Anthocyanin and Polyphenolic Composition of Fresh And
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Anthocyanin and Polyphenolic Composition of Fresh and Processed Cherries A. CHAOVANALIKIT AND R.E. WROLSTAD ABSTRACT: The distribution of anthocyanin pigments and polyphenolics in 1 sour cherry (Prunus cerasus) and 3 sweet cherry (Prunus avium) cultivars was determined by high-performance liquid chromatography with diode array detection. Changes during frozen storage, canning, and brining were also monitored. Sweet cherry cultivars differed qualitatively with respect to the minor anthocyanins. Hydroxycinnamates are the major class of polyphenolics in sweet cherries, whereas flavanols are in the majority in Montmorency cherries. Hydroxycinnamates were greatly affected by processing and storage, whereas flavonol glycosides were quite stable. Half of the anthocyanins and polyphenolics were transferred to the syrup with canning, and nearly all were transferred to brine during brining. Keywords: anthocyanins, polyphenolics, canning, brining, frozen storage Food Chemistry and Toxicology Introduction cherries (Dekazos 1970; Chandra and others Although all cherry cultivars have some t is widely accepted that a diet rich in 1992); cyanidin-3-arabinosylrutinoside, cy- anthocyanin pigmentation in the skins, the Ifruits and vegetables will reduce the risk anidin-3-gentiobioside, and peonidin-3-ru- amounts vary tremendously (Chaovanali- of several oxidative stress diseases, includ- tinoside have also been reported to be kit and Wrolstad 2003). Some varieties have ing coronary heart disease, cancer, stroke, present (Schaller and Von Elbe 1968; Deka- pigmentation in the flesh, for example, and dementia. These health benefits are as- zos 1970; Shrikhande and Francis 1973a; Bing, and others do not, for example, Royal cribed to phytochemicals such as caro- Chandra and others 2001). Ann and Montmorency. The distribution of tenoids and polyphenolics, which include Hydroxycinnamates are a major class of individual phenolics and polyphenolic anthocyanin pigments, flavan-3-ols, procy- polyphenolics that are present in cherries. classes in skins, flesh, and pits has not been anidins, flavonol glycosides, phenolic acids, Schaller and Von Elbe (1970) identified 6 iso- reported. Pits in particular are a substantial and ellagic-acid derivatives (Ames and oth- mers of caffeoylquinic acid, 4 isomers of p- cherry-processing waste and could be a po- ers 1993; Halliwell and others 1995; Hortog coumaroylquinic acid, caffeic acid, and p-cou- tential source of polyphenolics for nutra- and others 1995; Porter and others 2001; Avi- maric acid in Montmorency cherries. ceutical or antioxidant use. ram and Fuhrman 2002; Bors and Michel Neochlorogenic acid and 3Ј-p-coumaroylqui- We recently reported how total anthocy- 2002). Our laboratory has recently investi- nic acid have been identified in sweet cherries anins, total phenolics, and antioxidant gated the anthocyanin pigment and total (Gao and Mazza 1995; Friedrich and Lee 1998; properties of sweet cherries are altered phenolic contents of cherries along with Mozetic and others 2002). The presence of when sweet cherries are processed by can- their antioxidant properties (Chaovanalikit caffeoyltartatric acid in sweet and sour cher- ning and brining and stored at freezing tem- and Wrolstad 2003). The antioxidant prop- ries and 4Ј-p-coumaroylquinic acid in sour peratures (Chaovanalikit and Wrolstad erties of sour cherries have been extensively cherries has also been reported (Friedrich 2004). Processing clearly had an impact on investigated by Michigan workers (Wang and Lee 1998). Flavonols and flavonol glyco- all 3 parameters. In some instances, antiox- and others 1999c; Wang and others 2000; sides are another important class of cherry idant properties actually increased, while Seeram and others 2002). polyphenolics, the rutinosides and glucosides total phenolics showed little change. Know- The major anthocyanin pigments in sweet of quercetin and kaempferol being reported ing how individual compounds and and sour cherries have been identified. Cy- by several workers in sweet and sour cherries polyphenolic classes are affected by pro- anidin-3-rutinoside, cyanidin-3-glucoside, (Schaller and Von Elbe 1970; Shrikhande and cessing may help to understand the rela- peonidin-3-rutinoside, peonidin-3-gluco- Francis 1973b; Henning and Herrmann tionship between polyphenolics and their side, and pelargonidin-3-rutinoside have 1980). In addition, Shrikhande and Francis antioxidant properties. been identified in Bing and other sweet cher- (1973b) reported the presence of quercetin- Our objectives were to identify the an- ry cultivars (Lynn and Luh 1964; Gao and 4Јglucoside, kaempferol-3-rhamnoside-4Ј- thocyanins and polyphenolics in sweet and Mazza 1995; Mozetic and others 2002). Cya- galactoside (tentative), and kaempferol-4Ј- sour cherries and to measure their distribu- nidin-3-glucosylrutinoside, cyanidin-3-ruti- glucoside (tentative). Henning and tion in skins, flesh, and pits. In addition, we noside, cyanidin-3-glucoside, and cyanidin- Herrmann (1980) isolated the 3,4Ј-bigluco- would like to monitor how they were quali- 3-sophoroside have been identified in sour sides of kaempferol and quercetin from sweet tatively and quantitatively affected with cherries and identified the galactoside of frozen storage, canning, and brining. MS 20030394 Submitted 7/11/03, Revised 9/26/03, quercetin and kaempferol and the rhamno- Accepted 9/26/03. Authors Chaovanalikit and Materials and Methods Wrolstad are with the Dept. of Food Science and side of quercetin in cherries. Friedrich and Lee Technology, Oregon State Univ., 100 Wiegand Hall, (1998) found the flavanol epicatechin in both Corvallis, OR 97331-6602. Direct inquiries to author sweet and sour cherries and procyanidins in Standards Wrolstad (E-mail: [email protected]). sour cherries. Phenolic standards (protocatechuic acid, Cherry anthocyanin and polyphenolic composition . chlorogenic acid, epicatechin, caffeic acid, p- immersed in water and heated at 100 °C for adsorbed onto a C-18 Sep-Pak mini-column coumaric acid, and quercetin-3-rutinoside) 12 min. The canned fruits were cooled by (Waters Assoc., Milford, Mass., U.S.A.), were purchased from Sigma Chemical Co. placing them in 25 °C water and then stored whereas sugars, acids, and other water-sol- (St. Louis, Mo., U.S.A.). Quercetin-3-gluco- at 2 °C and 22 °C. The canning experiment uble compounds were removed by washing side, quercetin-3-rhamnoside, kaempfereol- was replicated twice. the mini-column with 10 mL of 0.01% aque- 3-glucoside, and kaempferol-3-rutinoside Brined cherries. Royal Ann and Bing ous HCl (v/v). Then, the mini-column was were purchased from Extrasynthese (Genay, cherries with stems (about 1 kg) were each dried with nitrogen gas. Polyphenolics were France). Concord grape juice concentrate placed in 4-L glass jars. The bisulfite brine was subsequently eluted with 5 mL of ethyl ac- (Welch Food Inc., Concord, Mass., U.S.A.) added to the fruit-containing jars until the etate. Anthocyanins were eluted with 5 mL was purchased at a local supermarket, fruits were covered. Bisulfite brine solution of acidified methanol. whereas cranberry, black currant, red rasp- was prepared by dissolving 220 g of sodium The ethyl acetate fraction containing the berry, and strawberry juice concentrates metabisulfite, 202 g of calcium chloride, and polyphenolics and the methanol fraction Food Chemistry and Toxicology were provided by Kerr Concentrates Inc. 10 g citric acid in 10 L of water. This gave a containing the anthocyanins were concen- (Salem, Ore., U.S.A.). solution, which was 2.2% sodium met- trated to dryness using a Büchi rotavapor-R abisulfite, 2% calcium chloride, and 0.1% (Brinkmann Instruments, Westbury, N.Y., Sources of cherry samples citric acid. The pH was about 3.0. Plastic U.S.A.) at 40 °C. The polyphenolics and an- Rainier sweet cherries were provided by wrap covered the glass jars to allow for air thocyanins were redissolved in acidified the Mid-Columbia Experiment Station, diffusion. The brined fruit was stored for 12 water and stored at –70 °C. Samples were Hood River, Ore. Two varieties of sweet cher- mo at 22 °C. After 12 mo, cherries were filtered through a 0.45-M Millipore filter ries, Bing and Royal Ann, and 1 variety of washed with running cold water for about 5 paper (Type HA, Millipore Corp., Bedford, sour cherries, Montmorency, were harvested d, until sulfur dioxide content of cherries Mass., U.S.A.) before high-performance liq- at the Lewis Brown Horticultural Farm, Or- was less than 200 parts per million. Washed uid chromatography (HPLC) injection. egon State Univ. Dept. of Horticulture, Cor- brined cherries were frozen with liquid nitro- vallis, Ore. Oregon Cherry Growers, Inc., gen and stored at –70 °C. The spent brine Acid hydrolysis of anthocyanins Salem, Ore., supplied Bing and Royal Ann solution was also stored at –70 °C. Acid hydrolysis was performed by the pro- cherries for the brining experiment and also cedure as described by Durst and Wrolstad provided Bing cherries for canning and fro- Extraction of anthocyanins and (2001). Five milliliters of 2 N HCl were add- zen storage experiments. Cherries were de- polyphenolics ed to purified anthocyanins (about 1 mL) in livered to the Dept. of Food Science and Samples were liquid nitrogen powdered a screw-cap test tube, flushed with nitrogen, Technology, Oregon State Univ., Corvallis, using a stainless-steel Waring Blender. Pow- and capped. The purified compound was Ore., and then were stored at 2 °C before dered samples (about 10