CN111034902B - High-stability pigment derivative and preparation method thereof - Google Patents
High-stability pigment derivative and preparation method thereof Download PDFInfo
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- CN111034902B CN111034902B CN201911278914.3A CN201911278914A CN111034902B CN 111034902 B CN111034902 B CN 111034902B CN 201911278914 A CN201911278914 A CN 201911278914A CN 111034902 B CN111034902 B CN 111034902B
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- China
- Prior art keywords
- proanthocyanidin
- parts
- anthocyanin
- glucoside
- pigment derivative
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- 238000002360 preparation method Methods 0.000 title claims description 6
- 150000004636 anthocyanins Chemical class 0.000 claims abstract description 50
- 235000010208 anthocyanin Nutrition 0.000 claims abstract description 49
- 229930002877 anthocyanin Natural products 0.000 claims abstract description 49
- 239000004410 anthocyanin Substances 0.000 claims abstract description 49
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- XMOCLSLCDHWDHP-UHFFFAOYSA-N L-Epigallocatechin Natural products OC1CC2=C(O)C=C(O)C=C2OC1C1=CC(O)=C(O)C(O)=C1 XMOCLSLCDHWDHP-UHFFFAOYSA-N 0.000 claims abstract description 6
- DZYNKLUGCOSVKS-UHFFFAOYSA-N epigallocatechin Natural products OC1Cc2cc(O)cc(O)c2OC1c3cc(O)c(O)c(O)c3 DZYNKLUGCOSVKS-UHFFFAOYSA-N 0.000 claims abstract description 6
- PFTAWBLQPZVEMU-DZGCQCFKSA-N (+)-catechin Chemical compound C1([C@H]2OC3=CC(O)=CC(O)=C3C[C@@H]2O)=CC=C(O)C(O)=C1 PFTAWBLQPZVEMU-DZGCQCFKSA-N 0.000 claims abstract description 4
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- PFTAWBLQPZVEMU-UKRRQHHQSA-N (-)-epicatechin Chemical compound C1([C@H]2OC3=CC(O)=CC(O)=C3C[C@H]2O)=CC=C(O)C(O)=C1 PFTAWBLQPZVEMU-UKRRQHHQSA-N 0.000 claims abstract description 4
- ADRVNXBAWSRFAJ-UHFFFAOYSA-N catechin Natural products OC1Cc2cc(O)cc(O)c2OC1c3ccc(O)c(O)c3 ADRVNXBAWSRFAJ-UHFFFAOYSA-N 0.000 claims abstract description 4
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- KQNPFQTWMSNSAP-UHFFFAOYSA-N isobutyric acid Chemical compound CC(C)C(O)=O KQNPFQTWMSNSAP-UHFFFAOYSA-N 0.000 claims description 6
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- 150000007524 organic acids Chemical class 0.000 claims description 5
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 claims description 4
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- WBYWAXJHAXSJNI-SREVYHEPSA-N Cinnamic acid Chemical compound OC(=O)\C=C/C1=CC=CC=C1 WBYWAXJHAXSJNI-SREVYHEPSA-N 0.000 claims description 3
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 3
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- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
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- 238000005286 illumination Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000012994 industrial processing Methods 0.000 description 1
- 230000003859 lipid peroxidation Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 235000009584 malvidin Nutrition 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000010297 mechanical methods and process Methods 0.000 description 1
- 239000002207 metabolite Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 238000007344 nucleophilic reaction Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- QCDYQQDYXPDABM-UHFFFAOYSA-N phloroglucinol Chemical compound OC1=CC(O)=CC(O)=C1 QCDYQQDYXPDABM-UHFFFAOYSA-N 0.000 description 1
- 229960001553 phloroglucinol Drugs 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 229920002414 procyanidin Polymers 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- OVVGHDNPYGTYIT-BNXXONSGSA-N rutinose Chemical compound O[C@@H]1[C@H](O)[C@@H](O)[C@H](C)O[C@H]1OC[C@@H]1[C@@H](O)[C@H](O)[C@@H](O)[C@H](O)O1 OVVGHDNPYGTYIT-BNXXONSGSA-N 0.000 description 1
- 210000003296 saliva Anatomy 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000005556 structure-activity relationship Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- FGMPLJWBKKVCDB-UHFFFAOYSA-N trans-L-hydroxy-proline Natural products ON1CCCC1C(O)=O FGMPLJWBKKVCDB-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
- A23L5/00—Preparation or treatment of foods or foodstuffs, in general; Food or foodstuffs obtained thereby; Materials therefor
- A23L5/40—Colouring or decolouring of foods
- A23L5/42—Addition of dyes or pigments, e.g. in combination with optical brighteners
- A23L5/47—Addition of dyes or pigments, e.g. in combination with optical brighteners using synthetic organic dyes or pigments not covered by groups A23L5/43 - A23L5/46
- A23L5/48—Compounds of unspecified constitution characterised by the chemical process for their preparation
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23V—INDEXING SCHEME RELATING TO FOODS, FOODSTUFFS OR NON-ALCOHOLIC BEVERAGES AND LACTIC OR PROPIONIC ACID BACTERIA USED IN FOODSTUFFS OR FOOD PREPARATION
- A23V2002/00—Food compositions, function of food ingredients or processes for food or foodstuffs
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Nutrition Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Food Science & Technology (AREA)
- Polymers & Plastics (AREA)
- Coloring Foods And Improving Nutritive Qualities (AREA)
- Saccharide Compounds (AREA)
Abstract
The invention discloses a high-stability pigment derivative, wherein the number average molecular weight of the pigment derivative is 523-168 Da, the content of epicatechin in a structural unit is 5-30%, the content of catechin is 3-75%, the content of gallocatechin is 1-13%, the content of epigallocatechin is 1-5%, the content of catechin gallate is 1-16%, and the content of epicatechin gallate is 2-17%. The pigment derivative provided by the invention belongs to a natural anthocyanin derivative, is not influenced by a hypothesis salt ← → chalcone ← → quinone alkali ← → methanol pseudobase chemical equilibrium, can keep stable red in an acidic to neutral (pH 1.0-7.0) solution, is not influenced by pH, oxygen, a reduction type bleaching agent and temperature, and solves the problem of poor color stability of natural anthocyanin.
Description
Technical Field
The invention relates to the field of food additives, in particular to a pigment.
Background
Anthocyanin is a natural plant pigment, and widely exists in red fruit and vegetable peels. After the color conversion period begins, the anthocyanin content in the fruit and vegetable peels gradually rises, so that the peels gradually turn into red or bright purple, and the anthocyanin content also reaches the maximum value after the fruit and vegetable are mature. Part of vegetable, fruit and peel is as follows: passion fruit shells, grapes, passion fruit, purple sweet potato peels and the like are rich in anthocyanin, and the maximum content can reach 400mg/g of dry basal peels. From the chemical structure, anthocyanin itself contains a large amount of phenolic hydroxyl groups and benzene ring structures, and belongs to polyphenol substances, and the reducibility of the phenolic hydroxyl groups is one of the commonness of the polyphenol compounds. A plurality of phenolic hydroxyl groups in anthocyanin molecules can be used as H donors, and the structure of the anthocyanin catechol A ring further enhances the reducibility of the anthocyanin catechol A ring, so that the anthocyanin catechol A ring can realize an antioxidant function through two ways of dissociation of the phenolic hydroxyl groups and free radical elimination. It has been clarified that oxygen radicals are important factors causing various diseases and aging, and also cause lipid peroxidation. The ability of anthocyanin to scavenge free radicals is very significant as a major member of polyphenol family. Therefore, anthocyanin, a natural pigment, can provide food with attractive color and also has obvious health-care function, and has obvious value for being used as a functional food additive.
In the industrial production and processing process of food, the vegetable, fruit and peel rich in anthocyanin is not suitable for direct eating due to poor taste. In order to avoid affecting the quality of the product, most food processing companies remove the pericarp of the vegetable or fruit by mechanical processing or manual removal. Such as: grape skin is removed by an air bag squeezer in a squeezing stage in the wine processing process; when the passion fruit beverage is processed, firstly, shells are removed by a manual or mechanical method; after the cleaning stage is finished, the peel of the purple sweet potato is removed by a peeler; during the production process of blueberry juice, pomace is removed by precipitation and filtration. Therefore, a large amount of byproducts such as pericarp and fruit shell are generated in the food processing process every year, but due to the problem of stability, even if anthocyanin is obtained by extraction, separation and purification, the anthocyanin is difficult to be directly used as natural edible pigment or antioxidant in the production process of food or health care products. In reality, food enterprises usually adopt direct landfill or incineration to treat anthocyanin-rich fruit and vegetable peels, which is not only a great waste of precious resources, but also can cause certain negative effects on the ecological environment.
The typical structural formula of the anthocyanin is divided according to the characteristics of chemical structures
The benzopyran derivative with C6-C3-C6 basic skeleton is prepared by linking anthocyanidin (including geranium pigment, cornflower pigment, delphinium pigment, peony pigment, petunia pigment, malvidin, etc.) with glucoside (glucose, rhamnose, galactose, rutinose, etc.), wherein the linking position of anthocyanidin and glucoside is mainly at C-3 position of C ring and C-5 position of A ring.
However, it has to be said that anthocyanins themselves are not stable. The colored anthocyanin is mainly a compound with a charge pseudonymous salt structure, the pseudonymous salt structure is very easy to lose charges in an alkaline, neutral or weakly acidic solution environment, and is converted into a colorless chalcone, quinine or methanopseudobase structure to form precipitates, as shown in the following figure, the process of converting the pseudonymous salt into other colorless structures is very easy to be influenced by factors such as temperature, pH, illumination, oxygen and the like, and meanwhile, part of antioxidants (such as sulfite) added in the food production process can also accelerate the decolorizing process of the anthocyanin.
Therefore, the anthocyanin easily loses the original color after long-term storage. The conversion of anthocyanin into colorless structure is commonly found in beverage products (such as wine, mulberry wine and fruit juice), and the phenomenon can cause the loss of attractive color and luster of the beverage, also can cause the loss of fullness of mouthfeel, and reduces the balance of mouthfeel structures such as sourness, sweetness and acerbity of the beverage so as to reduce the taste characteristics of the beverage, and finally causes the great reduction of the sensory quality of the beverage. The property of the anthocyanin shortens the shelf life of the fruit juice beverage and greatly limits the actual development and utilization value of the anthocyanin. Therefore, it is a technical problem how to obtain a pigment derivative with high stability by anthocyanin.
Disclosure of Invention
The present invention has been made in view of the above-mentioned technical disadvantages, and an object of the present invention is to provide a highly stable dye derivative and a method for producing the same.
The technical scheme adopted by the invention is as follows: a highly stable dye derivative having a number average molecular weight of 523 to 168Da, and having a structural unit comprising 5 to 30% of epicatechin, 3 to 75% of catechin, 1 to 13% of gallocatechin, 1 to 5% of epigallocatechin, 1 to 16% of catechin gallate and 2 to 17% of epicatechin gallate.
In order to further improve the scheme, the average particle diameter of the pigment derivative is 30-180 nm when the concentration is 4g \ L.
A method for preparing the pigment derivative with high stability as described above comprises the following operation steps: firstly, mixing 2-18 parts of anthocyanin and 200-5000 parts of distilled water, fully stirring for 1-25 min, then adding 0.3-100 parts of proanthocyanidin, fully stirring for 1-10 h, then adding 0.5-15 parts of cross-linking agent, fully stirring for 1-25 min, then adding 0.1-0.6 part of organic acid, uniformly mixing, sealing, placing in a dark environment at the temperature of 10-45 ℃ for 5-45 days, and drying to obtain the finished product.
The invention takes anthocyanin and proanthocyanidin as raw materials, utilizes the basic principle that an aldehyde cross-linking agent easily attacks the C-4 position of anthocyanin to form derivatives, selects proper aldehyde substances, enables the aldehyde substances to form bridge bonds between the anthocyanin and proanthocyanidin to form pigment derivatives, and enables the anthocyanin to be no longer influenced by the chemical balance of the fictile salt ← → chalcone ← → quinine base ← → methanol pseudobase, thus finally obtaining the pigment derivatives with stable color.
Among them, proanthocyanidin is a polyphenol substance, and is widely found in foods such as tea leaves, grape skins, persimmon skins, etc., and food processing by-products. Because proanthocyanidin can be mutually combined with protein rich in hydroxyproline in saliva, the food can be endowed with special sensory characteristics of astringency, and sweet and full mouthfeel can be provided for foods such as tea beverages, wine, persimmon beverages and the like, so that the proanthocyanidin is often used as a food additive for beverage production. During the brewing process of wine, it is found that some red wines gradually change from purplish red to brick red as aging progresses. This is because the color of red wine is mainly derived from anthocyanin in the pseudosalt structure at the early stage of brewing, and as the aging process proceeds, part of yeast fermentation metabolites can attack the C4 position of anthocyanin ring by nucleophilic reaction to combine with it and make it be derivatized, and the reaction products can continue to react with proanthocyanidin in grape to produce pigment with stable color. The pigment derivative of the present invention comprises three components of anthocyanin, crosslinking agent and proanthocyanidin as compared with other pigment derivatives, and is more stable than anthocyanin and pigment derivatives prepared only from anthocyanin and other crosslinking agent, and has the ability to withstand the influence of pH, temperature, oxygen and even bleaching agent. The invention utilizes the phenomenon and principle discovered in wine to prepare the polypigment by the mutual reaction of anthocyanin and proanthocyanidin. The inventors found that the reaction rate between proanthocyanidins and anthocyanins is significantly affected by the structure of proanthocyanidins. The binding reaction sites of the proanthocyanidins and the anthocyanins are C-8 position and C-4 position of A ring of the terminal structural units, and experiments show that the higher the molecular weight of the proanthocyanidins, the more branched chain structures are provided, so that the terminal structural units (active sites) are provided, and the more rapid dynamic speed of the anthocyanin-proanthocyanidins binding reaction is shown. More importantly, however, these pigment derivatives are not present in solution in a stable form. Precipitation experiments show that the larger the molecular weight of proanthocyanidin is, the more obvious the hydrophobic property is, and after the binding reaction occurs, the proanthocyanidin is easier to mutually aggregate in water to form micelles with larger particle sizes, and then precipitation is generated. The inventor has found that the precipitation effect has a critical point molecular weight. When the polymerization degree of the proanthocyanidin is less than 6, the steric hindrance between the structural units is small, and the connecting bond can rotate to a certain degree under the influence of a solvent, so that a hydrophilic group is exposed on the surface, and a hydrophobic group is wrapped in the molecule. However, when the polymerization degree is more than 6, the branched structure gradually increases with the increase of the polymerization degree, and the steric hindrance between the structural units becomes large, and the rotation of the linkage of the structural units is restricted, so that the hydrophobicity becomes stronger. Therefore, when selecting raw materials, the invention takes proanthocyanidin with more hydrophilic structural units and moderate molecular weight as raw materials. The proanthocyanidin has the average particle size of 30-180 nm (concentration is 4 g/L) in aqueous solution, and has stable colloid chemical property, and the formed polymeric pigment has the average particle size of 80-210 nm and can be stably existed in the solution.
In order to further improve the scheme, the crosslinking agent is selected from at least one of acetaldehyde, acetaldehyde diethyl acetal, propionaldehyde, butyraldehyde, valeraldehyde, caproaldehyde, heptaldehyde and lauraldehyde.
In order to further improve the scheme, the anthocyanin is selected from at least one of malvidin-3-glucoside, pelargonidin-3-glucoside, delphinidin-3-glucoside, morning glory-3-glucoside, methyl anthocyanin-3-glucoside, cyanidin-3-glucoside and pelargonidin-3-glucoside.
In a further improvement of the above aspect, the proanthocyanidin is at least one selected from the group consisting of a proanthocyanidin-based proanthocyanidin, a proanthocyanidin-based proanthocyanidin mixture, and the average polymerization degree is 1.5-5.5.
In order to further improve the scheme, the organic acid is at least one selected from formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, 2-ethyl butyric acid, caproic acid, cinnamic acid and tartaric acid.
The invention has the beneficial effects that:
(1) The pigment derivative provided by the invention belongs to a natural anthocyanin derivative, is not influenced by a hypothesis salt ← → chalcone ← → quinone alkali ← → methanol pseudobase chemical equilibrium, can keep stable red in an acidic to neutral (pH 1.0-7.0) solution, is not influenced by pH, oxygen, a reduction type bleaching agent and temperature, and solves the problem of poor color stability of natural anthocyanin.
(2) The preparation method of the pigment derivative fully utilizes the structure-activity relationship of the anthocyanin-proanthocyanidin combined reaction, so that the reaction speed of the anthocyanin and the proanthocyanidin is the fastest, the production efficiency of the pigment derivative is increased, and the stability of the pigment derivative is also greatly improved.
(3) According to the preparation method of the pigment derivative, the used anthocyanin and proanthocyanidin are derived from plants, belong to natural products, have no biological toxicity, the cross-linking agent is a substance allowed to be used in national standard food additives (GB 2760-2016), and the raw materials are wide in source and low in price, so that the pigment derivative is suitable for industrial production.
Detailed Description
The present invention is specifically described below with reference to examples in order to facilitate understanding of the present invention by those skilled in the art. It is to be expressly understood that the examples are for illustrative purposes only and are not to be construed as limiting the scope of the present invention, as those skilled in the art will appreciate that various modifications and adaptations of the present invention as set forth herein are possible and can be made without departing from the spirit and scope of the present invention. Meanwhile, the raw materials mentioned below are not specified and are all commercial products; the process steps or preparation methods not mentioned in detail are all those known to the person skilled in the art. The following materials were used in parts by weight.
Example 1
Adding 2 parts of malvidin-3-glucoside into a reactor, adding 1000 parts of distilled water, stirring for 25 minutes, adding 1.2 parts of proanthocyanidin with the average polymerization degree of 1.5 for forming the proanthocyanidin, fully stirring for 1 hour, adding 1.5 parts of acetaldehyde diethyl acetal, stirring for 25 minutes, adding 0.2 part of cinnamic acid after the mixing treatment is finished, wherein the pH value of the system is 5.6, sealing the reactor in a dark place, standing for 120 days at the temperature of 20 ℃, and opening the reactor to dry to obtain a finished product.
Example 2
Adding 15 parts of malvidin-3-glucoside into a reactor, adding 200 parts of distilled water, stirring for 25 minutes, adding 60 parts of proanthocyanidin with the average polymerization degree of 2.7 and the protocyanine shaping proanthocyanidin, fully stirring for 1 hour, adding 10 parts of propionaldehyde, stirring for 25 minutes, adding 0.4 part of tartaric acid after the mixing treatment is finished, wherein the pH value of the system is 1.2, sealing the reactor in a dark place, standing for 270 days at the temperature of 35 ℃, opening the reactor, and drying to obtain the finished product.
Example 3
Adding 10 parts of pelargonium pigment-3-glucoside into a reactor, adding 5000 parts of distilled water, stirring for 25 minutes, adding 90 parts of proanthocyanidin with the average polymerization degree of 3.8 and the protocyanine shaping proanthocyanidin, fully stirring for 1 hour, adding 12 parts of acetaldehyde, stirring for 25 minutes, adding 0.2 part of caproic acid after the mixing treatment is finished, wherein the pH value of the system is 1.2, sealing the reactor in a dark place, standing for 5 days at the temperature of 25 ℃, and opening the reactor to dry to obtain the finished product.
Example 4
Adding 15 parts of cyanidin-3-glucoside into a reactor, adding 2000 parts of distilled water, stirring for 25 minutes, adding 80 parts of protodelphinium-shaped proanthocyanidin with the average polymerization degree of 5.5, fully stirring for 1 hour, adding 14 parts of butyraldehyde, stirring for 25 minutes, adding 0.1 part of 2-ethylbutyric acid after the mixing treatment is finished, keeping the pH of the system at 3.2, sealing the reactor in a dark place, standing for 220 days at the temperature of 10 ℃, opening the reactor, and drying to obtain the finished product.
Example 5
Adding 6 parts of delphinidin-3-glucoside into a reactor, adding 4000 parts of distilled water, stirring for 25 minutes, adding 80 parts of proanthocyanidin with the average polymerization degree of 4.2, fully stirring for 1 hour, adding 0.5 part of valeraldehyde, stirring for 25 minutes, adding 0.6 part of butyric acid after the mixing treatment is finished, keeping the pH of the system at 1.0, sealing the reactor in a dark place, standing for 200 days at the temperature of 45 ℃, opening the reactor, and drying to obtain the finished product.
Example 6
Adding 4 parts of morning glory essence-3-glucoside into a reactor, adding 300 parts of distilled water, stirring for 25 minutes, adding 0.3 part of proanthocyanidin-Prodelphinidin mixed type proanthocyanidin with the average polymerization degree of 5.2, fully stirring for 1 hour, adding 15 parts of propionaldehyde, stirring for 25 minutes, adding 0.5 part of isobutyric acid after the mixing treatment is finished, wherein the pH of the system is 5.2, sealing the reactor in the dark, standing for 180 days at the temperature of 25 ℃, and then opening the reactor to dry to obtain a finished product.
Example 7
Adding 16 parts of malvidin-3-glucoside into a reactor, adding 4500 parts of distilled water, stirring for 25 minutes, adding 60 parts of proanthocyanidin-proanthocyanin mixed type proanthocyanidin with the average polymerization degree of 3.3, fully stirring for 1 hour, adding 8 parts of hexanal, stirring for 25 minutes, adding 0.1 part of propionic acid after the mixing treatment is finished, wherein the pH value of the system is 5.6, sealing the reactor in a dark place, standing for 20 days at the temperature of 35 ℃, and opening the reactor to dry to obtain the finished product.
Example 8
Adding 3 parts of cyanidin-3-glucoside into a reactor, adding 3500 parts of distilled water, stirring for 25 minutes, adding 100 parts of proanthocyanidin-procyanidine mixed type proanthocyanidin with the average polymerization degree of 1.6, fully stirring for 1 hour, adding 6 parts of heptaldehyde, stirring for 25 minutes, adding 0.3 part of acetic acid after the mixing treatment is finished, wherein the pH value of the system is 3.6, sealing the reactor in a dark place, standing for 10 days at the temperature of 45 ℃, and opening the reactor to dry to obtain the finished product.
Example 9
Adding 18 parts of methyl anthocyanin-3-glucoside into a reactor, adding 2500 parts of distilled water, stirring for 25 minutes, adding 50 parts of a cyanine-procyanidin mixed type proanthocyanidin with an average degree of polymerization of 2.1, fully stirring for 1 hour, adding 10 parts of lauraldehyde, stirring for 25 minutes, adding 0.6 part of formic acid after the mixing treatment is finished, keeping the pH of the system at 1.0, sealing the reactor in a dark place, standing for 120 days at the temperature of 20 ℃, opening the reactor, and drying to obtain the finished product.
Example 10: stability detection
In order to examine the properties of the pigment derivatives prepared using anthocyanins and proanthocyanidins according to the present invention, the average polymerization degree and the structural unit composition of the pigment derivatives were measured by phloroglucinol degradation method, and the micelle diameter thereof was measured at a concentration of 2g/L by Dynamic Light Scattering (DLS), and the results are shown in Table 1.
TABLE 1 average degree of polymerization, structural unit composition and average particle diameter of pigment derivatives
In order to examine the content of the pigment derivative in the samples prepared in the examples, the content of the pigment derivative was analyzed using Somers pigment analysis method, and the results are shown in table 2.
TABLE 2 content of pigment derivatives measured by Somers pigment assay (mg/g sample, calculated as malvidin-3-glucoside equivalent)
The pigment derivatives prepared in the above examples were dissolved in a buffer solution (pigment derivative concentration: 0.5 g/L) having a pH of 1.0 to 7.0, left to stand for 72 hours, and then the absorbance at 520nm was examined using a spectrophotometer (cell thickness: 1 cm), and the results are shown in Table 3, comparing the absorbance with natural anthocyanin malvidin-3-glucoside having a concentration of 0.5 g/L. The results show that the obtained pigment derivative has obviously higher stability than natural anthocyanin malvidin-3-glucoside.
TABLE 3 absorbance at 520nm of the pigment derivative at a concentration of 0.5g/L (cell thickness of 1 cm)
| pH1.0 | pH2.3 | pH3.1 | pH4.2 | pH5.6 | pH6.3 | pH7.0 | |
| Example 1 | 1.38 | 1.36 | 1.31 | 1.02 | 1.01 | 1.02 | 0.98 |
| Example 2 | 1.24 | 1.24 | 1.11 | 1.21 | 1.16 | 1.03 | 1.00 |
| Example 3 | 1.55 | 1.52 | 1.34 | 1.28 | 1.33 | 1.21 | 1.26 |
| Example 4 | 1.32 | 1.33 | 1.31 | 1.21 | 1.15 | 1.16 | 1.00 |
| Example 5 | 1.01 | 1.02 | 1.06 | 0.94 | 0.92 | 0.91 | 0.85 |
| Example 6 | 1.26 | 1.24 | 1.18 | 1.16 | 1.13 | 1.12 | 1.01 |
| Example 7 | 1.28 | 1.21 | 1.10 | 1.17 | 1.16 | 1.13 | 1.04 |
| Example 8 | 1.37 | 1.34 | 1.26 | 1.23 | 1.27 | 1.21 | 1.06 |
| Example 9 | 1.52 | 1.45 | 1.33 | 1.32 | 1.25 | 1.13 | 1.02 |
| Malvidin-3-glucoside | 1.92 | 1.63 | 1.41 | 0.83 | 0.62 | 0.51 | 0.31 |
The above embodiments are preferred embodiments of the present invention, and all similar processes and equivalent variations to those of the present invention should fall within the protection scope of the present invention.
Claims (5)
1. A high-stability pigment derivative characterized by: the pigment derivative has a number average molecular weight of 523-168 Da, and has a structural unit with an epicatechin content of 5-30%, a catechin content of 3-75%, a gallocatechin content of 1-13%, an epigallocatechin content of 1-5%, a catechin galloyl ester content of 1-16%, and an epicatechin galloyl ester content of 2-17%;
the preparation method of the high-stability pigment derivative comprises the following operation steps: mixing 2-18 parts of anthocyanin and 200-5000 parts of distilled water, fully stirring for 1-25 min, then adding 0.3-100 parts of proanthocyanidin, fully stirring for 1-10 h, then adding 0.5-15 parts of cross-linking agent, fully stirring for 1-25 min, then adding 0.1-0.6 part of organic acid, uniformly mixing, sealing, placing in a dark environment at the temperature of 10-45 ℃ for 5-45 days, and drying to obtain a finished product;
the cross-linking agent is at least one selected from acetaldehyde, acetaldehyde diethyl acetal, propionaldehyde, butyraldehyde, valeraldehyde, caproaldehyde, heptaldehyde and lauraldehyde;
the proanthocyanidin is selected from at least one of proanthocyanidin shaping, proanthocyanidin shaping and proanthocyanidin-proanthocyanidin mixed type, and has an average polymerization degree of 1.5-5.5.
2. The highly stable pigment derivative according to claim 1, wherein: when the concentration is 4g \, the average grain diameter of the pigment derivative is 30-180 nm.
3. A process for preparing the highly stable pigment derivatives according to claim 1 or 2, characterized by comprising the following steps: mixing 2-18 parts of anthocyanin and 200-5000 parts of distilled water, fully stirring for 1-25 min, then adding 0.3-100 parts of proanthocyanidin, fully stirring for 1-10 h, then adding 0.5-15 parts of cross-linking agent, fully stirring for 1-25 min, then adding 0.1-0.6 part of organic acid, uniformly mixing, sealing, placing in a dark environment at the temperature of 10-45 ℃ for 5-45 days, and drying to obtain a finished product;
the cross-linking agent is at least one of acetaldehyde, acetaldehyde diethyl acetal, propionaldehyde, butyraldehyde, valeraldehyde, caproaldehyde, heptaldehyde and lauraldehyde;
the proanthocyanidin is at least one selected from the group consisting of proanthocyanidin-fixed form, and a mixed form of proanthocyanidin-procarbazine, and has an average degree of polymerization of 1.5 to 5.5.
4. The method for preparing a highly stable pigment derivative according to claim 3, wherein: the anthocyanin is at least one selected from malvidin-3-glucoside, pelargonidin-3-glucoside, delphinidin-3-glucoside, morning glory-plant-extract-3-glucoside, methyl anthocyanin-3-glucoside, cyanidin-3-glucoside and pelargonidin-3-glucoside.
5. The method for preparing a highly stable pigment derivative according to claim 3, wherein: the organic acid is at least one selected from formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, 2-ethyl butyric acid, caproic acid, cinnamic acid and tartaric acid.
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