Mechanistic studies on the oxidation of ascorbic Acid and hydroquinone by a {mn(4)o(6)}(4+) core in aqueous media.
Summary of "Mechanistic studies on the oxidation of ascorbic Acid and hydroquinone by a {mn(4)o(6)}(4+) core in aqueous media."
Described in this work is the kinetics of oxidation of ascorbic acid and hydroquinone by a tetranuclear Mn(IV) oxidant, [Mn(4)(μ-O)(6)(bipy)(6)](4+) (1(4+), bipy =2,2(/)-bipyridine), in aqueous solution over a wide pH range 1.5-6.0. In particular, below pH 3.0, protonation on the oxo-bridge of 1(4+) results in the formation of [Mn(4)(μ-O)(5)(μ-OH)(bipy)(6)](5+) (1H(5+)) as an additional oxidant over 1(4+). Both ascorbic acid and ascorbate whereas only hydroquinone and none of its protolytic species were found to be reactive reducing agents in these reactions. Analysis of the rate data clearly established that the oxo-bridge protonated oxidant 1H(5+) is kinetically far more superior to 1(4+) in oxidizing ascorbic acid and hydroquinone. Rates of these reactions are substantially lowered in D(2)O-enriched media in comparison to that in H(2)O media. An initial one electron one proton transfer electroprotic rate step could be mechanistically conceived. DFT studies established that among the two sets of terminal and central Mn(IV) atoms in the tetranuclear oxidant, one of the two terminal Mn(IV) is reduced to Mn(III) at the rate step that we can intuitively predict considering the probable positive charge distribution on the Mn(IV) atoms.
Affiliation
Department of Chemistry, Jadavpur University, Kolkata 700 032, India.
Journal Details
This article was published in the following journal.
Name: The journal of physical chemistry. A
ISSN: 1520-5215
Pages: 4882-93
Links
- PubMed Source: http://www.ncbi.nlm.nih.gov/pubmed/21517065
- DOI: http://dx.doi.org/10.1021/jp202690a
Medical and Biotech [MESH] Definitions
Hexuronic Acids
Term used to designate tetrahydroxy aldehydic acids obtained by oxidation of hexose sugars, i.e. glucuronic acid, galacturonic acid, etc. Historically, the name hexuronic acid was originally given to ascorbic acid.
Ascorbic Acid Deficiency
A condition due to a dietary deficiency of ascorbic acid (vitamin C), characterized by malaise, lethargy, and weakness. As the disease progresses, joints, muscles, and subcutaneous tissues may become the sites of hemorrhage. Ascorbic acid deficiency frequently develops into SCURVY in young children fed unsupplemented cow's milk exclusively during their first year. It develops also commonly in chronic alcoholism. (Cecil Textbook of Medicine, 19th ed, p1177)
L-gulonolactone Oxidase
An enzyme involved in the metabolism of ASCORBIC ACID and aldarate. It catalyzes the oxidation of L-gulono-1,4-lactone to L-xylo-hex-3-ulonolactone.
Ascorbic Acid
A six carbon compound related to glucose. It is found naturally in citrus fruits and many vegetables. Ascorbic acid is an essential nutrient in human diets, and necessary to maintain connective tissue and bone. Its biologically active form, vitamin C, functions as a reducing agent and coenzyme in several metabolic pathways. Vitamin C is considered an antioxidant.
2,3-diketogulonic Acid
Metabolite of ASCORBIC ACID and the oxidized form of the lactone DEHYDROASCORBIC ACID.
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