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In iron-catalyzed lipid peroxidation the antioxidant activity of CU and its acetylated derivatives has been ascribed to iron chelation by the α,γ-diketone moiety; e.g., see: Sreejayan, N.; Rao, M. N. A. J. Pharm. Pharmacol. 1994, 46, 1013-1016. See also: Began, G.; Sudharshan, E.; Udaya Sankar, K.; Appu Rao, A. G. J. Agric. Food Chem. 1999, 47, 4992-4997.
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For the 3 year period (2000 to 2002-end), Chemical Abstracts (SciFinder) lists 956 papers with the word curcumin. Among this number, 248 papers contain the word pair curcumin and antioxidant.
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For 2,4-pentanedione (acetylacetone), the [keto-enol]/[diketo] ratios are 42, 4.8, 2.9, 1.2, and 0.23 in cyclohexane, 1,4-dioxane, methanol, acetonitrile, and water, respectively, and equilibration is extremely slow, e.g., 15 h in methanol. See: Mills, S. G.; Beak, P. J. Org. Chem. 1985, 50, 1216-1224.
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Thermochemistry alone does not dictate the relative rates of H-atom abstractions from OH and CH groups. It is well-known that for equal thermodynamic driving forces H-atom abstractions by oxygen-centered radicals (and other radicals) are several orders of magnitude faster from an OH group than from a CH group.
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.) in acetonitrile has been recently reported, see: Nakanishi, M.; Miyazaki, K.; Shimada, T.; Iizuka, Y.; Inami, K.; Mochizuki, M.; Urano, S.; Okuda, H.; Ozawa, T.; Fukuzumi, S.; Ikota, N.; Fukuhara, K. Org. Biomol. Chem. 2003, 1, 4085-4088.
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4344709820
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+/alkane (ca. 50).
-
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47
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4344655086
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note
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λmax ∼ 50 000).
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48
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4344633417
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a of CU were assigned by these workers to the ionization of particular OH groups, see Discussion.
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4344711894
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note
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Equation 7 is a remarkably reliable kinetic guideline for "pure" HAT processes (see e.g., Table 3) but it appears to be rarely, if ever, precisely obeyed (see e.g., refs 11, 12, and 29). Too much should not, therefore, be read into any minor kinetic "inconsistencies".
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61
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0001107787
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5O-H) which are -1.8 and -2.6 kcal/mol, respectively. These calculations were performed using the B3LYP functional with the medium-level model MLM1 as described in: DiLabio, G. A.; Pratt, D. A.; LoFaro, A. D.; Wright, J. S. J. Phys. Chem. A 1999, 103, 1653-1661.
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4344626649
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4344711895
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note
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64
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4344607162
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Unpublished results
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Litwinienko, G. Unpublished results.
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Litwinienko, G.1
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65
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4344609181
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note
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. by delocalization of the unpaired electron over the atoms in this group and by conjugation through a vinyl group.
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66
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Inczedy, J., Lengyel, T., Ure, A. M., Eds.; Blackwell Science: Cambridge, MA (online version)
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IUPAC Compendium of Analytical Nomenclature, 3rd ed.; Inczedy, J., Lengyel, T., Ure, A. M., Eds.; Blackwell Science: Cambridge, MA 1998 (online version: http://www.iupac.org/publications/analytical_compendium/.
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(1998)
IUPAC Compendium of Analytical Nomenclature, 3rd Ed.
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