WO2024021552A1 - High-brightness low-redness gardenia blue pigment, and prepartion method therefor - Google Patents

High-brightness low-redness gardenia blue pigment, and prepartion method therefor Download PDF

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WO2024021552A1
WO2024021552A1 PCT/CN2023/073852 CN2023073852W WO2024021552A1 WO 2024021552 A1 WO2024021552 A1 WO 2024021552A1 CN 2023073852 W CN2023073852 W CN 2023073852W WO 2024021552 A1 WO2024021552 A1 WO 2024021552A1
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Prior art keywords
gardenia blue
redness
brightness
blue pigment
low
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PCT/CN2023/073852
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French (fr)
Chinese (zh)
Inventor
王永强
金子恒
文雁君
李林正
潘天义
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河南中大恒源生物科技股份有限公司
格力高营养食品株式会社
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Priority to CN202211626921.XA priority Critical patent/CN118206885A/en
Application filed by 河南中大恒源生物科技股份有限公司, 格力高营养食品株式会社 filed Critical 河南中大恒源生物科技股份有限公司
Priority to US18/369,101 priority patent/US20240034884A1/en
Publication of WO2024021552A1 publication Critical patent/WO2024021552A1/en

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F30/00—Fixed transformers not covered by group H01F19/00
    • H01F30/06—Fixed transformers not covered by group H01F19/00 characterised by the structure
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F27/00—Details of transformers or inductances, in general
    • H01F27/28—Coils; Windings; Conductive connections
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/16—Printed circuits incorporating printed electric components, e.g. printed resistor, capacitor, inductor
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02B—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
    • Y02B70/00—Technologies for an efficient end-user side electric power management and consumption
    • Y02B70/10—Technologies improving the efficiency by using switched-mode power supplies [SMPS], i.e. efficient power electronics conversion e.g. power factor correction or reduction of losses in power supplies or efficient standby modes

Definitions

  • the invention belongs to the technical field of pigment extraction, and specifically relates to a high-brightness, low-redness gardenia blue pigment and a preparation method thereof.
  • Gardenia blue pigment is a recognized water-soluble natural blue pigment, mainly used in food, cosmetics, dyes and pharmaceutical industries. There are currently many methods for preparing gardenia blue, but gardenia blue produced by traditional methods has the disadvantages of low brightness, high redness and high cost.
  • Chinese invention patent CN104099373A discloses a method for producing gardenia blue pigment. However, using the test method of L*, a* and b*, the brightness L* of the gardenia blue pigment generated by this method is measured to be 62 to 63, a* The value is -8 ⁇ -10, which not only has low brightness, but also has high redness.
  • Chinese invention patent CN113748169A discloses gardenia blue pigment and its manufacturing method.
  • soybean peptides, sesame peptides or rice peptides are expensive and have high production costs.
  • soybean peptides are recognized as an allergen, and soybean peptides need to be removed during the process, further increasing their production costs.
  • the purpose of the present invention is to provide a gardenia blue pigment with high brightness and low redness and a preparation method thereof, so as to solve the problem of low brightness, high redness and cost of preparing gardenia blue pigment by the existing method. higher question.
  • the invention discloses a method for preparing gardenia blue pigment with high brightness and low redness.
  • the steps are as follows: 1) Weigh genipin liquid and amino acid with a molar ratio of 1: (0.375 ⁇ 0.75) and perform polymerization reaction to obtain a gardenia blue precursor; 2) Carry out oxidation and color development treatment on the gardenia blue precursor, and monitor the color value and hue at intervals until the color value and hue do not change to obtain gardenia blue; 3) Ultrafiltrate gardenia blue to remove impurities, concentrate, and dry to obtain gardenia blue pigment with high brightness and low redness.
  • the color value of genipin is E10 to E40.
  • the amino acid is one or more of phenylalanine, tryptophan, glycine and tyrosine.
  • the reaction condition is to stand in exposed air at room temperature.
  • the oxidant used in the oxidation and coloring treatment is compressed air, ozone, hydrogen peroxide, peracetic acid or other oxidants commonly used in food.
  • step 2) during the oxidation treatment, stirring is performed at a speed of 200 rpm.
  • the method for monitoring the color value and hue is: weigh the gardenia blue after the color development is completed, and dilute it with ultrapure water to obtain a diluted liquid; use a UV-visible spectrophotometer to measure the diluted liquid. ⁇ max to obtain the color value; adjust the absorbance of the diluted solution at ⁇ max to 1.000 ⁇ 0.001, and use a colorimeter to measure the L*, a* and b* values of the diluted solution with an absorbance of 1.000 ⁇ 0.001.
  • the conditions for measuring hue using a colorimeter are: light source D65, observation angle 10 degrees.
  • the invention also discloses the gardenia blue pigment prepared by the above preparation method.
  • the L* of the gardenia blue pigment is 67.72 ⁇ 68.56, a* is -27.88 ⁇ -19.59, and b* is -29.01 ⁇ -25.02.
  • the invention provides a method for preparing a gardenia blue pigment with high brightness and low redness.
  • Genipin and peptides have better effects; using genipin and amino acids as the main raw materials, they are highly safe.
  • amino acids are lower in cost than soybean peptides, sesame peptides and rice peptides, are not prone to sensitization, and are applicable to a wider range of conditions.
  • the gardenia blue pigment obtained by this method has L* of 67.72 ⁇ 68.56, a* of -27.88 ⁇ -19.59, and b* of -29.01 ⁇ -25.02, so it has high brightness and low
  • the characteristics of redness can be used in coloring food, beverages, cosmetics, pharmaceutical products, etc.
  • the present invention provides a method for preparing high-brightness, low-redness and low-cost gardenia blue pigment, which is divided into three steps, specifically as follows: Step 1. Preparation of gardenia blue precursor. Weigh genipin liquid with a molar ratio of 1: (0.375 ⁇ 0.75) and amino acids for polymerization reaction to obtain gardenia blue precursor; Wherein, the genipin liquid is obtained by enzymatic hydrolysis of cellulase, a by-product of gardenia yellow extracted from gardenia fruit; the concentration of genipin liquid is based on color value, and the color value is limited to 10 to 40 The preferred color value range is 20-30, and the more preferred color value range is 24-26.
  • the amino acid is one or more of phenylalanine, tryptophan, tyrosine and glycine, all of which are commercially available products.
  • the effective content is not limited, and the preferred content is 90% to 100%.
  • the specific addition amount Conversion processing is required.
  • the molar ratio is preferably 1:(0.4-0.7), more preferably 1:(0.5-0.6).
  • the reaction conditions include, but are not limited to, standing in exposed air at room temperature.
  • Step 2 Oxidation and color development of gardenia blue precursor. Oxidize the gardenia blue precursor obtained in step 1, and monitor the color value and hue until the color value and hue do not change significantly within 1 hour to obtain gardenia. blue; Among them, the oxidants used in the oxidation treatment include but are not limited to compressed air, ozone, hydrogen peroxide, peracetic acid or other oxidants commonly used in food; compressed air is preferably used as the oxidant.
  • the specific method for monitoring color price and hue is as follows: 1) Weigh a small amount of gardenia blue after color development and dilute it with ultrapure water to obtain a diluent; according to GB 28311-2012, use a UV-visible spectrophotometer to measure the maximum absorption wavelength ⁇ max of the diluent (the formula is as follows) , get the color price: Among them, A: the absorbance of the sample at the maximum absorption wavelength ⁇ max ; c: the concentration of the sample liquid to be tested, g/mL; 100: concentration conversion coefficient; 2) At the maximum absorption wavelength ⁇ max , adjust the absorbance of the diluent in step 1) to 1.000 ⁇ 0.001, and use a colorimeter (model: CM-5; Konica-Minolta, Japan) to measure the hue.
  • a colorimeter model: CM-5; Konica-Minolta, Japan
  • Measurement conditions light source D65, observation angle 10 degrees; measure the L* value, a* value and b* value of the sample, where the L* value, a* value and b* value represent the brightness, red-green value and yellow-blue value respectively.
  • the experimental results are based on the arithmetic mean of parallel measurement results.
  • the absolute difference between two independent determination results obtained under repeated conditions shall not exceed 2%.
  • Step 3 Refining, purification and spray drying. Under normal temperature conditions, perform ultrafiltration and purification of the gardenia blue obtained in step 2 to remove impurities and concentrate. The refined concentrate is obtained and spray-dried to obtain a gardenia blue pigment with high brightness and low redness.
  • the steps for exploring the preparation method are as follows: Set the concentration of genipin liquid to E25, change the addition ratio of genipin and amino acids, and use genipin liquid and soybean peptide as the control group to verify the impact of the molar ratio of genipin and amino acids on the color results.
  • the verification results are shown in Table 1: Table 1 Effect of genipin and different amino acid addition ratios on color development results
  • the a* values are -25.16, -31.38, -26.52 and -13.08 respectively.
  • the brightness of phenylalanine and tyrosine is high and the redness is low.
  • the molar ratio of genipin to amino acid is 1:1, the brightness increases slightly, but the redness increases significantly. From the color data of genipin and soybean peptide, it can be seen that when the ratio of the two is changed, the hue is almost unchanged, the brightness is higher, and the redness is relatively low.
  • the present invention selects phenylalanine as the reaction raw material.
  • the color value of phenylalanine gardenia blue is the highest.
  • the brightness L* of the coloring liquid is 67.87, and the redness a* is -25.16.
  • the present invention specifically selects phenylalanine as the optimal reaction raw material.
  • the following experiment uses phenylalanine and genipin as raw materials. By changing the addition ratio of genipin and phenylalanine, while maintaining the target color tone, combined with the color value of the gardenia blue material liquid at the end of the color development, To further determine the addition ratio range of genipin and amino acids.
  • the present invention prepares gardenia blue with high brightness, low redness and low cost by adjusting the addition ratio of genipin and amino acids, and utilizing the preparation of gardenia blue precursor and the process of gardenia blue oxidation and color development. Improved the application quality of Gardenia Blue.
  • Table 4 are a detailed introduction to the present invention.
  • Example 1 Preparation of Gardenia Blue Precursor Mix the high color value gardenia glycoside enzymatic hydrolyzate (i.e. genipin liquid) with water, dilute the material solution to a color value of E25, weigh 850 g of the diluted solution, and raise the temperature to 35 °C. After the temperature stabilizes, add 1 g sodium hydrogen phosphate dihydrate and 7 g sodium hydrogen phosphate dihydrate. Use 30% NaOH solution to adjust the pH to 7.49. Add 16.5 g phenylalanine. Keep it for 24 hours to obtain the gardenia blue precursor.
  • gardenia glycoside enzymatic hydrolyzate i.e. genipin liquid
  • the final color solution After 30 hours of oxidation and color development, the final color solution has a color value and a maximum absorption wavelength of 599.5 nm. It is then refined with an ultrafiltration membrane and spray-dried to obtain gardenia blue powder.
  • Example 2 Preparation of Gardenia Blue Precursor Mix the high color value gardenia glycoside enzymatic hydrolyzate (i.e. genipin liquid) with water, dilute the material solution to a color value of E25, weigh 850 g of the diluted solution, and raise the temperature to 35 °C, after the temperature stabilizes, add 1g sodium hydrogen phosphate dihydrate and 7 g sodium hydrogen phosphate dihydrate, adjust the pH value to 7.51 with 30% NaOH solution, add 16.5 g phenylalanine, and maintain After 24 hours, a gardenia blue precursor was obtained.
  • gardenia glycoside enzymatic hydrolyzate i.e. genipin liquid
  • the final color solution After 31 hours of oxidation and color development, the final color solution has a color value and a maximum absorption wavelength of 600 nm. It is then refined with an ultrafiltration membrane and spray-dried to obtain gardenia blue powder.
  • Example 3 Preparation of Gardenia Blue Precursor Mix the high color value gardenia glycoside enzymatic hydrolyzate (i.e. genipin liquid) with water, dilute the material solution to a color value of E20, weigh 850 g of the diluted solution, and raise the temperature to 35 °C, after the temperature stabilizes, add 1g sodium hydrogen phosphate dihydrate and 7 g sodium hydrogen phosphate dihydrate, adjust the pH value to 7.48 with 30% NaOH solution, add 13.2 g phenylalanine, and keep After 24 hours, a gardenia blue precursor was obtained.
  • gardenia glycoside enzymatic hydrolyzate i.e. genipin liquid
  • the final color solution After 30 hours of oxidation and color development, the final color solution has a color value and a maximum absorption wavelength of 602 nm. It is then refined with an ultrafiltration membrane and spray-dried to obtain gardenia blue powder.
  • Example 4 Preparation of Gardenia Blue Precursor Mix the high color value gardenia glycoside enzymatic hydrolyzate (i.e. genipin liquid) with water, dilute the material solution to a color value of E25, weigh 850 g of the diluted solution, and raise the temperature to 35 °C. After the temperature stabilizes, add 1 g sodium hydrogen phosphate dihydrate and 7 g sodium hydrogen phosphate dihydrate. Use 30% NaOH solution to adjust the pH to 7.42. Add 19.43 g phenylalanine. Keep it for 24 hours to obtain the gardenia blue precursor.
  • gardenia glycoside enzymatic hydrolyzate i.e. genipin liquid
  • the final color solution After 29 hours of oxidation and color development, the final color solution has a color value and a maximum absorption wavelength of 598.5 nm. It is then refined with an ultrafiltration membrane and spray-dried to obtain gardenia blue powder.
  • Example 5 Preparation of Gardenia Blue Precursor Mix the high color value gardenia glycoside enzymatic hydrolyzate (i.e. genipin liquid) with water, dilute the material solution to a color value of E25, weigh 850 g of the diluted solution, and raise the temperature to 35 °C. After the temperature stabilizes, add 1 g sodium hydrogen phosphate dihydrate and 7 g sodium hydrogen phosphate dihydrate. Use 30% NaOH solution to adjust the pH to 7.47. Add 24.75 g phenylalanine. Keep it for 24 hours to obtain the gardenia blue precursor.
  • gardenia glycoside enzymatic hydrolyzate i.e. genipin liquid

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Abstract

Disclosed are a high-brightness low-redness gardenia blue pigment and a preparation method therefor, belonging to the technical field of pigment extraction. Using as a raw material a gardenia extract enzymolysis product genipin, weighing a molar ratio 1:(0.375-0.75) of genipin to amino acid (phenylalanine, tryptophan, glycine, or tyrosine), and under normal conditions, a polymerization reaction occurring, generating a gardenia blue precursor; then subjecting the gardenia blue precursor to oxidation coloring and ultrafiltration membrane refining, and finally performing spray drying to obtain a high-brightness, low-redness, and low-cost gardenia blue pigment.

Description

一种高亮度、低红度的栀子蓝色素及其制备方法A kind of gardenia blue pigment with high brightness and low redness and preparation method thereof 技术领域Technical field
本发明属于色素提取技术领域，具体涉及一种高亮度、低红度的栀子蓝色素及其制备方法。The invention belongs to the technical field of pigment extraction, and specifically relates to a high-brightness, low-redness gardenia blue pigment and a preparation method thereof.
背景技术Background technique
栀子蓝色素是一种公认的水溶天然蓝色素，主要应用在食品、化妆品、染料和医药等行业。目前栀子蓝的制备方法有很多，但是用传统方法生产的栀子蓝有亮度低、红度高及成本较高的缺点。中国发明专利CN104099373A公开了一种栀子蓝色素的生产方法，但是利用L*，a*和b*的测试方法，测得该方法生成的栀子蓝色素亮度L*为62～63，a*值为-8～-10，不但亮度低，且红度较高。中国发明专利CN113748169A公开了栀子蓝色素及其制造方法，通过不含氧和通入氧气等两个步骤，利用京尼平，与大豆肽、芝麻肽和大米肽进行无通气反应及通气呈色，合成了一种亮度高、红度低的栀子蓝，在与本发明相同条件下测试的L*值，a*值和b*值与本发明类似。但是大豆肽、芝麻肽或大米肽价格昂贵，生产成本较高，且大豆肽被公认为一种过敏原，工艺中需去除大豆肽，进一步增加了其生产成本。Gardenia blue pigment is a recognized water-soluble natural blue pigment, mainly used in food, cosmetics, dyes and pharmaceutical industries. There are currently many methods for preparing gardenia blue, but gardenia blue produced by traditional methods has the disadvantages of low brightness, high redness and high cost. Chinese invention patent CN104099373A discloses a method for producing gardenia blue pigment. However, using the test method of L*, a* and b*, the brightness L* of the gardenia blue pigment generated by this method is measured to be 62 to 63, a* The value is -8~-10, which not only has low brightness, but also has high redness. Chinese invention patent CN113748169A discloses gardenia blue pigment and its manufacturing method. Through two steps of excluding oxygen and introducing oxygen, genipin is used to react with soybean peptide, sesame peptide and rice peptide without ventilation and to produce color through ventilation. , a gardenia blue with high brightness and low redness was synthesized. The L* value, a* value and b* value tested under the same conditions as the present invention were similar to those of the present invention. However, soybean peptides, sesame peptides or rice peptides are expensive and have high production costs. Moreover, soybean peptides are recognized as an allergen, and soybean peptides need to be removed during the process, further increasing their production costs.
技术问题technical problem
为了克服上述现有技术的缺点，本发明的目的在于提供一种高亮度、低红度的栀子蓝色素及其制备方法，解决现有方法制备栀子蓝色素亮度低、红度高及成本较高的问题。In order to overcome the shortcomings of the above-mentioned prior art, the purpose of the present invention is to provide a gardenia blue pigment with high brightness and low redness and a preparation method thereof, so as to solve the problem of low brightness, high redness and cost of preparing gardenia blue pigment by the existing method. higher question.
技术解决方案Technical solutions
本发明公开了一种高亮度、低红度的栀子蓝色素的制备方法，步骤如下：
1）称取摩尔比为1:（0.375～0.75）的京尼平液体和氨基酸进行聚合反应，得到栀子蓝前体；
2）对栀子蓝前体进行氧化呈色处理，并间隔监测色价及色调，直至色价及色调不发生变化，得到栀子蓝；
3）对栀子蓝进行超滤，去除杂质，浓缩，干燥，得到高亮度、低红度的栀子蓝色素。 The invention discloses a method for preparing gardenia blue pigment with high brightness and low redness. The steps are as follows:
1) Weigh genipin liquid and amino acid with a molar ratio of 1: (0.375~0.75) and perform polymerization reaction to obtain a gardenia blue precursor;
2) Carry out oxidation and color development treatment on the gardenia blue precursor, and monitor the color value and hue at intervals until the color value and hue do not change to obtain gardenia blue;
3) Ultrafiltrate gardenia blue to remove impurities, concentrate, and dry to obtain gardenia blue pigment with high brightness and low redness.
优选地，步骤1）中，所述京尼平的色价为E10～E40。Preferably, in step 1), the color value of genipin is E10 to E40.
优选地，步骤1）中，氨基酸为苯丙氨酸、色氨酸、甘氨酸和酪氨酸中的一种或几种。Preferably, in step 1), the amino acid is one or more of phenylalanine, tryptophan, glycine and tyrosine.
优选地，步骤1）中，反应条件为静置于室温裸露的空气中。Preferably, in step 1), the reaction condition is to stand in exposed air at room temperature.
优选地，步骤2）中，氧化呈色处理使用的氧化剂为压缩空气、臭氧、双氧水、过氧乙酸或者其他食品中常用氧化剂。Preferably, in step 2), the oxidant used in the oxidation and coloring treatment is compressed air, ozone, hydrogen peroxide, peracetic acid or other oxidants commonly used in food.
优选地，步骤2）中，氧化处理的同时，以速度为200转/分钟进行搅拌。Preferably, in step 2), during the oxidation treatment, stirring is performed at a speed of 200 rpm.
优选地，步骤2）中，所述监测色价及色调的方法为：称取呈色结束后的栀子蓝，并用超纯水稀释，得到稀释液；用紫外-可见分光光度计测定稀释液的λ max，得到色价；在λ max处调节稀释液吸光度为1.000±0.001，用色差仪测定吸光度为1.000±0.001稀释液的L*、a*和b*值。 Preferably, in step 2), the method for monitoring the color value and hue is: weigh the gardenia blue after the color development is completed, and dilute it with ultrapure water to obtain a diluted liquid; use a UV-visible spectrophotometer to measure the diluted liquid. λ max to obtain the color value; adjust the absorbance of the diluted solution at λ max to 1.000±0.001, and use a colorimeter to measure the L*, a* and b* values of the diluted solution with an absorbance of 1.000±0.001.
进一步优选地，利用色差仪测定色调的条件为：光源D65，观察角10度。Further preferably, the conditions for measuring hue using a colorimeter are: light source D65, observation angle 10 degrees.
本发明还公开了上述制备方法制得的栀子蓝色素。The invention also discloses the gardenia blue pigment prepared by the above preparation method.
优选地，所述栀子蓝色素的L*为67.72~68.56，a*为-27.88~-19.59，b*为-29.01~-25.02。Preferably, the L* of the gardenia blue pigment is 67.72~68.56, a* is -27.88~-19.59, and b* is -29.01~-25.02.
有益效果beneficial effects
本发明提供的一种高亮度、低红度的栀子蓝色素的制备方法，首先通过改变京尼平和氨基酸的添加比例，即京尼平与氨基酸的摩尔添加比例大于1，能够得到相较京尼平与多肽更好的效果；以京尼平与氨基酸作为主要原料，安全性高，同时，氨基酸相比大豆肽、芝麻肽和大米肽成本更低，且不易致敏，适用条件更广。在生产成本更低的基础上，通过该方法得到的栀子蓝色素的L*为67.72~68.56，a*为-27.88~-19.59，b*为-29.01~-25.02，因而具有高亮度和低红度的特点，能够应用于饮食品、化妆品、医药制品等的着色中。The invention provides a method for preparing a gardenia blue pigment with high brightness and low redness. First, by changing the addition ratio of genipin and amino acids, that is, the molar addition ratio of genipin to amino acids is greater than 1. Genipin and peptides have better effects; using genipin and amino acids as the main raw materials, they are highly safe. At the same time, amino acids are lower in cost than soybean peptides, sesame peptides and rice peptides, are not prone to sensitization, and are applicable to a wider range of conditions. On the basis of lower production cost, the gardenia blue pigment obtained by this method has L* of 67.72~68.56, a* of -27.88~-19.59, and b* of -29.01~-25.02, so it has high brightness and low The characteristics of redness can be used in coloring food, beverages, cosmetics, pharmaceutical products, etc.
本发明的实施方式Embodiments of the invention
为了使本技术领域的人员更好地理解本发明方案，下面将对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例仅仅是本发明一部分的实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都应当属于本发明保护的范围。In order to enable those skilled in the art to better understand the solutions of the present invention, the technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only embodiments of a part of the present invention, rather than All examples. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts should fall within the scope of protection of the present invention.
需要说明的是，本发明的说明书和权利要求书中的术语“第一”、“第二”等是用于区别类似的对象，而不必用于描述特定的顺序或先后次序。应该理解这样使用的数据在适当情况下可以互换，以便这里描述的本发明的实施例能够以除了在这里图示或描述的那些以外的顺序实施。此外，术语“包括”和“具有”以及他们的任何变形，意图在于覆盖不排他的包含，例如，包含了一系列步骤或单元的过程、方法、***、产品或设备不必限于清楚地列出的那些步骤或单元，而是可包括没有清楚地列出的或对于这些过程、方法、产品或设备固有的其它步骤或单元。It should be noted that the terms "first", "second", etc. in the description and claims of the present invention are used to distinguish similar objects and are not necessarily used to describe a specific order or sequence. It is to be understood that the data so used are interchangeable under appropriate circumstances so that the embodiments of the invention described herein are capable of being practiced in sequences other than those illustrated or described herein. In addition, the terms "including" and "having" and any variations thereof are intended to cover non-exclusive inclusions, e.g., a process, method, system, product, or apparatus that encompasses a series of steps or units and need not be limited to those explicitly listed. Those steps or elements may instead include other steps or elements not expressly listed or inherent to the process, method, product or apparatus.
下面对本发明做进一步详细描述：
本发明提供的一种高亮度、低红度及低成本栀子蓝色素的制备方法，分为三个步骤进行，具体如下：
步骤一、栀子蓝前体的制备
称取摩尔比为1:（0.375～0.75）的京尼平液体和氨基酸进行聚合反应，得到栀子蓝前体；
其中，所述京尼平液体是栀子果中提取栀子黄后的副产物经过纤维素酶的酶解制得的；京尼平液体浓度以色价计，色价限制在10～40之间，优选的色价范围为20～30，更优选的色价范围为24～26。所述氨基酸为苯丙氨酸、色氨酸、酪氨酸和甘氨酸中的一种或几种，均为市售产品，有效含量不限，优选的含量为90%～100%，具体添加量需进行折算处理。所述摩尔比优选1:（0.4～0.7），更优选为1:（0.5～0.6）。所述反应条件包括但不限于静置于室温裸露的空气中。 The present invention is described in further detail below:
The invention provides a method for preparing high-brightness, low-redness and low-cost gardenia blue pigment, which is divided into three steps, specifically as follows:
Step 1. Preparation of gardenia blue precursor. Weigh genipin liquid with a molar ratio of 1: (0.375~0.75) and amino acids for polymerization reaction to obtain gardenia blue precursor;
Wherein, the genipin liquid is obtained by enzymatic hydrolysis of cellulase, a by-product of gardenia yellow extracted from gardenia fruit; the concentration of genipin liquid is based on color value, and the color value is limited to 10 to 40 The preferred color value range is 20-30, and the more preferred color value range is 24-26. The amino acid is one or more of phenylalanine, tryptophan, tyrosine and glycine, all of which are commercially available products. The effective content is not limited, and the preferred content is 90% to 100%. The specific addition amount Conversion processing is required. The molar ratio is preferably 1:(0.4-0.7), more preferably 1:(0.5-0.6). The reaction conditions include, but are not limited to, standing in exposed air at room temperature.
步骤二、栀子蓝前体氧化呈色
对步骤一得到的栀子蓝前体进行氧化处理，并监测色价及色调，直至色价及色调在1小时内不发生较大变化，得到栀子蓝；
其中，所述氧化处理使用的氧化剂包括但不限于压缩空气、臭氧、双氧水、过氧乙酸或者其他食品中常用氧化剂；优先选用压缩空气作为氧化剂。所述监测色价及色调的具体方法如下：
1）称取少量呈色结束后的栀子蓝，用超纯水稀释，得到稀释液；根据GB 28311-2012，采用紫外-可见分光光度计测定稀释液的最大吸收波长λ max（公式如下），得到色价：
其中，A：样品在最大吸收波长λ max下的吸光度；c：被测试样液浓度，g/mL；100：浓度换算系数；
2）在最大吸收波长λ max处，调节步骤1）中稀释液的吸光度为1.000±0.001，利用色差仪（型号：CM-5；柯尼卡-美能达，日本）测定色调，测定条件：光源D65，观察角10度；测定样品的L*值、a*值和b*值，其中，L*值、a*值和b*值分别表示亮度、红绿值和黄蓝值。 Step 2. Oxidation and color development of gardenia blue precursor. Oxidize the gardenia blue precursor obtained in step 1, and monitor the color value and hue until the color value and hue do not change significantly within 1 hour to obtain gardenia. blue;
Among them, the oxidants used in the oxidation treatment include but are not limited to compressed air, ozone, hydrogen peroxide, peracetic acid or other oxidants commonly used in food; compressed air is preferably used as the oxidant. The specific method for monitoring color price and hue is as follows:
1) Weigh a small amount of gardenia blue after color development and dilute it with ultrapure water to obtain a diluent; according to GB 28311-2012, use a UV-visible spectrophotometer to measure the maximum absorption wavelength λ max of the diluent (the formula is as follows) , get the color price:
Among them, A: the absorbance of the sample at the maximum absorption wavelength λ max ; c: the concentration of the sample liquid to be tested, g/mL; 100: concentration conversion coefficient;
2) At the maximum absorption wavelength λ max , adjust the absorbance of the diluent in step 1) to 1.000±0.001, and use a colorimeter (model: CM-5; Konica-Minolta, Japan) to measure the hue. Measurement conditions: light source D65, observation angle 10 degrees; measure the L* value, a* value and b* value of the sample, where the L* value, a* value and b* value represent the brightness, red-green value and yellow-blue value respectively.
实验结果以平行测定结果的算术平均值为准。在重复条件下获得的两次独立测定结果的绝对差值不得超过2%。The experimental results are based on the arithmetic mean of parallel measurement results. The absolute difference between two independent determination results obtained under repeated conditions shall not exceed 2%.
步骤三、精制纯化及喷雾干燥
在常温条件下，对步骤二得到的栀子蓝进行超滤精制，去除杂质并浓缩。得到精制浓缩液并进行喷雾干燥，得到高亮度、低红度的栀子蓝色素。 Step 3. Refining, purification and spray drying. Under normal temperature conditions, perform ultrafiltration and purification of the gardenia blue obtained in step 2 to remove impurities and concentrate. The refined concentrate is obtained and spray-dried to obtain a gardenia blue pigment with high brightness and low redness.
为了确定栀子蓝色素的最优制备方法，对制备方法的探究步骤如下：
设定京尼平液体浓度为E25，改变京尼平与氨基酸的添加比例，以京尼平液体与大豆肽作为对照组，验证京尼平与氨基酸摩尔比对呈色结果的影响，验证结果见表1：
表1 京尼平与不同氨基酸添加比例对呈色结果的影响
In order to determine the optimal preparation method of gardenia blue pigment, the steps for exploring the preparation method are as follows:
Set the concentration of genipin liquid to E25, change the addition ratio of genipin and amino acids, and use genipin liquid and soybean peptide as the control group to verify the impact of the molar ratio of genipin and amino acids on the color results. The verification results are shown in Table 1:
Table 1 Effect of genipin and different amino acid addition ratios on color development results
分析表1的数据可知，改变京尼平与苯丙氨酸、色氨酸、酪氨酸和甘氨酸的添加比例，其△E值分别为9.10、16.95、7.68和7.94，呈色结果相差较大；而改变京尼平与大豆肽的添加比例，△E值为1.44，两种成分不同的添加比例对呈色结果几乎没有影响。从京尼平与不同原料的不同呈色结果还可以看出，在京尼平和氨基酸摩尔比为1:0.5时，苯丙氨酸、色氨酸、酪氨酸和甘氨酸的L*值分别为67.87、64.3、67.24和62.75，a*值分别为-25.16、-31.38、-26.52和-13.08，苯丙氨酸和酪氨酸的亮度较高且红度低。而在京尼平和氨基酸摩尔比为1:1时，亮度稍微增高，但是红度明显增加。从京尼平与大豆肽的呈色数据看出，改变两者的比例，色调几乎不变，亮度较高，红度液比较低。从以上对数据的分析得知，改变京尼平苯丙氨酸、色氨酸、酪氨酸和甘氨酸的添加比例对呈色结果影响较大，而京尼平与大豆肽添加比例对呈色结果没有影响。Analysis of the data in Table 1 shows that when the addition ratio of genipin to phenylalanine, tryptophan, tyrosine and glycine is changed, the △E values are 9.10, 16.95, 7.68 and 7.94 respectively, and the color results are quite different. ; When changing the addition ratio of genipin and soybean peptide, the △E value is 1.44. Different addition ratios of the two ingredients have almost no impact on the color results. It can also be seen from the different color results of genipin and different raw materials that when the molar ratio of genipin to amino acids is 1:0.5, the L* values of phenylalanine, tryptophan, tyrosine and glycine are 67.87 respectively. , 64.3, 67.24 and 62.75, the a* values are -25.16, -31.38, -26.52 and -13.08 respectively. The brightness of phenylalanine and tyrosine is high and the redness is low. When the molar ratio of genipin to amino acid is 1:1, the brightness increases slightly, but the redness increases significantly. From the color data of genipin and soybean peptide, it can be seen that when the ratio of the two is changed, the hue is almost unchanged, the brightness is higher, and the redness is relatively low. From the above analysis of the data, it is known that changing the addition ratio of genipin phenylalanine, tryptophan, tyrosine and glycine has a greater impact on the color results, while the addition ratio of genipin and soybean peptide has a greater impact on the color development. The results have no impact.
为了进一步验证上述结论的正确性，即改变京尼平与苯丙氨酸、色氨酸、酪氨酸和甘氨酸的添加比例对色调有影响，而非其他因素也可以对呈色结果造成影响，本发明特增加了另外一项实验，物料浓度对呈色结果的影响。In order to further verify the correctness of the above conclusion, that is, changing the addition ratio of genipin to phenylalanine, tryptophan, tyrosine and glycine has an impact on the color tone, but not other factors can also affect the color results, The present invention adds another experiment, the influence of material concentration on color results.
因表1中苯丙氨酸的呈色结果色价及色调较好，本发明选用苯丙氨酸作为反应原料。设定京尼平与苯丙氨酸的摩尔浓度比分别为0.2 mol/L:0.2 mol/L、0.15 mol/L:0.15 mol/L、0.1 mol/L:0.1 mol/L及0.2 mol/L:0.1 mol/L，并通过制备工艺步骤一和步骤二的工艺方法进行实验。Because the coloring results of phenylalanine in Table 1 have good color value and hue, the present invention selects phenylalanine as the reaction raw material. Set the molar concentration ratios of genipin and phenylalanine to 0.2 mol/L:0.2 mol/L, 0.15 mol/L:0.15 mol/L, 0.1 mol/L:0.1 mol/L and 0.2 mol/L respectively. :0.1 mol/L, and conduct experiments through the preparation process steps one and two.
表2 京尼平与苯丙氨酸摩尔浓度比对呈色结果的影响
Table 2 Effect of molar concentration ratio of genipin and phenylalanine on color development results
由表2实验数据可知，京尼平与苯丙氨酸浓度比为0.2 mol/L:0.2 mol/L、0.15 mol/L:0.15 mol/L和0.1 mol/L:0.1 mol/L时，其呈色液色差△E分别为0.44和0.88，三组色调几乎无差异，但是三组的色价随物料浓度的降低依次减小，分别为17.26、13.19和8.57。当京尼平与苯丙氨酸的摩尔浓度比为0.2 mol/L:0.1 mol/L时，呈色液亮度L*为68.37，红度a*为-25.6，且色差与上述三组色调色差△E为9.42，相差较大。从以上数据分析结果可以看出，改变物料浓度对色调的改变程度几乎无影响，降低苯丙氨酸的用量能有效降低呈色液的红度。It can be seen from the experimental data in Table 2 that when the concentration ratios of genipin and phenylalanine are 0.2 mol/L:0.2 mol/L, 0.15 mol/L:0.15 mol/L and 0.1 mol/L:0.1 mol/L, the The color difference ΔE of the coloring solution is 0.44 and 0.88 respectively. There is almost no difference in the hue of the three groups. However, the color values of the three groups decrease with the decrease of material concentration, which are 17.26, 13.19 and 8.57 respectively. When the molar concentration ratio of genipin and phenylalanine is 0.2 mol/L:0.1 mol/L, the brightness L* of the color liquid is 68.37, the redness a* is -25.6, and the color difference is the same as the color difference of the above three groups of hues △E is 9.42, which is a big difference. From the above data analysis results, it can be seen that changing the material concentration has almost no effect on the degree of change in hue, and reducing the amount of phenylalanine can effectively reduce the redness of the coloring solution.
结合京尼平与不同氨基酸添加比例对呈色结果的影响，以及京尼平与苯丙氨酸摩尔浓度比对呈色结果的影响可以得出，在相同的工艺条件下，只有通过降低氨基酸的使用量，即降低氨基酸与京尼平的添加比例，才能有效降低栀子蓝呈色液的红度，而大豆肽栀子蓝不受添加比例的影响。本发明为了得到亮度高、红度低的栀子蓝，需进一步确定京尼平与氨基酸的添加比例范围。在相同条件下，京尼平分别与苯丙氨酸、色氨酸、酪氨酸和甘氨酸呈色反应中，添加比例均为1:0.5时，苯丙氨酸栀子蓝的色价最高，且呈色液亮度L*为67.87，红度a*为-25.16，综合考虑色调及生产成本问题，本发明特选用苯丙氨酸作为最优的反应原料。Combining the effects of genipin and different amino acid addition ratios on the color results, as well as the effects of the molar concentration ratio of genipin and phenylalanine on the color results, it can be concluded that under the same process conditions, only by reducing the concentration of amino acids The usage amount, that is, reducing the addition ratio of amino acids to genipin, can effectively reduce the redness of Gardenia Blue color solution, while soybean peptide Gardenia Blue is not affected by the addition ratio. In order to obtain gardenia blue with high brightness and low redness, the present invention needs to further determine the addition ratio range of genipin and amino acids. Under the same conditions, in the color reaction of genipin with phenylalanine, tryptophan, tyrosine and glycine respectively, when the addition ratio is 1:0.5, the color value of phenylalanine gardenia blue is the highest. The brightness L* of the coloring liquid is 67.87, and the redness a* is -25.16. Considering the color tone and production cost, the present invention specifically selects phenylalanine as the optimal reaction raw material.
以下实验选用苯丙氨酸和京尼平作为原料，通过改变京尼平与苯丙氨酸的添加比例，在保持目标色调的同时，结合呈色结束时栀子蓝料液色价的高低，来进一步确定京尼平与氨基酸的添加比例范围。The following experiment uses phenylalanine and genipin as raw materials. By changing the addition ratio of genipin and phenylalanine, while maintaining the target color tone, combined with the color value of the gardenia blue material liquid at the end of the color development, To further determine the addition ratio range of genipin and amino acids.
设定京尼平与苯丙氨酸的摩尔比分别为1:0.25、1:0.375、1:0.5、1:0.75和1:1，并按照制备工艺步骤（1）和步骤（2）的工艺方法进行实验。Set the molar ratios of genipin and phenylalanine to 1:0.25, 1:0.375, 1:0.5, 1:0.75 and 1:1 respectively, and follow the preparation process steps (1) and (2). method to conduct experiments.
表3 京尼平与苯丙氨酸不同摩尔比对呈色结果的影响
Table 3 Effects of different molar ratios of genipin and phenylalanine on color development results
由表3数据可知，当京尼平与苯丙氨酸的摩尔比为1:0.25时，虽然呈色液红度较低（a*为-30.25），但是呈色液色价只有2.56，不符合生产需要，且b*为-12.78，栀子蓝呈色液稀释后呈偏绿色，而非蓝色。故当京尼平与苯丙氨酸的摩尔比为1:0.25时，并不能产生栀子蓝。当京尼平与苯丙氨酸摩尔比为1:1时，其L*值、a*值和b*值分别为68.52、-17.04和-30.26，虽然亮度较高，但是其红度也随之升高。而京尼平与苯丙氨酸在1:（0.375～0.75）范围内，栀子蓝亮度较高，且红度值较低。所以本发明京尼平与氨基酸最优的摩尔比范围是1:（0.375～0.75）。It can be seen from the data in Table 3 that when the molar ratio of genipin to phenylalanine is 1:0.25, although the redness of the coloring liquid is low (a* is -30.25), the color value of the coloring liquid is only 2.56. It meets the production needs, and b* is -12.78. After dilution, the gardenia blue color solution turns green instead of blue. Therefore, when the molar ratio of genipin to phenylalanine is 1:0.25, gardenia blue cannot be produced. When the molar ratio of genipin to phenylalanine is 1:1, its L* value, a* value and b* value are 68.52, -17.04 and -30.26 respectively. Although the brightness is high, its redness also changes with the of rising. While genipin and phenylalanine are in the range of 1: (0.375~0.75), Gardenia Blue has higher brightness and lower redness value. Therefore, the optimal molar ratio range of genipin and amino acids in the present invention is 1: (0.375-0.75).
本发明通过调节京尼平与氨基酸的添加比例，并利用栀子蓝前体的制备以及栀子蓝氧化呈色的工艺，制备出了高亮度、低红度且成本较低的栀子蓝，提升了栀子蓝的应用品质。以下实施例和表4是对本发明的详细介绍。The present invention prepares gardenia blue with high brightness, low redness and low cost by adjusting the addition ratio of genipin and amino acids, and utilizing the preparation of gardenia blue precursor and the process of gardenia blue oxidation and color development. Improved the application quality of Gardenia Blue. The following examples and Table 4 are a detailed introduction to the present invention.
实施例1
（1）栀子蓝前体的制备
将高色价栀子甙酶解液（即京尼平液体）与水混合，稀释料液至色价为E25，称取850 g稀释液，升高温度至35 ℃，待温度稳定后，添加1 g磷酸二氢钠•二水和7 g磷酸氢二钠•二水，用30%的NaOH溶液调节pH值至7.49，添加16.5 g苯丙氨酸，保持24小时，得到栀子蓝前体。 Example 1
(1) Preparation of Gardenia Blue Precursor Mix the high color value gardenia glycoside enzymatic hydrolyzate (i.e. genipin liquid) with water, dilute the material solution to a color value of E25, weigh 850 g of the diluted solution, and raise the temperature to 35 ℃. After the temperature stabilizes, add 1 g sodium hydrogen phosphate dihydrate and 7 g sodium hydrogen phosphate dihydrate. Use 30% NaOH solution to adjust the pH to 7.49. Add 16.5 g phenylalanine. Keep it for 24 hours to obtain the gardenia blue precursor.
（2）栀子蓝前体氧化呈色
对栀子蓝前体通入压缩空气，并开启搅拌，搅拌速度为200转/分钟，每隔1小时用紫外-可见分光光度计检测反应液的最大吸收波长λ max，以及最大吸收波长下的色价E λmax，并用色差仪检测吸光度为1.000±0.001的溶液色调，即L*值、a*值和b*值。 (2) Oxidation and color development of gardenia blue precursor. Pour compressed air into the gardenia blue precursor and start stirring. The stirring speed is 200 rpm. Use a UV-visible spectrophotometer to detect the maximum concentration of the reaction solution every hour. The absorption wavelength λ max , and the color value E λ max at the maximum absorption wavelength, and use a colorimeter to detect the solution hue with an absorbance of 1.000±0.001, that is, L* value, a* value and b* value.
经过30小时的氧化呈色，最终呈色液的色价，最大吸收波长599.5 nm，再经过超滤膜精制及喷雾干燥，得到栀子蓝粉体。栀子蓝粉体在波长599.5 nm，Abs=1.000时，其亮度L*为67.87，a*为-25.16，b*为-26.21。After 30 hours of oxidation and color development, the final color solution has a color value and a maximum absorption wavelength of 599.5 nm. It is then refined with an ultrafiltration membrane and spray-dried to obtain gardenia blue powder. When the wavelength of gardenia blue powder is 599.5 nm and Abs=1.000, its brightness L* is 67.87, a* is -25.16, and b* is -26.21.
实施例2
（1）栀子蓝前体的制备
将高色价栀子甙酶解液（即京尼平液体）与水混合，稀释料液至色价为E25，称取850 g稀释液，升高温度至35 ℃，待温度稳定后，添加1g磷酸二氢钠•二水和7 g磷酸氢二钠•二水，用30%的NaOH溶液调节pH值至7.51，添加16.5 g苯丙氨酸，保持24小时，得到栀子蓝前体。 Example 2
(1) Preparation of Gardenia Blue Precursor Mix the high color value gardenia glycoside enzymatic hydrolyzate (i.e. genipin liquid) with water, dilute the material solution to a color value of E25, weigh 850 g of the diluted solution, and raise the temperature to 35 ℃, after the temperature stabilizes, add 1g sodium hydrogen phosphate dihydrate and 7 g sodium hydrogen phosphate dihydrate, adjust the pH value to 7.51 with 30% NaOH solution, add 16.5 g phenylalanine, and maintain After 24 hours, a gardenia blue precursor was obtained.
（2）栀子蓝前体氧化呈色
对栀子蓝前体通入压缩空气，并开启搅拌，搅拌速度为200转/分钟，每隔1小时用紫外-可见分光光度计检测反应液的最大吸收波长λ max，以及最大吸收波长下的色价E λmax，并用色差仪检测吸光度为1.000±0.001的溶液色调，即L*值、a*值和b*值。 (2) Oxidation and color development of gardenia blue precursor. Pour compressed air into the gardenia blue precursor and start stirring. The stirring speed is 200 rpm. Use a UV-visible spectrophotometer to detect the maximum concentration of the reaction solution every hour. The absorption wavelength λ max , and the color value E λ max at the maximum absorption wavelength, and use a colorimeter to detect the solution hue with an absorbance of 1.000±0.001, that is, L* value, a* value and b* value.
经过31小时的氧化呈色，最终呈色液的色价，最大吸收波长600 nm，再经过超滤膜精制及喷雾干燥，得到栀子蓝粉体。栀子蓝粉体在波长600 nm，Abs=1.000时，其亮度L*为68.25，a*为-25.33，b*为-25.98。After 31 hours of oxidation and color development, the final color solution has a color value and a maximum absorption wavelength of 600 nm. It is then refined with an ultrafiltration membrane and spray-dried to obtain gardenia blue powder. When the wavelength of gardenia blue powder is 600 nm and Abs=1.000, its brightness L* is 68.25, a* is -25.33, and b* is -25.98.
实施例3
（1）栀子蓝前体的制备
将高色价栀子甙酶解液（即京尼平液体）与水混合，稀释料液至色价为E20，称取850 g稀释液，升高温度至35 ℃，待温度稳定后，添加1g磷酸二氢钠•二水和7 g磷酸氢二钠•二水，用30%的NaOH溶液调节pH值至7.48，添加13.2 g苯丙氨酸，保持24小时，得到栀子蓝前体。 Example 3
(1) Preparation of Gardenia Blue Precursor Mix the high color value gardenia glycoside enzymatic hydrolyzate (i.e. genipin liquid) with water, dilute the material solution to a color value of E20, weigh 850 g of the diluted solution, and raise the temperature to 35 ℃, after the temperature stabilizes, add 1g sodium hydrogen phosphate dihydrate and 7 g sodium hydrogen phosphate dihydrate, adjust the pH value to 7.48 with 30% NaOH solution, add 13.2 g phenylalanine, and keep After 24 hours, a gardenia blue precursor was obtained.
（2）栀子蓝前体氧化呈色
对栀子蓝前体通入压缩空气，并开启搅拌，搅拌速度为200转/分钟，每隔1小时用紫外-可见分光光度计检测反应液的最大吸收波长λ max，以及最大吸收波长下的色价E λmax，并用色差仪检测吸光度为1.000±0.001的溶液色调，即L*值、a*值和b*值。 (2) Oxidation and color development of gardenia blue precursor. Pour compressed air into the gardenia blue precursor and start stirring. The stirring speed is 200 rpm. Use a UV-visible spectrophotometer to detect the maximum concentration of the reaction solution every hour. The absorption wavelength λ max , and the color value E λ max at the maximum absorption wavelength, and use a colorimeter to detect the solution hue with an absorbance of 1.000±0.001, that is, L* value, a* value and b* value.
经过30小时的氧化呈色，最终呈色液的色价，最大吸收波长602 nm，再经过超滤膜精制及喷雾干燥，得到栀子蓝粉体。栀子蓝粉体在波长602 nm，Abs=1.000时，其亮度L*为68.56，a*为-27.88，b*为-25.02。After 30 hours of oxidation and color development, the final color solution has a color value and a maximum absorption wavelength of 602 nm. It is then refined with an ultrafiltration membrane and spray-dried to obtain gardenia blue powder. When the wavelength of gardenia blue powder is 602 nm and Abs=1.000, its brightness L* is 68.56, a* is -27.88, and b* is -25.02.
实施例4
（1）栀子蓝前体的制备
将高色价栀子甙酶解液（即京尼平液体）与水混合，稀释料液至色价为E25，称取850 g稀释液，升高温度至35 ℃，待温度稳定后，添加1 g磷酸二氢钠•二水和7 g磷酸氢二钠•二水，用30%的NaOH溶液调节pH值至7.42，添加19.43 g苯丙氨酸，保持24小时，得到栀子蓝前体。 Example 4
(1) Preparation of Gardenia Blue Precursor Mix the high color value gardenia glycoside enzymatic hydrolyzate (i.e. genipin liquid) with water, dilute the material solution to a color value of E25, weigh 850 g of the diluted solution, and raise the temperature to 35 ℃. After the temperature stabilizes, add 1 g sodium hydrogen phosphate dihydrate and 7 g sodium hydrogen phosphate dihydrate. Use 30% NaOH solution to adjust the pH to 7.42. Add 19.43 g phenylalanine. Keep it for 24 hours to obtain the gardenia blue precursor.
（2）栀子蓝前体氧化呈色
对栀子蓝前体通入压缩空气，并开启搅拌，搅拌速度为200转/分钟，每隔1小时用紫外-可见分光光度计检测反应液的最大吸收波长λ max，以及最大吸收波长下的色价E λmax，并用色差仪检测吸光度为1.000±0.001的溶液色调，即L*值、a*值和b*值。 (2) Oxidation and color development of gardenia blue precursor. Pour compressed air into the gardenia blue precursor and start stirring. The stirring speed is 200 rpm. Use a UV-visible spectrophotometer to detect the maximum concentration of the reaction solution every hour. The absorption wavelength λ max , and the color value E λ max at the maximum absorption wavelength, and use a colorimeter to detect the solution hue with an absorbance of 1.000±0.001, that is, L* value, a* value and b* value.
经过29小时的氧化呈色，最终呈色液的色价，最大吸收波长598.5 nm，再经过超滤膜精制及喷雾干燥，得到栀子蓝粉体。栀子蓝粉体在波长598.5 nm，Abs=1.000时，其亮度L*为67.72，a*为-25.01，b*为-27.13。After 29 hours of oxidation and color development, the final color solution has a color value and a maximum absorption wavelength of 598.5 nm. It is then refined with an ultrafiltration membrane and spray-dried to obtain gardenia blue powder. When the wavelength of gardenia blue powder is 598.5 nm and Abs=1.000, its brightness L* is 67.72, a* is -25.01, and b* is -27.13.
实施例5
（1）栀子蓝前体的制备
将高色价栀子甙酶解液（即京尼平液体）与水混合，稀释料液至色价为E25，称取850 g稀释液，升高温度至35 ℃，待温度稳定后，添加1 g磷酸二氢钠•二水和7 g磷酸氢二钠•二水，用30%的NaOH溶液调节pH值至7.47，添加24.75 g苯丙氨酸，保持24小时，得到栀子蓝前体。 Example 5
(1) Preparation of Gardenia Blue Precursor Mix the high color value gardenia glycoside enzymatic hydrolyzate (i.e. genipin liquid) with water, dilute the material solution to a color value of E25, weigh 850 g of the diluted solution, and raise the temperature to 35 ℃. After the temperature stabilizes, add 1 g sodium hydrogen phosphate dihydrate and 7 g sodium hydrogen phosphate dihydrate. Use 30% NaOH solution to adjust the pH to 7.47. Add 24.75 g phenylalanine. Keep it for 24 hours to obtain the gardenia blue precursor.
（2）栀子蓝前体氧化呈色
对栀子蓝前体通入压缩空气，并开启搅拌，搅拌速度为200转/分钟，每隔1小时用紫外-可见分光光度计检测反应液的最大吸收波长λ max，以及最大吸收波长下的色价E λmax，并用色差仪检测吸光度为1.000±0.001的溶液色调，即L*值、a*值和b*值。 (2) Oxidation and color development of gardenia blue precursor. Pour compressed air into the gardenia blue precursor and start stirring. The stirring speed is 200 rpm. Use a UV-visible spectrophotometer to detect the maximum concentration of the reaction solution every hour. The absorption wavelength λ max , and the color value E λ max at the maximum absorption wavelength, and use a colorimeter to detect the solution hue with an absorbance of 1.000±0.001, that is, L* value, a* value and b* value.
经过30小时的氧化呈色，最终呈色液的色价，最大吸收波长597 nm，再经过超滤膜精制及喷雾干燥，得到栀子蓝粉体。栀子蓝粉体在波长597 nm，Abs=1.000时，其亮度L*为68.55，a*为-19.59，b*为-29.01。After 30 hours of oxidation and color development, the final color solution has a color value and a maximum absorption wavelength of 597 nm. It is then refined with an ultrafiltration membrane and spray-dried to obtain gardenia blue powder. When the wavelength of gardenia blue powder is 597 nm and Abs=1.000, its brightness L* is 68.55, a* is -19.59, and b* is -29.01.
对实施例1~5制得的栀子蓝粉体以及购买的外样1（    栀子蓝色素，CAS:106441-42-3，购于河北创之源生物科技有限公司）、外样2（栀子蓝色素，CAS：106441-42-3，购于武汉拉那白医药化工有限公司）进行呈色对比，结果参见表4：
表4 不同实施例的呈色结果
The gardenia blue powder prepared in Examples 1 to 5 and the purchased external sample 1 (gardenia blue pigment, CAS: 106441-42-3, purchased from Hebei Chuangzhiyuan Biotechnology Co., Ltd.), external sample 2 ( Gardenia blue pigment, CAS: 106441-42-3, purchased from Wuhan Lanabai Pharmaceutical Chemical Co., Ltd.) was used for color comparison. The results are shown in Table 4:
Table 4 Coloration results of different embodiments
由表4可看出，实施例1~5制得的栀子蓝粉体的亮度均优于外样1和外样2，实施例1~5制得的栀子蓝粉体的红度均低于外样1，实施例1~4制得的栀子蓝粉体的红度均低于外样2，说明本方法制得的栀子蓝色素具有高亮度和低红度。It can be seen from Table 4 that the brightness of the gardenia blue powder prepared in Examples 1 to 5 is better than that of the external sample 1 and the external sample 2, and the redness of the gardenia blue powder prepared in Examples 1 to 5 is even better. Lower than the external sample 1, the redness of the gardenia blue powder prepared in Examples 1 to 4 is lower than that of the external sample 2, indicating that the gardenia blue pigment prepared by this method has high brightness and low redness.
以上内容仅为说明本发明的技术思想，不能以此限定本发明的保护范围，凡是按照本发明提出的技术思想，在技术方案基础上所做的任何改动，均落入本发明权利要求书的保护范围之内。The above contents are only for illustrating the technical ideas of the present invention and cannot be used to limit the protection scope of the present invention. Any changes made based on the technical ideas proposed by the present invention and based on the technical solutions shall fall within the scope of the claims of the present invention. within the scope of protection.

Claims (10)

  1. 一种高亮度、低红度的栀子蓝色素的制备方法，其特征在于，步骤如下：A method for preparing high-brightness, low-redness gardenia blue pigment, which is characterized in that the steps are as follows:
    1）称取摩尔比为1:（0.375～0.75）的京尼平液体和氨基酸进行聚合反应，得到栀子蓝前体；1) Weigh genipin liquid and amino acid with a molar ratio of 1: (0.375~0.75) and perform polymerization reaction to obtain a gardenia blue precursor;
    2）对栀子蓝前体进行氧化呈色处理，并间隔监测色价及色调，直至色价及色调不发生变化，得到栀子蓝；2) Carry out oxidation and color development treatment on the gardenia blue precursor, and monitor the color value and hue at intervals until the color value and hue do not change to obtain gardenia blue;
    3）对栀子蓝进行超滤，去除杂质，浓缩，干燥，得到高亮度、低红度的栀子蓝色素。3) Ultrafiltrate gardenia blue to remove impurities, concentrate, and dry to obtain gardenia blue pigment with high brightness and low redness.
  2.  根据权利要求1所述的一种高亮度、低红度的栀子蓝色素的制备方法，其特征在于，步骤1）中，所述京尼平的色价为E10～E40。The method for preparing a high-brightness, low-redness gardenia blue pigment according to claim 1, characterized in that in step 1), the color value of the genipin is E10 to E40.
  3.  根据权利要求1所述的一种高亮度、低红度的栀子蓝色素的制备方法，其特征在于，步骤1）中，氨基酸为苯丙氨酸、色氨酸、甘氨酸和酪氨酸中的一种或几种。The preparation method of a high-brightness, low-redness gardenia blue pigment according to claim 1, characterized in that in step 1), the amino acids are phenylalanine, tryptophan, glycine and tyrosine. one or several kinds.
  4.  根据权利要求1所述的一种高亮度、低红度的栀子蓝色素的制备方法，其特征在于，步骤1）中，反应条件为静置于室温裸露的空气中。The method for preparing a high-brightness, low-redness gardenia blue pigment according to claim 1, characterized in that in step 1), the reaction condition is to stand in exposed air at room temperature.
  5.  根据权利要求1所述的一种高亮度、低红度的栀子蓝色素的制备方法，其特征在于，步骤2）中，氧化呈色处理使用的氧化剂为压缩空气、臭氧、双氧水、过氧乙酸或者其他食品中常用氧化剂。The method for preparing a gardenia blue pigment with high brightness and low redness according to claim 1, characterized in that in step 2), the oxidizing agent used in the oxidation and color development treatment is compressed air, ozone, hydrogen peroxide, peroxide Acetic acid or other oxidizing agents commonly used in foods.
  6.  根据权利要求1所述的一种高亮度、低红度的栀子蓝色素的制备方法，其特征在于，步骤2）中，氧化处理的同时，以速度为200转/分钟进行搅拌。The method for preparing a high-brightness, low-redness gardenia blue pigment according to claim 1, characterized in that in step 2), during the oxidation treatment, the mixture is stirred at a speed of 200 rpm.
  7.  根据权利要求1所述的一种高亮度、低红度的栀子蓝色素的制备方法，其特征在于，步骤2）中，所述监测色价及色调的方法为：称取呈色结束后的栀子蓝，并用超纯水稀释，得到稀释液；用紫外-可见分光光度计测定稀释液的λ max，得到色价；在λ max处调节稀释液吸光度为1.000±0.001，用色差仪测定吸光度为1.000±0.001稀释液的L*、a*和b*值。 A method for preparing high-brightness, low-redness gardenia blue pigment according to claim 1, characterized in that in step 2), the method for monitoring color value and hue is: weighing after completion of color development Gardenia blue, and dilute it with ultrapure water to obtain a diluted solution; use a UV-visible spectrophotometer to measure the λ max of the diluted solution to obtain the color value; adjust the absorbance of the diluted solution at λ max to 1.000±0.001, and measure it with a colorimeter The absorbance is the L*, a* and b* value of the 1.000±0.001 dilution.
  8.  根据权利要求7所述的一种高亮度、低红度的栀子蓝色素的制备方法，其特征在于，利用色差仪测定色调的条件为：光源D65，观察角10度。The preparation method of a high-brightness, low-redness gardenia blue pigment according to claim 7, characterized in that the conditions for measuring the hue using a colorimeter are: light source D65, observation angle 10 degrees.
  9.  权利要求1~8任意一项所述的制备方法制得的栀子蓝色素。The gardenia blue pigment prepared by the preparation method described in any one of claims 1 to 8.
  10.  根据权利要求9所述的栀子蓝色素，其特征在于，所述栀子蓝色素的L*为67.72~68.56，a*为-27.88~-19.59，b*为-29.01~-25.02。The gardenia blue pigment according to claim 9, characterized in that the L* of the gardenia blue pigment is 67.72~68.56, a* is -27.88~-19.59, and b* is -29.01~-25.02.
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