CN111454588A - Method for preparing cochineal red aluminum-free lake pigment by using protein, product and application thereof - Google Patents

Method for preparing cochineal red aluminum-free lake pigment by using protein, product and application thereof Download PDF

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CN111454588A
CN111454588A CN202010280037.XA CN202010280037A CN111454588A CN 111454588 A CN111454588 A CN 111454588A CN 202010280037 A CN202010280037 A CN 202010280037A CN 111454588 A CN111454588 A CN 111454588A
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cochineal
aluminum
acid
protein
preparing
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CN111454588B (en
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陈洁
刘倩
刘熠
何志勇
曾茂茂
王召君
秦昉
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Shanghai Topyum Bio Technology Co ltd
Jiangnan University
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Jiangnan University
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    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09BORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B63/00Lakes
    • AHUMAN NECESSITIES
    • A23FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23LFOODS, 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
    • A23L5/00Preparation or treatment of foods or foodstuffs, in general; Food or foodstuffs obtained thereby; Materials therefor
    • A23L5/40Colouring or decolouring of foods
    • A23L5/42Addition of dyes or pigments, e.g. in combination with optical brighteners
    • A23L5/43Addition of dyes or pigments, e.g. in combination with optical brighteners using naturally occurring organic dyes or pigments, their artificial duplicates or their derivatives
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09BORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B1/00Dyes with anthracene nucleus not condensed with any other ring
    • C09B1/02Hydroxy-anthraquinones; Ethers or esters thereof
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09BORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B61/00Dyes of natural origin prepared from natural sources, e.g. vegetable sources

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Abstract

The invention discloses a method for preparing cochineal red aluminum-free lake pigment by utilizing protein and a product and application thereof, wherein the method comprises the steps of adding cochineal acid into a buffer solution with the pH value of 3 to prepare a pigment solution, adding metal ions, and fully stirring to obtain the cochineal acid pigment solution; adding protein into cochineal acid solution, mixing, adding polyphenol, stirring, centrifuging, lyophilizing precipitate, and grinding to obtain cochineal red non-aluminum lake pigment. The method for preparing the cochineal red aluminum-free lake pigment by using the protein is simple and convenient to operate, and the product does not contain aluminum, so that the safety of the product is not questioned. The cochineal red aluminum-free protein lake provided by the invention has a good color generation effect in an alkaline diluted iron solution and an alkaline calcium solution, and has a good dyeing effect on dough, minced fillet and cream.

Description

Method for preparing cochineal red aluminum-free lake pigment by using protein, product and application thereof
Technical Field
The invention belongs to the field of natural pigment development and utilization, and particularly relates to a method for preparing cochineal red aluminum-free lake pigment by using protein, a product and application thereof.
Background
Cochineal acid is a natural pigment extracted from cochineal, has strong light stability and thermal stability, and can be widely applied to the fields of food, medicine and cosmetics. However, the color of cochineal acid is easily changed by the environment, which affects its use in different systems. For example, as the pH changes from acidic to basic, cochineal acid may range in color from orange to red to purple; when meeting iron ions, the iron ions can turn into black purple; when added to starch or surimi products, the color changes to purple; when added to a creamer product, the color changes to a grayish green color.
Cochineal aluminum lake formed by cochineal acid and aluminum hydroxide has strong tinting strength and good color stability, so the cochineal aluminum lake is widely used in solid food dyeing. However, studies have shown that excessive intake of aluminum may lead to senile dementia, increase the incidence of breast cancer, and may affect the skeletal and neurological development of the newborn, raising the question about the safety of cochineal aluminum lakes. Therefore, there is a need to prepare an aluminum-free cochineal lake pigment to replace the use of cochineal aluminum lake in food products.
Disclosure of Invention
This section is for the purpose of summarizing some aspects of embodiments of the invention and to briefly introduce some preferred embodiments. In this section, as well as in the abstract and the title of the invention of this application, simplifications or omissions may be made to avoid obscuring the purpose of the section, the abstract and the title, and such simplifications or omissions are not intended to limit the scope of the invention.
The present invention has been made in view of the above and/or the safety problems associated with the use of the prior art cochineal red aluminum lakes in food products.
Therefore, an object of the present invention is to provide a method for preparing cochineal non-aluminum lake pigment by using protein, which overcomes the safety problem of cochineal aluminum lake.
In order to solve the technical problems, the invention provides the following technical scheme: a method for preparing cochineal red aluminum-free lake pigment by using protein is characterized by comprising the following steps: comprises the steps of (a) preparing a mixture of a plurality of raw materials,
adding carminic acid into a buffer solution with the pH value of 3 to prepare a pigment solution, adding metal ions, and fully stirring; adding protein into the pigment solution, fully and uniformly mixing, adding polyphenol, uniformly stirring, centrifuging, taking the precipitate, freeze-drying, and grinding to obtain the cochineal red aluminum-free protein lake.
In a preferred embodiment of the present invention, the cochineal red non-aluminum lake pigment is prepared from a protein, wherein the concentration of the cochineal acid pigment solution is 0.02-0.2%.
In a preferred embodiment of the present invention, the cochineal red non-aluminum lake pigment is prepared from protein, wherein the phosphate buffer is disodium hydrogen phosphate-citric acid buffer.
In a preferable embodiment of the present invention, the cochineal red aluminum-free lake pigment is prepared from protein, wherein the metal ions include potassium ions, calcium ions, magnesium ions and zinc ions, and the concentration of the metal ions is 0-0.1 mol/L.
The preferable embodiment of the method for preparing the cochineal red aluminum-free lake pigment by using the protein is that the protein comprises one of soybean protein isolate, casein, sodium caseinate and whey protein isolate, and the mass ratio of the protein to the cochineal acid is 1-50: 1.
In a preferred embodiment of the present invention, the protein is used to prepare cochineal red aluminum-free lake pigment, wherein the polyphenol comprises tannic acid, epigallocatechin gallate, etc. at a concentration of 0.05% to 2%.
In a preferred embodiment of the present invention, the method for preparing cochineal red aluminum-free lake pigment from protein comprises centrifuging at 2000rpm for 10 min.
Another object of the present invention is to provide a cochineal red non-aluminum protein lake with a more stable color in iron-containing solutions, calcium-containing solutions, starches, surimi, cream products.
The invention has the beneficial effects that: the method utilizes the ligand binding characteristic of the protein to prepare the cochineal red aluminum-free lake pigment, and has simple and convenient operation. The product does not contain aluminum, avoids the question of safety, has good color generation in the condition of low iron ion content and in starch and thin cream products, and has good application prospect in food dyeing.
The invention utilizes a protein-polyphenol compound to realize the embedding of the carminic acid, reduce the sensitivity of the carminic acid to the environment and ensure the color stability of the carminic acid, the protein can simultaneously interact with the carminic acid and the polyphenol, the embedding of the carminic acid can be realized while the protein-polyphenol compound is formed, the polyphenol and the protein form a compound to realize the precipitation of the protein, the color of the carminic acid is related to the pH environment, the tannic acid is faintly acid in an aqueous solution, and has a certain protection effect on the color of the carminic acid, the invention respectively selects whey protein isolate and calcium chloride from different proteins and metal ions, simultaneously preferably selects the mass ratio of the carminic acid to the whey protein isolate to be 1: 10, the concentration of the calcium chloride to be 0.01 mol/L, and under the condition that the mass percentage of the carminic acid to the carminic acid buffer solution is 0.02%, the precipitation amount is the best, and the pigment precipitation rate can reach 73.20%.
Detailed Description
In order to make the aforementioned objects, features and advantages of the present invention comprehensible, embodiments accompanied with examples are described in detail below.
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention, but the present invention may be practiced in other ways than those specifically described and will be readily apparent to those of ordinary skill in the art without departing from the spirit of the present invention, and therefore the present invention is not limited to the specific embodiments disclosed below.
Furthermore, reference herein to "one embodiment" or "an embodiment" means that a particular feature, structure, or characteristic described in connection with the embodiment is included in at least one implementation of the invention. The appearances of the phrase "in one embodiment" in various places in the specification are not necessarily all referring to the same embodiment, nor are separate or alternative embodiments mutually exclusive of other embodiments.
The invention is used for measuring the pigment precipitation rate:
(1) determination of cochineal acid content by high performance liquid chromatography
Chromatographic conditions GraceSmart C18 chromatographic column (5 μm, 4.6mm, × 250mm, Waters e2695), binary flow mobile phase A: 0.2% formic acid, B: acetonitrile, mobile phase gradient as shown in Table 1, flow rate 1m L/min, column temperature 30 ℃, sample size 10 μ L, wavelength range from 200nm to 600nm detected by diode array detector, and absorption wavelength of cochineal acid 494 nm.
TABLE 1
Figure BDA0002446226060000031
(2) Pigment precipitation rate (%) calculation method:
Figure BDA0002446226060000032
wherein C1 is the content of carminic acid in the pigment solution, and C2 is the content of carminic acid in the supernatant after centrifugation.
Example 1
This example provides a method for preparing cochineal red non-aluminum lake pigment using protein:
(1) preparing 0.2 mol/L disodium hydrogen phosphate solution and 0.1 mol/L citric acid solution, mixing, and controlling the pH value to be 3;
(2) adding the cochineal acid into the buffer solution obtained in the step (1) to prepare a cochineal acid buffer solution, wherein the mass of the cochineal acid accounts for 0.02% of the mass of the cochineal acid buffer solution;
(3) adding the isolated soy protein into the carminic acid buffer solution prepared in the step (2), fully stirring, and uniformly mixing to obtain a mixed solution of the isolated soy protein and the carminic acid, wherein the mass ratio of the carminic acid to the isolated soy protein is 1: 10;
(4) adding tannic acid into the soybean protein isolate-cochineal acid mixed solution prepared in the step (3), controlling the concentration of the tannic acid to be 0.1%, uniformly mixing, centrifuging the obtained solution at 2000rpm for 10min, taking the precipitate, freeze-drying, and grinding to obtain the cochineal red aluminum-free lake pigment; the precipitation rate of the cochineal red aluminum-free lake pigment was measured to be 60%.
Example 2
This example provides a method for preparing cochineal red non-aluminum lake pigment using protein:
(1) preparing 0.2 mol/L disodium hydrogen phosphate solution and 0.1 mol/L citric acid solution, mixing, and controlling the pH value to be 3;
(2) adding the cochineal acid into the buffer solution obtained in the step (1) to prepare a cochineal acid buffer solution, wherein the mass of the cochineal acid accounts for 0.02% of the mass of the cochineal acid buffer solution;
(3) adding casein into the carminic acid buffer solution prepared in the step (2), fully stirring, and uniformly mixing to obtain a casein-carminic acid mixed solution, wherein the mass ratio of the carminic acid to the casein is 1: 10;
(4) adding tannic acid into the casein-cochineal acid mixed solution prepared in the step (3), controlling the concentration of tannic acid to be 0.1%, uniformly mixing, centrifuging the obtained solution at 2000rpm for 10min, taking precipitate, freeze-drying, and grinding to obtain cochineal red aluminum-free lake pigment; the precipitation rate of the cochineal red aluminum-free lake pigment was measured to be 60%.
Example 3
This example provides a method for preparing cochineal red non-aluminum lake pigment using protein:
(1) preparing 0.2 mol/L disodium hydrogen phosphate solution and 0.1 mol/L citric acid solution, mixing, and controlling the pH value to be 3;
(2) adding the cochineal acid into the buffer solution obtained in the step (1) to prepare a cochineal acid buffer solution, wherein the mass of the cochineal acid accounts for 0.02% of the mass of the cochineal acid buffer solution;
(3) adding sodium caseinate into the carminic acid buffer solution prepared in the step (2), fully stirring, and uniformly mixing to obtain a sodium caseinate-carminic acid mixed solution, wherein the mass ratio of the carminic acid to the sodium caseinate is 1: 10;
(4) adding tannic acid into the mixed solution of sodium caseinate and cochineal acid prepared in the step (3), controlling the concentration of the tannic acid to be 0.1%, uniformly mixing, centrifuging the obtained solution at 2000rpm for 10min, taking the precipitate, freeze-drying, and grinding to obtain the cochineal red aluminum-free lake pigment; the precipitation rate of the cochineal red aluminum-free lake pigment was determined to be 37%.
Example 4
This example provides a method for preparing cochineal red non-aluminum lake pigment using protein:
(1) preparing 0.2 mol/L disodium hydrogen phosphate solution and 0.1 mol/L citric acid solution, mixing, and controlling the pH value to be 3;
(2) adding the cochineal acid into the buffer solution obtained in the step (1) to prepare a cochineal acid buffer solution, wherein the mass of the cochineal acid accounts for 0.02% of the mass of the cochineal acid buffer solution;
(3) adding whey protein isolate into the carminic acid buffer solution prepared in the step (2), fully stirring, and uniformly mixing to obtain a whey protein isolate-carminic acid mixed solution, wherein the mass ratio of the carminic acid to the whey protein isolate is 1: 10;
(4) adding epigallocatechin gallate (EGCG) into the whey protein isolate-cochineal acid mixed solution prepared in the step (3), controlling the concentration of epigallocatechin gallate (EGCG) to be 0.1%, uniformly mixing, centrifuging the obtained solution at 2000rpm for 10min, taking the precipitate, freeze-drying, and grinding to obtain cochineal red aluminum-free lake pigment; the precipitation rate of the cochineal red aluminum-free lake pigment was measured to be 33%.
Example 5
This example provides a method for preparing cochineal red non-aluminum lake pigment using protein:
(1) preparing 0.2 mol/L disodium hydrogen phosphate solution and 0.1 mol/L citric acid solution, mixing, and controlling the pH value to be 3;
(2) adding the cochineal acid into the buffer solution obtained in the step (1) to prepare a cochineal acid buffer solution, wherein the mass of the cochineal acid accounts for 0.02% of the mass of the cochineal acid buffer solution;
(3) adding whey protein isolate into the carminic acid buffer solution prepared in the step (2), fully stirring, and uniformly mixing to obtain a whey protein isolate-carminic acid mixed solution, wherein the mass ratio of the carminic acid to the whey protein isolate is 1: 10;
(4) adding tannic acid into the whey protein isolate-cochineal acid mixed solution prepared in the step (3), controlling the concentration of tannic acid to be 0.1%, uniformly mixing, centrifuging the obtained solution at 2000rpm for 10min, taking precipitate, freeze-drying, and grinding to obtain cochineal red aluminum-free lake pigment; the precipitation rate of the cochineal red aluminum-free lake pigment was measured to be 63%.
Examples 1 to 5 the results of measurement of the pigmentation ratio are shown in Table 2.
TABLE 2
Figure BDA0002446226060000061
As can be seen from Table 1, different proteins and polyphenols have a greater influence on the pigmentation rate, and the whey protein isolate and tannic acid are preferred in the present invention for the preparation of cochineal red aluminum-free lake pigments. This is probably due to the fact that the solubility of the whey protein isolate is high at pH, and it is sufficient to interact with cochineal and tannic acids. The tannin has a larger molecular weight than epigallocatechin gallate (EGCG), and contains more groups capable of interacting with protein, so that the amount of the precipitated protein is larger.
Example 6
This example provides a method for preparing cochineal red non-aluminum lake pigment using protein:
(1) preparing 0.2 mol/L disodium hydrogen phosphate solution and 0.1 mol/L citric acid solution, mixing, and controlling the pH value to be 3;
(2) adding the cochineal acid into the buffer solution obtained in the step (1) to prepare a cochineal acid buffer solution, wherein the mass of the cochineal acid accounts for 0.02% of the mass of the cochineal acid buffer solution;
(3) adding potassium chloride into the cochineal acid buffer solution to enable the concentration of the potassium chloride to reach 0.01 mol/L, and fully stirring;
(4) adding whey protein isolate into the carminic acid buffer solution prepared in the step (3), fully stirring, and uniformly mixing to obtain a whey protein isolate-carminic acid mixed solution, wherein the mass ratio of the carminic acid to the whey protein isolate is 1: 10;
(5) adding tannic acid into the whey protein isolate-cochineal acid mixed solution prepared in the step (4), controlling the concentration of tannic acid to be 0.1%, uniformly mixing, centrifuging the obtained solution at 2000rpm for 10min, taking precipitate, freeze-drying, and grinding to obtain cochineal red aluminum-free lake pigment; the precipitation rate of the cochineal red aluminum-free lake pigment was determined to be 69.74%.
Example 7
This example provides a method for preparing cochineal red non-aluminum lake pigment using protein:
(1) preparing 0.2 mol/L disodium hydrogen phosphate solution and 0.1 mol/L citric acid solution, mixing, and controlling the pH value to be 3;
(2) adding the cochineal acid into the buffer solution obtained in the step (1) to prepare a cochineal acid buffer solution, wherein the mass of the cochineal acid accounts for 0.02% of the mass of the cochineal acid buffer solution;
(3) adding magnesium chloride into the cochineal acid buffer solution to enable the concentration of the magnesium chloride to reach 0.01 mol/L, and fully stirring;
(4) adding whey protein isolate into the carminic acid buffer solution prepared in the step (3), fully stirring, and uniformly mixing to obtain a whey protein isolate-carminic acid mixed solution, wherein the mass ratio of the carminic acid to the whey protein isolate is 1: 10;
(5) adding tannic acid into the whey protein isolate-cochineal acid mixed solution prepared in the step (4), controlling the concentration of tannic acid to be 0.1%, uniformly mixing, centrifuging the obtained solution at 2000rpm for 10min, taking precipitate, freeze-drying, and grinding to obtain cochineal red aluminum-free lake pigment; the precipitation rate of the cochineal red aluminum-free lake pigment was measured to be 64.36%.
Example 8
This example provides a method for preparing cochineal red non-aluminum lake pigment using protein:
(1) preparing 0.2 mol/L disodium hydrogen phosphate solution and 0.1 mol/L citric acid solution, mixing, and controlling the pH value to be 3;
(2) adding the cochineal acid into the buffer solution obtained in the step (1) to prepare a cochineal acid buffer solution, wherein the mass of the cochineal acid accounts for 0.02% of the mass of the cochineal acid buffer solution;
(3) adding zinc chloride into the cochineal acid buffer solution to enable the concentration of the zinc chloride to reach 0.01 mol/L, and fully stirring;
(4) adding whey protein isolate into the carminic acid buffer solution prepared in the step (3), fully stirring, and uniformly mixing to obtain a whey protein isolate-carminic acid mixed solution, wherein the mass ratio of the carminic acid to the whey protein isolate is 1: 10;
(5) adding tannic acid into the whey protein isolate-cochineal acid mixed solution prepared in the step (4), controlling the concentration of tannic acid to be 0.1%, uniformly mixing, centrifuging the obtained solution at 2000rpm for 10min, taking precipitate, freeze-drying, and grinding to obtain cochineal red aluminum-free lake pigment; the precipitation rate of the cochineal red aluminum-free lake pigment was determined to be 60.59%.
Example 9
This example provides a method for preparing cochineal red non-aluminum lake pigment using protein:
(1) preparing 0.2 mol/L disodium hydrogen phosphate solution and 0.1 mol/L citric acid solution, mixing, and controlling the pH value to be 3;
(2) adding the cochineal acid into the buffer solution obtained in the step (1) to prepare a cochineal acid buffer solution, wherein the mass of the cochineal acid accounts for 0.02% of the mass of the cochineal acid buffer solution;
(3) adding calcium chloride into the cochineal acid buffer solution to enable the concentration of the calcium chloride to reach 0.01 mol/L, and fully stirring;
(4) adding whey protein isolate into the carminic acid buffer solution prepared in the step (3), fully stirring, and uniformly mixing to obtain a whey protein isolate-carminic acid mixed solution, wherein the mass ratio of the carminic acid to the whey protein isolate is 1: 10;
(5) adding tannic acid into the whey protein isolate-cochineal acid mixed solution prepared in the step (4), controlling the concentration of tannic acid to be 0.1%, uniformly mixing, centrifuging the obtained solution at 2000rpm for 10min, taking precipitate, freeze-drying, and grinding to obtain cochineal red aluminum-free lake pigment; the precipitation rate of the cochineal red aluminum-free lake pigment was determined to be 73.20%.
The results of measuring the pigmentation ratio in examples 6 to 9 are shown in Table 3.
TABLE 3
Figure BDA0002446226060000081
As can be seen from Table 3, different metal ions have a great influence on the pigment precipitation rate, and the precipitation rate is the greatest when calcium chloride is added, which can reach 73.20%.
Example 10
This example provides a method for preparing cochineal red non-aluminum lake pigment using protein:
(1) preparing 0.2 mol/L disodium hydrogen phosphate solution and 0.1 mol/L citric acid solution, mixing, and controlling the pH value to be 3;
(2) adding the cochineal acid into the buffer solution obtained in the step (1) to prepare a cochineal acid buffer solution, wherein the mass of the cochineal acid accounts for 0.02% of the mass of the cochineal acid buffer solution;
(3) adding whey protein isolate into the carminic acid buffer solution prepared in the step (2), fully stirring, and uniformly mixing to obtain a whey protein isolate-carminic acid mixed solution, wherein the mass ratio of the carminic acid to the whey protein isolate is 1: 10;
(4) adding tannic acid into the whey protein isolate-cochineal acid mixed solution prepared in the step (3), controlling the concentration of tannic acid to be 0.05%, uniformly mixing, centrifuging the obtained solution at 2000rpm for 10min, taking precipitate, freeze-drying, and grinding to obtain cochineal red aluminum-free lake pigment; the precipitation rate of the cochineal red aluminum-free lake pigment was measured to be 55.03%.
Example 11
This example provides a method for preparing cochineal red non-aluminum lake pigment using protein:
(1) preparing 0.2 mol/L disodium hydrogen phosphate solution and 0.1 mol/L citric acid solution, mixing, and controlling the pH value to be 3;
(2) adding the cochineal acid into the buffer solution obtained in the step (1) to prepare a cochineal acid buffer solution, wherein the mass of the cochineal acid accounts for 0.02% of the mass of the cochineal acid buffer solution;
(3) adding calcium chloride into the cochineal acid buffer solution to enable the concentration of the calcium chloride to reach 0.1 mol/L, and fully stirring;
(4) adding whey protein isolate into the carminic acid buffer solution prepared in the step (3), fully stirring, and uniformly mixing to obtain a whey protein isolate-carminic acid mixed solution, wherein the mass ratio of the carminic acid to the whey protein isolate is 1: 10;
(5) adding tannic acid into the whey protein isolate-cochineal acid mixed solution prepared in the step (4), controlling the concentration of tannic acid to be 0.1%, uniformly mixing, centrifuging the obtained solution at 2000rpm for 10min, taking precipitate, freeze-drying, and grinding to obtain cochineal red aluminum-free lake pigment; the precipitation rate of the cochineal red aluminum-free lake pigment was determined to be 36.43%.
Example 12
This example provides a method for preparing cochineal red non-aluminum lake pigment using protein:
(1) preparing 0.2 mol/L disodium hydrogen phosphate solution and 0.1 mol/L citric acid solution, mixing, and controlling the pH value to be 3;
(2) adding the cochineal acid into the buffer solution obtained in the step (1) to prepare a cochineal acid buffer solution, wherein the mass of the cochineal acid accounts for 0.02% of the mass of the cochineal acid buffer solution;
(3) adding calcium chloride into the cochineal acid buffer solution to enable the concentration of the calcium chloride to reach 0.01 mol/L, and fully stirring;
(4) adding whey protein isolate into the carminic acid buffer solution prepared in the step (3), fully stirring, and uniformly mixing to obtain a whey protein isolate-carminic acid mixed solution, wherein the mass ratio of the carminic acid to the whey protein isolate is 1: 10;
(5) adding tannic acid into the whey protein isolate-cochineal acid mixed solution prepared in the step (4), controlling the concentration of tannic acid to be 0.5%, uniformly mixing, centrifuging the obtained solution at 2000rpm for 10min, taking precipitate, freeze-drying, and grinding to obtain cochineal red aluminum-free lake pigment; the precipitation rate of the cochineal red aluminum-free lake pigment was determined to be 52.76%.
Example 13
This example provides a method for preparing cochineal red non-aluminum lake pigment using protein:
(1) preparing 0.2 mol/L disodium hydrogen phosphate solution and 0.1 mol/L citric acid solution, mixing, and controlling the pH value to be 3;
(2) adding the cochineal acid into the buffer solution obtained in the step (1) to prepare a cochineal acid buffer solution, wherein the mass of the cochineal acid accounts for 0.02% of the mass of the cochineal acid buffer solution;
(3) adding calcium chloride into the cochineal acid buffer solution to enable the concentration of the calcium chloride to reach 0.01 mol/L, and fully stirring;
(4) adding whey protein isolate into the carminic acid buffer solution prepared in the step (3), fully stirring, and uniformly mixing to obtain a whey protein isolate-carminic acid mixed solution, wherein the mass ratio of the carminic acid to the whey protein isolate is 1: 5;
(5) adding tannic acid into the whey protein isolate-cochineal acid mixed solution prepared in the step (4), controlling the concentration of tannic acid to be 0.1%, uniformly mixing, centrifuging the obtained solution at 2000rpm for 10min, taking precipitate, freeze-drying, and grinding to obtain cochineal red aluminum-free lake pigment; the precipitation rate of the cochineal red aluminum-free lake pigment was measured to be 28.01%.
Example 14
This example provides a method for preparing cochineal red non-aluminum lake pigment using protein:
(1) preparing 0.2 mol/L disodium hydrogen phosphate solution and 0.1 mol/L citric acid solution, mixing, and controlling the pH value to be 3;
(2) adding the cochineal acid into the buffer solution obtained in the step (1) to prepare a cochineal acid buffer solution, wherein the mass of the cochineal acid accounts for 0.02% of the mass of the cochineal acid buffer solution;
(3) adding calcium chloride into the cochineal acid buffer solution to enable the concentration of the calcium chloride to reach 0.01 mol/L, and fully stirring;
(4) adding whey protein isolate into the carminic acid buffer solution prepared in the step (3), fully stirring, and uniformly mixing to obtain a whey protein isolate-carminic acid mixed solution, wherein the mass ratio of the carminic acid to the whey protein isolate is 1: 50;
(5) adding tannic acid into the whey protein isolate-cochineal acid mixed solution prepared in the step (4), controlling the concentration of tannic acid to be 0.1%, uniformly mixing, centrifuging the obtained solution at 2000rpm for 10min, taking precipitate, freeze-drying, and grinding to obtain cochineal red aluminum-free lake pigment; the precipitation rate of the cochineal red aluminum-free lake pigment was determined to be 80.58%.
The results of measuring the pigmentation ratio in examples 10 to 14 are shown in Table 4.
TABLE 4
Figure BDA0002446226060000111
As can be seen from Table 4, the addition amount of tannic acid, the addition amount of metal ions and the ratio of protein to pigment have a great influence on the precipitation rate of pigment, and considering the cost problem of preparing lake-like pigment, the present invention preferably prepares lake-like cochineal pigment under the experimental conditions of 0.1% of tannic acid concentration, 0.01 mol/L of calcium chloride concentration and 1: 10 of pigment to protein mass ratio.
Example 15
(1) The cochineal red aluminum-free protein lake, commercial cochineal acid, and commercial cochineal red aluminum lake prepared in examples 5, 6, 7, 8, and 9 were added to sodium phosphate-citric acid buffer solution having a pH of 8, respectively, to prepare 0.25% lake solution, ferric chloride was added to the solution so that the concentration of ferric chloride was 0.001 mol/L, and the color change of the solution was observed, as shown in Table 5 below.
TABLE 5
Figure BDA0002446226060000112
The above example results demonstrate that the cochineal non-aluminum protein lake prepared according to the present invention exhibits a more consumer acceptable color in food products under alkaline conditions with relatively dilute iron ions compared to commercial cochineal acid, and provides a reference for the coloration of cochineal in iron-containing food products such as meat products.
(2) The cochineal red aluminum-free protein lake, commercial cochineal acid, and commercial cochineal red aluminum lake prepared in examples 5, 6, 7, 8, and 9 were added to a sodium phosphate-citric acid buffer solution having a pH of 8, respectively, to prepare a 0.25% lake solution, calcium chloride was added to the solution so that the calcium chloride concentration was 0.1 mol/L, and the color change of the solution was observed, as shown in Table 6 below.
TABLE 6
Figure BDA0002446226060000121
The above example results demonstrate that the cochineal red aluminum-free protein lake with potassium ions, calcium ions, magnesium ions and zinc ions, prepared by the method, has a more acceptable color in food under alkaline calcium-containing conditions, can achieve a similar dyeing effect as the commercial cochineal red aluminum lake, and meets the dyeing requirement of cochineal acid in calcium-containing food (such as milk products), compared with commercial cochineal acid.
(3) The cochineal red aluminum-free protein lake prepared in example 5, commercial cochineal acid and commercial cochineal red aluminum lake were added to dough made of wheat flour, respectively, and then dyed to observe the color of the dough;
respectively dyeing surimi by using the cochineal red aluminum-free protein lake, the commercial cochineal acid and the commercial cochineal red aluminum lake prepared in example 5, and observing the color of the surimi;
the cochineal red aluminum-free protein lake prepared in example 5, commercial cochineal acid, and commercial cochineal red aluminum lake were added to commercial cream, respectively, and the cream color was observed after dyeing. The results are given in Table 7 below.
TABLE 7
Example 5 Commercial cochineal acid Commercial cochineal red aluminum lake
Dough Orange color Purple color Pink colour
Minced fillet Purplish red color Purple color Pink colour
Commercial cream Orange color Grayish green Pink colour
From table 7, it can be seen that the cochineal red non-aluminum protein color lake prepared by the present invention shows more acceptable color in food products than commercial cochineal acid, such as dough (starch products), surimi (protein products) and cream (oil products), and can satisfy the dyeing requirement of cochineal red pigment in dough and cream food.
The invention provides a method for preparing cochineal red aluminum-free lake pigment by using protein, the product is simple to prepare, does not contain aluminum, avoids the question on the safety of the cochineal red aluminum-free lake pigment, has good color development under the conditions of low content of iron ions and calcium ions, and in starch and thin cream products, and has good application prospect in food dyeing.
The invention utilizes a protein-polyphenol compound to realize the embedding of the carminic acid, reduce the sensitivity of the carminic acid to the environment and ensure the color stability of the carminic acid, the protein can simultaneously interact with the carminic acid and the polyphenol, the embedding of the carminic acid can be realized while the protein-polyphenol compound is formed, the polyphenol and the protein form a compound to realize the precipitation of the protein, the color of the carminic acid is related to the pH environment, the tannic acid is faintly acid in an aqueous solution, and has a certain protection effect on the color of the carminic acid, the invention respectively selects whey protein isolate and calcium chloride from different proteins and metal ions, simultaneously preferably selects the mass ratio of the carminic acid to the whey protein isolate to be 1: 10, the concentration of the calcium chloride to be 0.01 mol/L, and under the condition that the mass percentage of the carminic acid to the carminic acid buffer solution is 0.02%, the precipitation amount is the best, and the pigment precipitation rate can reach 73.20%.
The cochineal red aluminum-free protein color lake prepared by the method disclosed by the invention has a color which is more acceptable to consumers in food under the conditions of low iron ion content and calcium ion content, and in dough (starch products) and cream (grease products).
It should be noted that the above-mentioned embodiments are only for illustrating the technical solutions of the present invention and not for limiting, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions may be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention, which should be covered by the claims of the present invention.

Claims (10)

1. A method for preparing cochineal red aluminum-free lake pigment by using protein is characterized by comprising the following steps: comprises the steps of (a) preparing a mixture of a plurality of raw materials,
adding carminic acid into a buffer solution with the pH value of 3 to prepare a pigment solution, adding metal ions, and fully stirring to obtain the carminic acid pigment solution;
adding protein into cochineal acid solution, mixing, adding polyphenol, stirring, centrifuging, lyophilizing precipitate, and grinding to obtain cochineal red non-aluminum lake pigment.
2. The method for preparing an aluminum-free lake pigment of cochineal red using protein according to claim 1, wherein the method comprises: the concentration of the cochineal acid pigment solution is 0.02-0.2%.
3. The method for preparing an aluminum-free lake pigment of cochineal red using protein according to claim 1, wherein the method comprises: the buffer solution is disodium hydrogen phosphate-citric acid buffer solution.
4. The method for preparing the aluminum-free lake pigment of cochineal red according to claim 1, wherein the metal ion comprises one of potassium ion, calcium ion, magnesium ion and zinc ion, and the concentration of the metal ion is 0-0.1 mol/L.
5. The method for preparing an aluminum-free lake pigment of cochineal red using protein according to claim 1, wherein the method comprises: the protein comprises one of soybean protein isolate, casein, sodium caseinate and whey protein isolate, and the mass ratio of the protein to the cochineal acid is 1-50: 1.
6. The method for preparing an aluminum-free lake pigment of cochineal red using protein according to claim 1, wherein the method comprises: the polyphenol comprises one of tannic acid and epigallocatechin gallate, and the concentration of the polyphenol is 0.05-2%.
7. The method for preparing an aluminum-free lake pigment of cochineal red using protein according to claim 1, wherein the method comprises: the centrifugation is carried out at 2000rpm for 10 min.
8. The method for producing cochineal red non-aluminum lake pigment according to any one of claims 1 to 7, wherein the method comprises: the obtained cochineal red aluminum-free lake pigment has a precipitation rate of 15-84%.
9. The product of the method for preparing cochineal red non-aluminum lake pigment according to any one of claims 1 to 7, wherein the method comprises a step of preparing a cochineal red non-aluminum lake pigment from protein.
10. The use of cochineal red non-aluminum lake pigment product according to claim 9, wherein: the use of said composition, comprising,
the color development application of cochineal red aluminum-free protein lake in iron-containing or calcium-containing solution;
application of cochineal red aluminum-free protein color lake in starch, minced fillet and cream products.
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