Vienna, Austria

    Adelia J. A. Aquino

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  1. Jing Wang
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  2. Farhan Siddique
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Correspondence to Frank H. Quina, Hans Lischka or Adelia J. A. Aquino.

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Wang, J., Siddique, F., Freitas, A.A. et al. A computational study of the ground and excited state acidities of synthetic analogs of red wine pyranoanthocyanins. Theor Chem Acc 139, 117 (2020). https://doi.org/10.1007/s00214-020-02633-9

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