Natural anthocyanin pigments/dyes and phenolic copigments/co-dyes form noncovalent complexes, which stabilize and modulate (in particular blue, violet, and red) colors in flowers, berries, and food products derived from them (including wines, jams, purees, and syrups). This noncovalent association and their electronic and optical implications constitute the copigmentation phenomenon. Over the past decade, experimental and theoretical studies have enabled a molecular understanding of copigmentation. This review revisits this phenomenon to provide a comprehensive description of the nature of binding (the dispersion and electrostatic components of π-π stacking, the hydrophobic effect, and possible hydrogen-bonding between pigment and copigment) and of spectral modifications occurring in copigmentation complexes, in which charge transfer plays an important role. Particular attention is paid to applications of copigmentation in food chemistry.
Flavonolignans from silymarin, the standardized plant extract obtained from thistle, exhibit various antioxidant activities, which correlate with the other biological and therapeutic properties of that extract. To highlight the mode of action of flavonolignans as free radical scavengers and antioxidants, 10 flavonolignans, selectively methylated at different positions, were tested in vitro for their capacity to scavenge radicals (DPPH and superoxide) and to inhibit the lipid peroxidation induced on microsome membranes. The results are rationalized on the basis of (i) the oxidation potentials experimentally obtained by cyclic voltammetry and (ii) the theoretical redox properties obtained by quantum-chemical calculations (using a polarizable continuum model (PCM)-density functional theory (DFT) approach) of the ionization potentials and the O-H bond dissociation enthalpies (BDEs) of each OH group of the 10 compounds. We clearly establish the importance of the 3-OH and 20-OH groups as H donors, in the presence of the 2,3 double bond and the catechol moiety in the E-ring, respectively. For silybin derivatives (i.e., in the absence of the 2,3 double bond), secondary mechanisms (i.e., electron transfer (ET) mechanism and adduct formation with radicals) could become more important (or predominant) as the active sites for H atom transfer (HAT) mechanism are much less effective (high BDEs).
Chalcones are natural compounds that are largely distributed in plants, fruits, and vegetables. They belong to the flavonoid group of molecules, and some of them exhibit numerous biological activities. The results of quantum chemical calculations (based on density functional theory, using the B3P86 exchange-correlation potential) are reported for 11 chalcones, in the gas phase and in the presence of an implicit solvent (using the conductor-like polarizable continuum model, C-PCM). These results are discussed in regard to the capacity of these chalcones to scavenge the 2,2-diphenyl-1-pycril-hydrazyl (DPPH) free radical. The O-H bond dissociation enthalpy (BDE) parameter, which is calculated for each OH group, seems to be the best indicator of the anti-radical property of these compounds. This demonstrates the importance of the H atom transfer mechanism to explain their capacity to scavenge the free radicals. The active sites are identified as the 6'-OH group and the 3,4-dihydroxy-catechol. The alpha,beta-double bond is influential in determining the activity.
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