CN114874640A - Method for improving color stability of mulberry red pigment based on mulberry anthocyanin derivative - Google Patents
Method for improving color stability of mulberry red pigment based on mulberry anthocyanin derivative Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B57/00—Other synthetic dyes of known constitution
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
- C07H1/00—Processes for the preparation of sugar derivatives
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
- C07H17/00—Compounds containing heterocyclic radicals directly attached to hetero atoms of saccharide radicals
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
- C07H17/00—Compounds containing heterocyclic radicals directly attached to hetero atoms of saccharide radicals
- C07H17/04—Heterocyclic radicals containing only oxygen as ring hetero atoms
- C07H17/06—Benzopyran radicals
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B68/00—Organic pigments surface-modified by grafting, e.g. by establishing covalent or complex bonds, in order to improve the pigment properties, e.g. dispersibility or rheology
- C09B68/40—Organic pigments surface-modified by grafting, e.g. by establishing covalent or complex bonds, in order to improve the pigment properties, e.g. dispersibility or rheology characterised by the chemical nature of the attached groups
- C09B68/44—Non-ionic groups, e.g. halogen, OH or SH
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/62—Detectors specially adapted therefor
- G01N30/72—Mass spectrometers
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N2030/022—Column chromatography characterised by the kind of separation mechanism
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Abstract
The invention provides a method for improving mulberry red pigment color stability based on mulberry anthocyanin derivatives, which comprises the steps of mixing a mulberry red pigment extract solution with a cysteine solution, heating at 80 ℃ under the conditions of nitrogen filling, sealing and light shielding to perform nucleophilic addition reaction to generate the mulberry anthocyanin derivatives. Compared with the original mulberry haematochrome, the mulberry anthocyanin derivative prepared by the invention has better thermal stability and can keep the color of the mulberry haematochrome solution for a long time. The treatment method for improving the color stability of the mulberry red pigment by using the addition reaction between cysteine and anthocyanin is simple, convenient and easy to implement, and can play a good role in inhibiting fading of anthocyanin pigments caused by heat treatment.
Description
Technical Field
The invention belongs to the technical field of natural pigment processing, and particularly relates to a method for improving color stability of mulberry red pigment based on mulberry anthocyanin derivatives.
Background
However, the mulberry is a hot berry, is greatly influenced by seasons and climates, is difficult to store at room temperature for a long time, is easy to rot at high temperature, and causes certain economic loss, so that the mulberry is very important for deep processing and development of high-value-added products. The mulberry contains rich anthocyanin substances, and can be applied to the natural edible pigment industry after separation, purification and extraction, such as vegetable juice (pulp) beverage, fruit wine, jelly, cake and other foods.
The mulberry haematochrome belongs to anthocyanin natural pigments, the main anthocyanin types of the mulberry haematochrome are cyanidin-3-O-glucoside and cyanidin-3-O-rutinoside, the mulberry haematochrome has stronger antioxidation, anti-inflammatory and antithrombotic effects, and the incidence rate of coronary heart disease and diabetic complications can be reduced. However, anthocyanins are sensitive to environmental factors such as temperature, pH, light, oxygen, enzymes, metal ions and the like in an aqueous solution state, and cause food discoloration, thereby limiting the wide application thereof in the food industry.
Several anthocyanin stabilizing methods and technologies mainly researched at present comprise addition of macromolecular food components, micromolecular auxiliary color effect, metal ion chelation effect, embedding technology and the like, but the methods are generally limited in application due to the problems of no long-acting stability, weakening of natural color, high cost, low safety and the like, so that the problem of remarkably improving the stability of anthocyanin and expanding the application range of natural anthocyanin is a difficult problem to be solved urgently.
Disclosure of Invention
In order to solve the technical problem of poor color stability of the mulberry red pigment in the prior art, the invention provides a method for improving the color stability of the mulberry red pigment based on mulberry anthocyanin derivatives.
The purpose of the invention is realized by the following technical scheme:
the invention aims to provide a method for improving mulberry red pigment color stability based on mulberry anthocyanin derivatives, which comprises the steps of mixing a mulberry anthocyanin extract (purchased from Tianjin peak biotechnology limited) solution with a cysteine solution under the condition of neutral pH, heating and reacting to generate the mulberry anthocyanin derivatives so as to improve the color stability of the mulberry red pigment.
In one embodiment of the present invention, the structural formula of the mulberry anthocyanin derivative is shown in I to VIII:
in one embodiment of the present invention, the mass ratio of mulberry anthocyanin extract to cysteine is 1: 1-15.
In one embodiment of the invention, the concentration of the mulberry anthocyanin extract solution is 0.1-0.2 mg/mL.
In one embodiment of the invention, the concentration of the cysteine solution is 0.1 to 3.0 mg/mL.
In one embodiment of the invention, the concentration of the cysteine solution is 0.16-2.4 mg/mL.
In one embodiment of the invention, the pH is in the range of 6 to 8.
In one embodiment of the invention, the temperature of the heating is 80-100 ℃.
In one embodiment of the invention, the heating time is 30-120 min.
In one embodiment of the invention, the mulberry anthocyanin derivative is subjected to component monitoring by using a high performance liquid chromatograph, and the detection conditions of the high performance liquid chromatograph are as follows:
a chromatographic column: XBridge C18, 250mm × 4.6mm in size, 5 μm in pore size; the detection wavelength is 513 nm; the column temperature is 30 ℃; the flow rate is 1.0 mL/min; the sample volume is 10 mu L; mobile phase a-2% aqueous formic acid, B-acetonitrile, gradient elution: 0min, 94% A, 6% B; 18min, 88% A, 12% B; 22min, 20% A, 80% B; 23min, 94% A, 6% B; 30min, 94% A, 6% B.
In one embodiment of the invention, the mulberry anthocyanin derivative is subjected to component separation and identification by using an ultra-high performance liquid chromatography-time-of-flight mass spectrometer, wherein the separation conditions of the ultra-high performance liquid chromatography are as follows:
a chromatographic column: BEH C18, size 100mm × 2.1mm i.d, pore size 1.7 μm; the detection wavelength is 513 nm; the column temperature is 45 ℃; the flow rate is 0.3 mL/min; the sample size is 5 mu L; mobile phase a-2% aqueous formic acid, B-acetonitrile, gradient elution: 0min, 6% B; 0-10min, 6% -16% B; 10-14min, 16% -25% B; 14-15min, 25% -50% B; 15-17min, 100% B; 17-20min, 100% -6% B.
In one embodiment of the present invention, the conditions identified by the mass spectrometry separation are:
the mass spectrum detection conditions are as follows: setting two channels, detecting the positive ion mode, and setting the conditions as follows: mass spectral range m/z 50-2000, collision energy of channel 1: 6.0eV, channel 2: 25.0eV, taper hole voltage: 30.0V, capillary voltage: 3.0kV, taper hole air flow rate: 10L/h, desolventizing air flow rate: 700L/h, ion source temperature: 100 ℃, desolventizing gas temperature: at 400 ℃.
The technical scheme of the invention has the following advantages:
the invention provides a method for improving color stability of mulberry red pigment based on mulberry anthocyanin derivatives, which aims at the problems that anthocyanin natural pigments in food are poor in stability and easy to degrade and fade under heat.A cysteine and mulberry anthocyanin extracts are mainly utilized to perform an addition reaction at high temperature, so that the cysteine is combined with C-6, C-7 or C-7 and C-8 of anthocyanin molecules, a pi conjugated structure of the prepared mulberry anthocyanin derivatives is not damaged and still retains a chromophore, and the stability of the anthocyanin derivatives is better than that of original anthocyanin through experiment measurement, so that the color stability of the mulberry under the heat treatment condition can be improved, and the bright color can be retained. The delta E of the pigment solution after heat treatment for 120min at 80 ℃ can be reduced by 31.0-56.1% through experimental determination. The processing method for improving the color stability of the mulberry red pigment by using the addition reaction between the cysteine and the anthocyanin is simple, convenient and easy to implement, and can play a good role in inhibiting fading of the anthocyanin pigment caused by heat treatment.
Drawings
In order that the present disclosure may be more readily and clearly understood, reference is now made to the following detailed description of the embodiments of the present disclosure taken in conjunction with the accompanying drawings, in which
FIG. 1 is a high performance liquid chromatogram of mulberry anthocyanin pigment with different concentrations of cysteine after heating in water bath at 80 deg.C/120 min in examples 1-4 of the present invention;
FIG. 2 is a high performance liquid chromatogram of mulberry anthocyanin pigment of example 4 of the present invention and comparative examples 1 to 4, to which cysteine was added after heating in water bath at 80 ℃ for various periods;
FIG. 3 is a high performance liquid chromatogram of mulberry anthocyanin pigment of comparative example 5 to 9 of the present invention, to which cysteine was added under the condition of pH 3.6 after heating in water bath at 80 ℃ for various times;
FIG. 4 is a high performance liquid chromatogram of mulberry anthocyanin pigment and derivatives thereof in example 11 of the present invention;
FIG. 5 is a mass spectrum of mulberry anthocyanin pigment and derivatives thereof in example 11 of the present invention; wherein, FIG. 5(a) is the mass spectrum of cyanidin-3-O-glucoside (C3G) in example 11 of the invention; FIG. 5(b) is a mass spectrum of cyanidin-3-O-rutinoside (C3R) in example 11 of the invention; FIG. 5(c) is a mass spectrum of the anthocyanin derivative (formula I or formula II) in example 11 of the present invention; FIG. 5(d) is a mass spectrum of an anthocyanin derivative (formula III or formula IV) in example 11 of the present invention; FIG. 5(e) is a mass spectrum of an anthocyanin derivative (formula V or formula VI) in example 11 of the invention; FIG. 5(f) is a mass spectrum of the anthocyanin derivative (formula VII or formula VIII) in example 11 of the present invention.
Detailed Description
The present invention is further described below in conjunction with the following figures and specific examples so that those skilled in the art may better understand the present invention and practice it, but the examples are not intended to limit the present invention.
Example 1:
dissolving mulberry red pigment extract (purchased from Tianjin peak biotechnology limited) and cysteine in phosphate buffer solution with pH of 6.8, respectively, preparing into 0.16mg/mL mulberry anthocyanin solution and 0.16mg/mL cysteine solution, and stirring at 300r/min until fully dissolving. Mixing mulberry anthocyanin solution and cysteine solution in equal volume, and stirring at 300r/min for 15min to obtain mixed solution. Placing the above solution in a glass bottle with a screw cap, sealing with nitrogen, heating in 80 deg.C water bath for 120min in dark place, and detecting whether mulberry anthocyanin derivative is generated by high performance liquid chromatography.
Example 2:
dissolving mulberry anthocyanin extract and cysteine in phosphate buffer solution with pH of 6.8, respectively, preparing into 0.16mg/mL mulberry anthocyanin solution and 0.8mg/mL cysteine solution, and stirring at 300r/min for dissolving completely. Mixing mulberry anthocyanin solution and cysteine solution in equal volume, and stirring at 300r/min for 15min to obtain mixed solution. Placing the above solution in a glass bottle with a screw cap, sealing with nitrogen, heating in 80 deg.C water bath for 120min in dark place, and detecting whether mulberry anthocyanin derivative is generated by high performance liquid chromatography.
Example 3:
dissolving mulberry anthocyanin extract and cysteine in phosphate buffer solution with pH of 6.8, respectively, preparing into 0.16mg/mL mulberry anthocyanin solution and 1.6mg/mL cysteine solution, and stirring at 300r/min for dissolving completely. Mixing mulberry anthocyanin solution and cysteine solution in equal volume, and stirring at 300r/min for 15min to obtain mixed solution. Placing the above solution in a glass bottle with a screw cap, sealing with nitrogen, heating in 80 deg.C water bath for 120min in dark place, and detecting whether mulberry anthocyanin derivative is generated by high performance liquid chromatography.
Example 4:
dissolving mulberry anthocyanin extract and cysteine in phosphate buffer solution with pH of 6.8, respectively preparing into 0.16mg/mL mulberry anthocyanin solution and 2.4mg/mL cysteine solution, and stirring at rotation speed of 300r/min until fully dissolving. Mixing mulberry anthocyanin solution and cysteine solution in equal volume, and stirring at 300r/min for 15min to obtain mixed solution. Placing the above solution in a glass bottle with a screw cap, sealing with nitrogen, heating in 80 deg.C water bath for 120min in dark place, and detecting whether mulberry anthocyanin derivative is generated by high performance liquid chromatography.
Example 5:
dissolving mulberry anthocyanin extract and cysteine in phosphate buffer solution with pH of 6.8, respectively, preparing into 0.16mg/mL mulberry anthocyanin solution and 0.16mg/mL cysteine solution, and stirring at 300r/min for dissolving completely. Mixing mulberry anthocyanin solution and cysteine solution in equal volume, and stirring at 300r/min for 15min to obtain mixed solution. Placing the above solution in a glass bottle with a screw cap, sealing with nitrogen, heating in 80 deg.C water bath for 120min in dark place, and measuring solution chromaticity.
Example 6:
dissolving mulberry anthocyanin extract and cysteine in phosphate buffer solution with pH of 6.8, respectively, preparing into 0.16mg/mL mulberry anthocyanin solution and 0.8mg/mL cysteine solution, and stirring at 300r/min for dissolving completely. Mixing mulberry anthocyanin solution and cysteine solution in equal volume, and stirring at 300r/min for 15min to obtain mixed solution. Placing the above solution in a glass bottle with a screw cap, sealing with nitrogen, heating in 80 deg.C water bath for 120min in dark place, and measuring solution chromaticity.
Example 7:
dissolving mulberry anthocyanin extract and cysteine in phosphate buffer solution with pH of 6.8, respectively, preparing into 0.16mg/mL mulberry anthocyanin solution and 1.6mg/mL cysteine solution, and stirring at 300r/min for dissolving completely. Mixing mulberry anthocyanin solution and cysteine solution in equal volume, and stirring at 300r/min for 15min to obtain mixed solution. Placing the above solution in a glass bottle with a screw cap, sealing with nitrogen, heating in 80 deg.C water bath for 120min in dark place, and measuring solution chromaticity.
Example 8:
dissolving mulberry anthocyanin extract and cysteine in phosphate buffer solution with pH of 6.8, respectively, preparing into 0.16mg/mL mulberry anthocyanin solution and 2.4mg/mL cysteine solution, and stirring at 300r/min for dissolving completely. Mixing mulberry anthocyanin solution and cysteine solution in equal volume, and stirring at 300r/min for 15min to obtain mixed solution. Placing the above solution in a glass bottle with a screw cap, sealing with nitrogen, heating in 80 deg.C water bath for 120min in dark place, and measuring solution chromaticity.
Comparative example 1:
the preparation method is the same as that of example 4, except that the water bath heating time is replaced by 0 min.
Comparative example 2:
the preparation method is the same as that of example 4, except that the water bath heating time is replaced by 30 min.
Comparative example 3:
the preparation method is the same as that of example 4, except that the water bath heating time is replaced by 60 min.
Comparative example 4:
the preparation method is the same as that of example 4, except that the water bath heating time is replaced by 90 min.
Comparative example 5:
the preparation method is the same as that of example 4, except that the buffer solution is replaced by citric acid buffer solution with pH 3.6, and the water bath heating time is replaced by 0 min.
Comparative example 6:
the preparation method is the same as that of example 4, except that the buffer solution is replaced by citric acid buffer solution with pH 3.6, and the water bath heating time is replaced by 30 min.
Comparative example 7:
the preparation method is the same as that of example 4, except that the buffer solution is replaced by citric acid buffer solution with pH 3.6, and the water bath heating time is replaced by 60 min.
Comparative example 8:
the preparation method is the same as that of example 4, except that the buffer solution is replaced by citric acid buffer solution with pH 3.6, and the water bath heating time is replaced by 90 min.
Comparative example 9:
the preparation was the same as in example 4 except that the buffer was replaced with a citric acid buffer solution at pH 3.6.
Example 9 high Performance liquid chromatography
(1) The samples from examples 1-4 were tested by high performance liquid chromatography.
The samples from examples 1-4 were tested by high performance liquid chromatography. Wherein the conditions of the liquid chromatography detection are as follows: a chromatographic column: XBridge C18, 250mm × 4.6mm in size, 5 μm in pore size; the detection wavelength is 513 nm; the column temperature is 30 ℃; the flow rate is 1.0 mL/min; the sample volume is 10 mu L; mobile phase a-2% aqueous formic acid, B-acetonitrile, gradient elution: 0min, 94% A, 6% B; 18min, 88% A, 12% B; 22min, 20% A, 80% B; 23min, 94% A, 6% B; 30min, 94% A, 6% B.
High performance liquid chromatograms of mulberry anthocyanin pigment with different concentrations of cysteine added after heating in water bath at 80 deg.C/120 min in examples 1-4 are shown in FIG. 1. As can be seen from fig. 1, as the concentration ratio of cysteine to mulberry anthocyanin extract increased, the two peak areas at retention times of 15.66min and 17.47min became smaller and larger, and the peak area at retention time of 21.12min became larger and larger. The two peaks at retention times of 15.66min and 17.47min are identified as cyanidin-3-O-glucoside and cyanidin-3-O-rutinoside, respectively, and the peak at 21.12min is a derivative of two anthocyanins. Shows that the generation of mulberry anthocyanin derivatives is in positive correlation with the concentration of cysteine.
(2) The samples of comparative examples 1-9 were subjected to HPLC analysis.
The samples of comparative examples 1-4 were tested by high performance liquid chromatography. Wherein the conditions of the liquid chromatography detection are as follows: a chromatographic column: XBridge C18, 250mm × 4.6mm in size, 5 μm in pore size; the detection wavelength is 513 nm; the column temperature is 30 ℃; the flow rate is 1.0 mL/min; the sample size is 10 mu L; mobile phase a-2% aqueous formic acid, B-acetonitrile, gradient elution: 0min, 94% A, 6% B; 18min, 88% A, 12% B; 22min, 20% A, 80% B; 23min, 94% A, 6% B; 30min, 94% A, 6% B.
High performance liquid chromatograms of mulberry anthocyanin pigment prepared by heating in water bath at 80 deg.C for different periods of time and adding cysteine in comparative examples 1-4 are shown in FIG. 2. As can be seen from FIG. 2, as the heating time was increased, the two peak areas at the retention time of 15.66min and 17.47min became smaller, and the peak area at the retention time of 21.12min became larger. Shows that the generation of mulberry anthocyanin derivatives is positively correlated with the heating time.
High performance liquid chromatograms of mulberry anthocyanin pigment prepared by heating in water bath at 80 deg.C for various times and adding cysteine at pH 3.6 in comparative examples 5-9 are shown in FIG. 3. As can be seen from fig. 3, no new chromatographic peak appeared with the increase of the heating time during the heat treatment, indicating that the addition reaction mentioned in the present invention could not occur under acidic conditions and no anthocyanin derivative was produced.
Example 10 evaluation of thermal stability
The color of the pigment solutions of examples 5 to 8 was evaluated for thermal stability, and the brightness (L), red-green (a), and yellow-blue (b) of the samples were measured by a spectrocolorimeter, and the colorimetric value (C), Hue angle (Hue °), and Hue difference value (Δ E) were calculated by the following formulas.
Wherein L 0 *、a 0 *、b 0 And is a colorimetric value of the pigment solution without heat treatment.
The results are shown in Table 1. It is known from a review of the literature: smaller values of L indicate darker colors, larger values of C indicate higher saturation, smaller values of Hue ° indicate more red-biased hues, and smaller values of Δ E indicate better color stability. As can be seen from table 1, the color of the pigment solution is redder, the saturation is higher, and the color stability is improved as L, Hue ° and Δ E of examples 5 to 8 are decreased and C is increased compared with the control group (the preparation method of the control group is the same as that of example 5, except that the addition amount of cysteine is 0), and the color improvement and stabilization effects are more obvious as the mass ratio of cysteine is increased from example 5 to example 8, and Δ E is decreased by 31.0%, 40.9%, 52.7% and 56.1% respectively compared with the control group.
TABLE 1 evaluation results of thermal stability of color of pigment solutions in examples 5 to 8
Example 11: structural identification of derivatives
Dissolving mulberry anthocyanin extract and cysteine in phosphate buffer solution with pH of 6.8, respectively, preparing into 0.16mg/mL mulberry anthocyanin solution and 2.4mg/mL cysteine solution, and stirring at 300r/min for dissolving completely. Mixing mulberry anthocyanin solution and cysteine solution in equal volume, and stirring at 300r/min for 15min to obtain mixed solution. Placing the solution in a glass bottle with a screw cap, filling nitrogen, sealing, heating in water bath at 80 ℃ for 120min in the dark, and separating and identifying the sample by using ultra-high performance liquid chromatography flight time mass spectrometry, wherein the ultra-high performance liquid chromatography separation conditions are as follows: a chromatographic column: BEH C18, size 100mm × 2.1mm i.d, aperture 1.7 μm; the detection wavelength is 513 nm; the column temperature is 45 ℃; the flow rate is 0.3 mL/min; the sample injection amount is 5 mu L; mobile phase a-2% aqueous formic acid, B-acetonitrile, gradient elution: 0min, 6% B; 0-10min, 6% -16% B; 10-14min, 16% -25% B; 14-15min, 25% -50% B; 15-17min, 100% B; 17-20min, 100% -6% B. The mass spectrum detection conditions are as follows: setting two channels, detecting the positive ion mode, and setting the conditions as follows: mass spectral range m/z 50-2000, collision energy of channel 1: 6.0eV, channel 2: 25.0eV, taper hole voltage: 30.0V, capillary voltage: 3.0kV, taper hole air flow rate: 10L/h, desolventizing air flow rate: 700L/h, ion source temperature: 100 ℃, desolventizing gas temperature: at 400 deg.c.
As shown in fig. 4 and 5, it can be seen from fig. 4 and 5 that peaks 1 and 2 in fig. 4 correspond to fig. 5(a) and 5(b), peaks 1 correspond to cyanidin-3-O-glucoside (C3G), and peaks 2 correspond to cyanidin-3-O-rutinoside (C3R), which are all anthocyanins present in the mulberry anthocyanin extract.
The positive ion molecular weights in fig. 5(c) correspond to: C3G mw (449) + cysteine mw (121) - (18+2), and m/z 388 fragment ion was obtained from m/z 287+ cysteine mw (121) - (18+2), indicating that the binding site of cysteine to C3G is located on the host structure and not on the glycoside, and that the compound absorbs at 513nm, indicating that the pi-conjugated structure of the yellow melting salt is still retained. Cysteine can combine with C3G at C-6, C-7 or C-7, C-8 position during heat treatment to form new anthocyanin derivatives (formula I or formula II). The peak 4 corresponds to the adduct of C3R and cysteine, and FIG. 5(d) shows the corresponding mass spectrum, and the structural formula is shown as formula III or formula IV in the same way.
The mass spectrum of peak 5 is shown in fig. 5(e), where the positive ion molecular weight corresponds to: C3G molecular weight (449) + cysteine molecular weight (121) -18, also illustrated is an adduct of C3G with cysteine, with a binding site at C-7 or C-5, and having the structure of formula V or formula VI. Similarly, the mass spectrum of peak 6 is shown in fig. 5(f) and corresponds to the adduct of C3R and Cys, and the structure is shown in formula vii or formula viii.
Therefore, the method for improving the mulberry haematochrome based on the mulberry anthocyanin derivative provided by the invention obviously improves the color stability of the mulberry haematochrome. The anthocyanin derivative with similar color and higher stability as the original anthocyanin is synthesized by the addition reaction of cysteine and mulberry anthocyanin under the heat treatment, and after the heat treatment, the delta E of a pigment solution containing the mulberry anthocyanin derivative can be reduced by 31.0 to 56.1 percent after the heat treatment for 120min at 80 ℃. The processing method for preparing the mulberry anthocyanin derivative and improving the stability of the mulberry red pigment by utilizing the addition reaction of the cysteine and the mulberry anthocyanin is simple and convenient to operate, can play a good role in inhibiting fading and browning of the mulberry red pigment caused by heat treatment, and has a good application prospect.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications of the invention may be made without departing from the spirit or scope of the invention.
Claims (10)
1. A method for improving color stability of mulberry red pigment based on mulberry anthocyanin derivatives is characterized by mixing a mulberry anthocyanin extract solution with a cysteine solution under the condition of neutral pH, and heating for reaction to generate the mulberry anthocyanin derivatives so as to improve the color stability of the mulberry red pigment.
2. The method according to claim 1, wherein said mulberry anthocyanin derivative has the structural formula I-VIII:
3. the method according to claim 1, wherein the mass ratio of mulberry anthocyanin extract to cysteine is 1: 1-15.
4. The method of claim 1, wherein the concentration of the mulberry anthocyanin extract solution is 0.1 to 0.2 mg/mL.
5. The method of claim 1, wherein the cysteine solution is at a concentration of 0.1-3.0 mg/mL.
6. The method of claim 5, wherein the cysteine solution is at a concentration of 0.16-2.4 mg/mL.
7. The method of claim 1, wherein the pH is in the range of 6-8.
8. The method of claim 1, wherein the heating is at a temperature of 80-100 ℃.
9. The method of claim 1, wherein the heating time is 30-120 min.
10. The method of claim 1, wherein the mixed solution after reaction is subjected to component separation and identification by using an ultra performance liquid chromatography-time-of-flight mass spectrometer, and the separation conditions of the ultra performance liquid chromatography are as follows: mobile phase a-2% aqueous formic acid, B-acetonitrile, gradient elution: 0min, 6% B; 0-10min, 6% -16% B; 10-14min, 16% -25% of B; 14-15min, 25% -50% B; 15-17min, 100% B; 17-20min, 100% -6% B.
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| CN101778576A (en) * | 2007-03-15 | 2010-07-14 | 欧博康有限公司 | stabilized anthocyanin compositions |
| CN109730318A (en) * | 2018-11-21 | 2019-05-10 | 北京市林业果树科学研究院 | It is a kind of improve fraise glycosides stability composition and its application |
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