Antioxidant Scavenging of the Superoxide Radical by Yerba Mate ( Ilex paraguariensis) and Black Tea (Camellia sinensis) Plus Caffeic and Chlorogenic Acids, as Shown via DFT and Hydrodynamic Voltammetry.

Publisher: MDPI Country of Publication: Switzerland NLM ID: 101092791 Publication Model: Electronic Cited Medium: Internet ISSN: 1422-0067 (Electronic) Linking ISSN: 14220067 NLM ISO Abbreviation: Int J Mol Sci Subsets: MEDLINE

Original Publication: Basel, Switzerland : MDPI, [2000-

Superoxides*/chemistry ; Superoxides*/metabolism ; Caffeic Acids*/chemistry ; Chlorogenic Acid*/chemistry ; Ilex paraguariensis*/chemistry ; Antioxidants*/chemistry ; Camellia sinensis*/chemistry; Density Functional Theory ; Free Radical Scavengers/chemistry ; Electrochemical Techniques ; Plant Extracts/chemistry

We describe the antioxidant capability of scavenging the superoxide radical of several tea and yerba mate samples using rotating ring-disk electrochemistry (RRDE). We directly measured superoxide concentrations and detected their decrease upon the addition of an antioxidant to the electrochemical cell. We studied two varieties of yerba mate, two varieties of black tea from Bangladesh, a sample of Pu-erh tea from China, and two components, caffeic acid and chlorogenic acid. All of these plant infusions and components showed strong antioxidant activities, virtually annihilating the available superoxide concentration. Using density functional theory (DFT) calculations, we describe a mechanism of superoxide scavenging via caffeic and chlorogenic acids. Superoxide can initially interact at two sites in these acids: the H4 catechol hydrogen (a) or the acidic proton of the acid (b) . For (a) , caffeic acid needs an additional π-π superoxide radical, which transfers electron density to the ring and forms a HO 2 ^- anion. A second caffeic acid proton and HO 2 ^- anion forms H 2 O 2 . Chlorogenic acid acts differently, as the initial approach of superoxide to the catechol moiety (a) is enough to form the HO 2 ^- anion. After an additional acidic proton of chlorogenic acid is given to HO 2 ^- , three well-separated compounds arise: (1) a carboxylate moiety, (2) H 2 O 2 , and a (3) chlorogenic acid semiquinone. The latter can capture a second superoxide in a π-π manner, which remains trapped due to the aromatic ring, as for caffeic acid. With enough of both acids and superoxide radicals, the final products are equivalent: H 2 O 2 plus a complex of the type [X-acid-η-O 2 ], X = caffeic, chlorogenic. Chlorogenic acid (b ) is described by the following reaction: 2 O 2 ^•- + 2 chlorogenic acid → 2 chlorogenic carboxylate + O 2 + H 2 O 2 , and so, it acts as a non-enzymatic superoxide dismutase (SOD) mimic, as shown via the product formation of O 2 plus H 2 O 2 , which is limited due to chlorogenic acid consumption. Caffeic acid (b) differs from chlorogenic acid, as there is no acidic proton capture via superoxide. In this case, approaching a second superoxide to the H4 polyphenol moiety forms a HO 2 ^- anion and, later, an H 2 O 2 molecule upon the transfer of a second caffeic acid proton.

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Keywords: Camellia sinensis; DFT; Ilex paraguariensis; caffeic acid; chlorogenic acid; hydrodynamic voltammetry; superoxide scavenging

11062-77-4 (Superoxides)
0 (Caffeic Acids)
318ADP12RI (Chlorogenic Acid)
U2S3A33KVM (caffeic acid)
0 (Antioxidants)
0 (Free Radical Scavengers)
0 (Plant Extracts)

Date Created: 20240914 Date Completed: 20240914 Latest Revision: 20240916

20240916

PMC11394812

10.3390/ijms25179342

39273291