Acylated Anthocyanins from Red Cabbage and Purple Sweet Potato Can Bind Metal Ions and Produce Stable Blue Colors.

Red cabbage (RC) and purple sweet potato (PSP) are naturally rich in acylated cyanidin glycosides that can bind metal ions and develop intramolecular π-stacking interactions between the cyanidin chromophore and the phenolic acyl residues. In this work, a large set of RC and PSP anthocyanins was investigated for its coloring properties in the presence of iron and aluminum ions. Although relatively modest, the structural differences between RC and PSP anthocyanins, i.e., the acylation site at the external glucose of the sophorosyl moiety (C2-OH for RC vs. C6-OH for PSP) and the presence of coordinating acyl groups (caffeoyl) in PSP anthocyanins only, made a large difference in the color expressed by their metal complexes. For instance, the Al3+-induced bathochromic shifts for RC anthocyanins reached ca. 50 nm at pH 6 and pH 7, vs. at best ca. 20 nm for PSP anthocyanins. With Fe2+ (quickly oxidized to Fe3+ in the complexes), the bathochromic shifts for RC anthocyanins were higher, i.e., up to ca. 90 nm at pH 7 and 110 nm at pH 5.7. A kinetic analysis at different metal/ligand molar ratios combined with an investigation by high-resolution mass spectrometry suggested the formation of metal-anthocyanin complexes of 1:1, 1:2, and 1:3 stoichiometries. Contrary to predictions based on steric hindrance, acylation by noncoordinating acyl residues favored metal binding and resulted in complexes having much higher molar absorption coefficients. Moreover, the competition between metal binding and water addition to the free ligands (leading to colorless forms) was less severe, although very dependent on the acylation site(s). Overall, anthocyanins from purple sweet potato, and even more from red cabbage, have a strong potential for development as food colorants expressing red to blue hues depending on pH and metal ion.

Molar absorptivities (ε) and spectral and colorimetric characteristics of purple sweet potato anthocyanins.

Purple sweet potato, a source of acylated cyanidin and peonidin derivatives, is commercially available as a food colorant. Our objectives were to determine molar absorptivities (ε), spectral and colorimetric properties of purple sweet potato anthocyanins. Anthocyanins were isolated by semi-preparative HPLC, weighed, dried, and redissolved in acidic methanol or water. Anthocyanins were diluted in pH 1-9; ε, spectra, and color were measured on the methanolic and aqueous solutions. Higher ε were obtained in 0.1% HCl methanol (10,797-31,257 L/(mol × cm)) than in aqueous solution pH 1 (8861-24,303 L/(mol × cm)). Peonidin-3-sophoroside-5-glucoside had greatest ε in pH 1, but in alkaline pH, ε of acylated Peonidin-3-sophoroside-5-glucoside derivatives were greatest. Generally monoacylation decreased ε while diacylation increased ε. Location of acylation also affected ε of two Peonidin isomers (pH 1: 15,999 and 21,011 L/(mol × cm)). All anthocyanins expressed red-pink hues (330°-13.2°) in acidic pH and blues (230°-262°) in alkaline pH.

Molar absorptivity (ε) and spectral characteristics of cyanidin-based anthocyanins from red cabbage.

Red cabbage extract contains mono and di-acylated cyanidin (Cy) anthocyanins and is often used as food colorants. Our objectives were to determine the molar absorptivity (ε) of different red cabbage Cy-derivatives and to evaluate their spectral behaviors in acidified methanol (MeOH) and buffers pH 1-9. Major red cabbage anthocyanins were isolated using a semi-preparatory HPLC, dried and weighed. Pigments were dissolved in MeOH and diluted with either MeOH (0.1% HCl) or buffers to obtain final concentrations between 5×10(-5) and 1×10(-3) mol/L. Spectra were recorded and ε calculated using Lambert-Beer's law. The ε in acidified MeOH and buffer pH 1 ranged between ~16,000-30,000 and ~13,000-26,000 L/mol cm, respectively. Most pigments showed higher ε in pH 8 than pH 2, and lowest ε between pH 4 and 6. There were bathochromic shifts (81-105 nm) from pH 1 to 8 and hypsochromic shifts from pH 8 to 9 (2-19 nm). Anthocyanins molecular structures and the media were important variables which greatly influenced their ε and spectral behaviors.

Anthocyanins contents, profiles, and color characteristics of red cabbage extracts from different cultivars and maturity stages.

Red cabbage (Brassica oleracea L.) is an excellent source of food colorant. This study aimed to evaluate the anthocyanin pigment contents and profiles from seven red cabbage cultivars at two maturity stages (8 weeks apart) and evaluate their color characteristics and behavior under acidic and neutral pH. Anthocyanin concentrations ranged from 1111 to 1780 mg Cy3G/100 g DM and did not increase with time. Cultivar and maturation affected pigment profile. Some varieties accumulated ≥30% of diacylated pigments, and proportions of monoacylated pigments decreased with time. Extracts from selected varieties at first harvesting time produced colors similar (λmax = 520 nm and ΔE = 6.1-8.8) to FD&C Red No. 3 at pH 3.5. At pH 7, extracts from the second harvest with s higher proportion of diacylation produced λmax ≃ 610 nm, similar to FD&C Blue No. 2. Cultivar selection and maturation affected color and stability of red cabbage extracts at different pH values.