Thomas M. Collins

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.

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-Beers 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.

Evaluating the role of metal ions in the bathochromic and hyperchromic responses of cyanidin derivatives in acidic and alkaline pH

In many food products, colorants derived from natural sources are increasingly popular due to consumer demand. Anthocyanins are one class of versatile and abundant naturally occurring chromophores that produce different hues in nature, especially with metal ions and other copigments assisting. The effects of chelation of metal ions (Mg(2+), Al(3+), Cr(3+), Fe(3+), and Ga(3+)) in factorial excesses to anthocyanin concentration (0-500×) on the spectral characteristics (380-700nm) of cyanidin and acylated cyanidin derivatives were evaluated to better understand the color evolution of anthocyanin-metal chelates in pH 3-8. In all pH, anthocyanins exhibited bathochromic and hyperchromic shifts. Largest bathochromic shifts most often occurred in pH 6; while largest hyperchromic shifts occurred in pH 5. Divalent Mg(2+) showed no observable effect on anthocyanin color while trivalent metal ions caused bathochromic shifts and hue changes. Generally, bathochromic shifts on anthocyanins were greatest with more electron rich metal ions (Fe(3+)≈Ga(3+)>Al(3+)>Cr(3+)).

Spectral and colorimetric characteristics of metal chelates of acylated cyanidin derivatives

Colorants derived from nature are increasingly popular due to consumer demand. Anthocyanins are a class of naturally occurring pigments that produce red-purple-blue hues in nature, especially when interacting with metal ions and co-pigments. The role of various acylations of cyanidin (Cy) derivatives on color expression and stability of Al3+ and Fe3+ chelates in pH 6-7 were evaluated by spectrophotometry (380-700nm) and colorimetry (CIE-L∗a∗b∗) during dark, ambient storage (48h). Increased substitution generally increased λmax of Cy chelates: malonic acid monoacylation<triglycosylated Cy<Cy monoacylated with hydroxycinnamic acids<diacylated Cy. Patterns were similar regarding bathochromic shifts. Acyl moieties of diacylated Cy with smaller substitution patterns resulted in greater λmax, and no pattern emerged for monoacylated cyanidin. Pigment stability was improved with increasing proportions of metal ions and acylation. Stability followed that diacylated cyanidin (p-coumaric-sinapic>ferulic-sinapic>sinapic-sinapic)>monoacylated (malonic≈sinapic>ferulic>p-coumaric).

Effects of hydroxycinnamic acids on blue color expression of cyanidin derivatives and their metal chelates

Mechanisms to recreate many anthocyanin blue hues in nature are not fully understood, but interactions with metal ions and phenolic compounds are thought to play important roles. Bluing effects of hydroxycinnamic acids on cyanidin and chelates were investigated by addition of the acids to triglycosylated cyanidin (0-50×[anthocyanin]) and by comparison to hydroxycinnamic acid monoacylated and diacylated Cy fractions by spectrophotometry (380-700nm) and colorimetry in pH 5-8. With no metal ions, λmax and absorbance was greatest for cyanidin with diacylation>monoacylation>increasing [acids]. Hydroxycinnamic acids added to cyanidin solutions weakly impacted color characteristics (ΔE<5); while acylation (covalent acid attachment) resulted in ΔE 5-15. Triglycosylated cyanidin expressed blue color (pH 7-8), suggesting glycosylation pattern also plays a role. Al3+ chelation increased absorbance 2-42× and λmax≳40nm (pH 5-6) compared to added hydroxycinnamic acids. Metal chelation and aromatic diacylation resulted in the most blue hues.

Effects of Growth Temperature and Postharvest Cooling on Anthocyanin Profiles in Juvenile and Mature Brassica oleracea

The effects of growth temperatures on anthocyanin content and profile were tested on juvenile cabbage and kale plants. The effects of cold storage time were evaluated on both juvenile and mature plants. The anthocyanin content in juvenile plants ranged from 3.82 mg of cyanidin-3,5-diglucoside equivalent (Cy equiv)/g of dry matter (dm) at 25 °C to 10.00 mg of Cy equiv/g of dm at 16 °C, with up to 76% diacylated anthocyanins. Cold storage of juvenile plants decreased the total amount of anthocyanins but increased the diacylated anthocyanin content by 3-5%. In mature plants, cold storage reduced the total anthocyanin content from 22 to 12.23 mg/g after 5 weeks of storage in red cabbage, while the total anthocyanin content increased after 2 weeks of storage from 2.34 to 3.66 mg of Cy equiv/g of dm in kale without having any effect on acylation in either morphotype. The results obtained in this study will be useful for optimizing anthocyanin production.

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.