KR20110023169A - Anthocyanidin and anthocyanins maded from omija pigment - Google Patents

Abstract

PURPOSE: Anthocyanidin and anthocyanins made from Schizandrae Fructus pigment are provided to obtain Cya-3-0-rutinoside, Cya-3-0-glucoside, and Cyanidin by acid-decomposing Cya-3-0-xylrut and a standard pigment composition in which single or 2-4 kinds of pigment are mixed. CONSTITUTION: A method for preparing a standard pigment composition comprises the steps of: adding HCl and trifluoroacetic acid(TFA) to Schizandrae Fructus fruit juice in order to become 2-4 mole; heating an acid additive solution for decomposition so that Cya-3-0-rutinoside becomes Cya-3-0-glucoside, Cya-3-0-xylrut, and Cyanidin; fractionizing the heated material with Isoamyl butanol to fractionize anthocyanidin and anthocyanins; and concentrating Isoamyl butanol fractions, and quick freezing and drying the fractions.

Description

Anthocyanidin and anthocyanins maded from Omija pigment

The present invention utilizes cyanidin-3 using cyanidin-3-O- (2G-0-xylosiluroside) (Cya-3-0-xylrut), a major anthocyanin that accounts for more than 90% of the total pigment of Schizandra chinensis. -A method for making glucoside (Cya-3-0-glucoside), cyanidin-3-rutinoside (Cya-3-0-rutinoside) and cyanidin and a mixture of single and two to four pigments It relates to a standard pigment composition.

The pigment of Schizandra chinensis fruit red color is flavonoid cyanidin-based anthocyanin.

Anthocyanins exist in glycosides in the vacuoles or cytoplasm of plants, and when hydrolyzed, anthocyanidins, sugars and non-saccharides, are produced. Anthocyanidins are largely classified into six types, and cyanidin, which is magenta, is the most common substance, orange is due to pelargonidin, which has one hydroxyl (OH) group than cyanidin, Terminal colors, red and blue are due to delphinidin, which has one more hydroxyl group than cyanidin. In addition to these three non-saccharides, there are peonidin, which is a derivative of cyanidin, which is methylester, and petunidin and malvidin, which are derivatives of delphinidin.

Anthocyanin pigments are composed of a combination of anthocyanidins and sugars. In some cases, hundreds of species exist in nature due to the combination of aromatic or non-aromatic organic acids. There are currently over 300 species of chemical structure identified (Jung Myung-geun, Samcheok University).

Several studies have been attempted to find out the types of red anthocyanins of Schizandra chinensis, but each investigator reports different findings and requires precise analysis.

Kim et al. (1973, Korean J. Food Sci. Technol. 5 (3): 178-182), in the paper on the general ingredients, organic acids, and anthocyanin pigments of Schizandra chinensis, the major anthocyanin of Schizandra chinensis was peonidin-3-glucoside. , Song (1982, Master's Thesis, Chonbuk National University) also found that the main pigments of Schizandra chinensis were peonidin-3-glucoside (70.8%) and cyanidin-3-glucoside (23.1%). Total anthocyanin content was reported as 84.74mg%.

Ryu et al. (1998, The 30th Fall Conference of Korea Breeding Society 96-97) showed that the main pigments of Schizandra chinensis were petunidin-3-glucoside (P3G) and cyanidin-3-glucoside (C3G). And 67.1 mg% P3G and 31.24 mg% C3G. Lee et al. (1999, Final Research Report by the Ministry of Agriculture and Forestry) reported the color reaction of AlC ₃ of Schizandra chinensis in the development of cultivation and mass propagation technology and the development of special ingredients and natural beverages of Jeju Schisandra chinensis. Was peonidin-3-glucoside and the total amount was 86.54mg%.

However, Cho et al. (2003, Korean J. Food Sci. Technol. 35 (1): 23-27) said that the pigment of Schizandra chinensis cyanidin-3-glucoside accounted for 91% of the total anthocyanin. In J. Food Culture 18 (5): 475-482), the main pigments of Schisandra chinensis were cyanidin-3-glucoside (91%), delphinidin-3-glucoside (1%), and cyanidin-3-arabinoside (3%). Four unidentified peaks accounted for 6%.

Recently, Kim et al. (2009, Journal of Food Science 74: 134-140) said that the main pigment of Schizandra chinensis in "Structural and Antioxidant Capability of Main Anthocyanin Extracted from Schizandra" is cyanidin-3-O- (2G-0- Xyloxylutinroside) (Cya-3-0-xylrut).

Thus, one of the causes of the different results reported by the researchers in the identification of Schizandra chinensis was due to the lack of a standard suitable for Schizandra pigment analysis. There is a need for standard pigment compositions necessary for the analysis of Schizandra pigments, as well as for the analysis of anthocyanins and anthocyanidins present in nature, or analysis of processed product pigment components.

When quantitatively analyzing the components of anthocyanin using HPLC, the standard of anthocyanin to be analyzed must be present. Analysis using HPLC is not possible without the reference material because the analysis results are interpreted by comparison of the retention time of the standard and the sample components. In addition, there is a difference in retention time depending on the amount of sample, sample preparation method, and reproducibility of HPLC. In some cases, after mixing and analyzing a sample of a certain concentration in a standard, whether the peak of the analytical sample and the peak of the standard are combined into one. It may be necessary to perform a peak test to verify that. In particular, in order to know what kind of anthocyanins, it is natural to have a standard that is mixed with many kinds of anthocyanins. However, anthocyanins and anthocyanidins are so diverse that they are not readily available, and some representative ones are sold, but the price is very high.

The present invention uses cyanidin-3-O- (2G-0-xylosiluroside) (Cya-3-) to make a standard pigment composition in which a single and two to four pigments are mixed using a Schizandra pigment anthocyanin. 0-xylrut) to separate xylose to make cyanidin-3-rutinoside (Cya-3-0-rutinoside), and to separate rhamnose from cyanidin-3-rutinroside (Cya-3-0-rutinoside) To make cyanidin-3-glucoside, and finally to separate glucose from cyanidin-3-glucoside to make cyanidin. The problem was to make a standard pigment composition by mixing single and two to four pigments using the components.

In order to find out how to make 1 anthocyanidin and 3 anthocyanins using Schisandra chinensis, the following steps are carried out.

Step 1: investigating the acid solution and its concentration capable of degrading Schisandra chinensis

Step 2: Investigate temperature and time to decompose by adding acid solution

Step 3: pure separation of anthocyanin and anthocyanidin from the acid pyrolysate

Step 4: Concentrate the solvent fractions, and dissolve the concentrate with water to freeze-dry.

Step 5: Mix the ingredients made to make the required anthocyanin standard pigment composition

In the present invention, the anthocyanin of Schizandra chinensis revealed that cyanidin-3-O- (2G-0-xylosiluroside) (Cya-3-0-xylrut) is composed of 93.8% or more, and cyanidin-3-O Acid Decomposition of (2G-0-Xyloxylutinside) (Cya-3-0-xylrut) to Cyanidin-3-rutinoside, Cyanidin-3-glucoside (Cya-3-0-glucoside) and cyanidin were made and a solution was made to make a standard pigment composition in which single or two to four pigments were mixed.

Cyanidin-3-rutinroside (Cya-3-0) using Cyanidin-3-O- (2G-0-xylosiluroside) (Cya-3-0-xylrut) -2 kinds of anthocyanins, such as -rutinoside) and cyanidin-3-glucoside, and 1 type of anthocyanidin, Cyanidin, and a single or 2 to 4 pigments The detailed contents promoted step by step in order to find out how to make a mixture composition is as follows.

Example 1: Investigate the acid solution and its concentration capable of degrading Schisandra chinensis

Analysis of Schisandra chinensis by HPLC showed a major peak at 14.5 minutes as shown in FIG. 1. The area percentage of the peak was 93.86%, which was the peak of Schisandra chinensis anthocyanin, but HPLC analysis did not reveal what kind of anthocyanin the peak appeared at 14.5 minutes. In order to know specifically the composition and content of the peak indicated by 14.5 minutes by HPLC analysis, a standard should be present.

To make the standard pigment composition of anthocyanidin using the pigment of Schizandra chinensis juice, the concentration of hydrochloric acid (HCl) and trifluoroacetic acid (TFA) was adjusted to 1 to 4 mol, and anthocyanin was analyzed by HPLC. Both TFAs were effective in separating sugars from anthocyanins, glycosides, and as both concentrations increased, the rate of anthocyanin degradation as shown in FIGS. 2, 3, and 4 was faster.

Run 2: investigate temperature and time to decompose by adding acid solution

The anthocyanin and anthocyanidins were analyzed by HPLC while digesting the Schisandra chinensis solution so that the concentrations of hydrochloric acid (HCl) and trifluoroacetic acid (TFA) were 2 moles for 20 minutes at a temperature of 80 to 100 ° C. As shown in FIG. 2, the analysis was performed as shown in FIG. 3 at 5 minutes and FIG. 4 at 20 minutes. These results suggest that adjusting the acid concentration, temperature, and decomposition time can produce mixed standard pigment compositions containing anthocyanidins and anthocyanidins and containing two to three anthocyanins. .

Example 3: Pure fractionation of anthocyanin and anthocyanidin from acid pyrolysate

In order to fractionate the anthocyanidins and anthocyanins from the acid-heat decomposition products, isoamyl butanol was mixed with the acid-heat decomposition products in the same amount and fractionated. It was thought that it could be used effectively.

Figure 1 shows the major peak of cyanidin-3-O- (2G-0-xylosiluroside (Cya-3-0-xylrut) at 14.5 min by HPLC analysis of Schizandra chinensis.

FIG. 2 shows cyanidin-3-O- (2G-0-xylosiluroside (Cya-3-0-xylrut), 10.43 at 13.55 min in the initial (2-5 min) HPLC analysis table of Schizandra pigment. 4 cyanidin-3-glucosides in minutes, cyanidin-3-rutyroside in 14.65 minutes and cyanidins in 24.18 minutes Peaks appear.

FIG. 3 shows two peaks of cyanidin-3-glucoside (Cya-3-0-glucoside) at 10.9 min and Cyanidin at 23.93 min with acid digestion medium (6-10 min) HPLC analysis table of Schizandra chinensis. Will appear.

4 shows two peaks of cyanidin-3-glucoside (Cya-3-0-glucoside) at 11.83 minutes and Cyanidin at 23.96 minutes with the end-acid (20-30 minutes) HPLC analysis table of Schizandra chinensis. Will appear.

FIG. 5 is a HPLC analysis of the acid degradation initial product of Schizandra chinensis for 3 days, followed by HPLC analysis. In 17.82 minutes, cyanidin-3-O- (2G-0-xylocilutinside, Three peaks appeared at 13.6 minutes: Cya-3-0-glucoside and 18.55 minutes at Cya-3-0-rutinoside.

Claims (2)

(A) Hydrochloric acid (HCl) and trifluoroacetic acid (TFA) were added to 2-4 mol of Schizandra chinensis solution. (B) The acid addition liquid was heated at 80 to 100 ° C., so that the cyanidin-3-O- (2G-0-xylosiluroside (Cya-3-0-xylrut) was converted to cyanidin-3-glucoside (Cya). -3-0-glucoside), cyanidin-3-rutyroside (Cya-3-0-rutinoside) and cyanidin (Cyanidin) (C) the acid pyrolysate was fractionated with isoamyl butanol to purely separate anthocyanin and anthocyanidin. (D) Concentration of Isoamyl butanol fractions and rapid freeze drying to form anthocyanin standard pigment compositions Cyanidin-3-O- (2G-0-xyloxylutinroside (Cya-3-0-) produced by adjusting the heating time by adding an acid in (B) of claim 1 to 5 to 30 minutes. xylrut), cyanidin-3-glucoside (Cya-3-0-glucoside), cyanidin-3-rutyroside (Cya-3-0-rutinoside) and cyanidin alone or two to four Mixed Schizandra-derived Pigment Composition

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