CN110122813B - Method for realizing 4D printing of color jelly by utilizing spontaneous color change of blueberry anthocyanin - Google Patents

Method for realizing 4D printing of color jelly by utilizing spontaneous color change of blueberry anthocyanin Download PDF

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CN110122813B
CN110122813B CN201910420994.5A CN201910420994A CN110122813B CN 110122813 B CN110122813 B CN 110122813B CN 201910420994 A CN201910420994 A CN 201910420994A CN 110122813 B CN110122813 B CN 110122813B
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color
printing
anthocyanin
layer
parts
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CN110122813A (en
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张慜
郭超凡
安迈·加扎勒
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Jiangnan University
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Jiangnan University
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Priority to PCT/CN2019/123526 priority patent/WO2020233101A1/en
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    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
    • A23L21/00—Marmalades, jams, jellies or the like; Products from apiculture; Preparation or treatment thereof
    • A23L21/10—Marmalades; Jams; Jellies; Other similar fruit or vegetable compositions; Simulated fruit products
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
    • A23L21/00—Marmalades, jams, jellies or the like; Products from apiculture; Preparation or treatment thereof
    • A23L21/10—Marmalades; Jams; Jellies; Other similar fruit or vegetable compositions; Simulated fruit products
    • A23L21/12—Marmalades; Jams; Jellies; Other similar fruit or vegetable compositions; Simulated fruit products derived from fruit or vegetable solids
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
    • A23L33/00—Modifying nutritive qualities of foods; Dietetic products; Preparation or treatment thereof
    • A23L33/10—Modifying nutritive qualities of foods; Dietetic products; Preparation or treatment thereof using additives
    • A23L33/105—Plant extracts, their artificial duplicates or their derivatives
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
    • A23L5/00—Preparation or treatment of foods or foodstuffs, in general; Food or foodstuffs obtained thereby; Materials therefor
    • A23L5/30—Physical treatment, e.g. electrical or magnetic means, wave energy or irradiation
    • A23L5/32—Physical treatment, e.g. electrical or magnetic means, wave energy or irradiation using phonon wave energy, e.g. sound or ultrasonic waves
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
    • A23L5/00—Preparation or treatment of foods or foodstuffs, in general; Food or foodstuffs obtained thereby; Materials therefor
    • A23L5/40—Colouring or decolouring of foods
    • A23L5/42—Addition of dyes or pigments, e.g. in combination with optical brighteners
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D11/00—Solvent extraction
    • B01D11/02—Solvent extraction of solids
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D11/00—Solvent extraction
    • B01D11/02—Solvent extraction of solids
    • B01D11/0261—Solvent extraction of solids comprising vibrating mechanisms, e.g. mechanical, acoustical
    • B01D11/0265—Applying ultrasound
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D11/00—Solvent extraction
    • B01D11/02—Solvent extraction of solids
    • B01D11/0288—Applications, solvents
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23V—INDEXING SCHEME RELATING TO FOODS, FOODSTUFFS OR NON-ALCOHOLIC BEVERAGES AND LACTIC OR PROPIONIC ACID BACTERIA USED IN FOODSTUFFS OR FOOD PREPARATION
    • A23V2002/00—Food compositions, function of food ingredients or processes for food or foodstuffs
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P90/00—Enabling technologies with a potential contribution to greenhouse gas [GHG] emissions mitigation
    • Y02P90/30—Computing systems specially adapted for manufacturing

Abstract

The invention provides a method for realizing 4D printing of color jelly by utilizing spontaneous color change of blueberry anthocyanin, relates to a food processing technology, and belongs to the technical field of food processing. The method comprises the steps of fully mixing two raw materials, blending, homogenizing, gelatinizing, cooling, loading and degassing the two raw materials, and then carrying out layer-by-layer alternate 3D printing on a multi-material color-carrying layer and a multi-material color-controlling layer by using a double-nozzle printer according to an established 3D printing model. The color of the printed color-carrying layer jelly is changed from purple red within 2min according to the pH value of the contacted color-changing layer to: red; purple color; blue in color. The change of the fourth dimension is realized on the basis of 3D printing. The food printed by the method has richer visual effect, and the personalized and diversified production of the product can be realized.

Description

Method for realizing 4D printing of color jelly by utilizing spontaneous color change of blueberry anthocyanin
Technical Field
The invention relates to a method for realizing 4D printing of color jelly by utilizing spontaneous color change of blueberry anthocyanin, which is mainly used for 3D printing of jelly food containing natural fruit and vegetable anthocyanin, relates to a food processing technology and belongs to the technical field of food processing.
Background
The core principle of the 3D printing method is to print layer by layer and superpose layers into a three-dimensional pattern. Specifically, 3D printing includes three processes, one is to design a three-dimensional pattern using computer software, such as CAD; secondly, slicing the three-dimensional pattern to form a multi-layer two-dimensional plane graph and a printing track of each layer; thirdly, the numerical control system is used for controlling the path of the printer and finishing the printing. Compared with the traditional die manufacturing method, the 3D printing technology can realize the manufacturing of products with highly complex structures, improve the precision and quality of the products, save materials to the maximum extent, realize flexible design and personalized customization, and realize batch customization production, so that the rapid manufacturing becomes economic and economical.
With the increasing demands of consumers on the taste, appearance and health of foods, the customization degree of foods is also increasing, so that 3D printing technology of foods is receiving more and more attention and development. The goal of 3D printing of food is an order-by-order mode of production with higher production efficiency and lower coverage cost. Compared with the traditional supply chain mode, the supply chain for 3D printing greatly reduces the distribution cost and simplifies the customized food service.
So-called 4D printing, precisely a material that is capable of automatic deformation, with only specific conditions (such as temperature, humidity, etc.) and without any need to connect any complex electromechanical devices, allows a fourth dimensional change to be made according to the product design, which usually involves color, flavor and shape. Khoo et al (2015) propose 4D printing as a process of building physical objects using appropriate additive manufacturing techniques, laying down a series of stimulus responsive composite or multi-materials with different properties. After construction, the object reacts to stimuli from the natural environment or through human intervention, resulting in changes in the physical or chemical state over time. The 4D printing technology is not only a revolution of production tools, but also a technology that induces future changes in the way the entire business ecology is architected by changes in production data, and thus subversion will be not just manufacturing technology. However, the current concept of 4D printing has very limited research and application in the food field. The method for realizing 4D printing of the color jelly by the spontaneous color change and catalytic color change of the blueberry anthocyanin is characterized in that two jelly materials with different properties are constructed and laid by a 3D printing technology, so that the two materials are mutually blended and stimulated at the joint, and finally, the color change phenomenon occurs spontaneously to realize 4D change, and the composite 4D printing is also realized.
Anthocyanins are also called anthocyanidins, are water-soluble natural pigments widely existing in plants in nature, and are colored aglycones obtained by hydrolyzing anthocyanins. The main color-producing substances in fruits, vegetables and flowers are mostly related to the plants. Under the condition of different pH values of plant cell vacuoles, the anthocyanin enables the petals to present colorful colors. The anthocyanin molecule has a high molecular conjugation system, contains acidic and basic groups, and is easily dissolved in polar solvents such as water, methanol, ethanol, dilute alkali, dilute acid and the like. The ultraviolet light and the visible light have strong absorption, the maximum absorption wavelength of the ultraviolet light is near 280nm, and the maximum absorption wavelength of the visible light is within the range of 500-550 nm. The anthocyanin substance changes with the change of pH value, and is red at pH 7, purple at pH 7-8 and blue at pH > 11. Anthocyanins belong to the class of bioflavonoids, and the most important physiological active functions of flavonoids are free radical scavenging and antioxidant capacity. With the development of science and technology, people pay more and more attention to the safety of food additives, and the development and utilization of natural additives become the general trend of additive development and use. The anthocyanin can be used as a nutrition enhancer in food, can also be used as a food preservative to replace synthetic preservatives such as benzoic acid and the like, can be used as a food colorant to be applied to common beverages and food, and meets the total requirements of people on nature, safety and health of food additives.
Li et al (2019) disclose a 3D printing material (publication No. CN109198650A) for food rich in dietary fiber, which is prepared by uniformly mixing modified dietary fiber, starch, gluten protein powder, seasonings, water, vegetable oil, gelatin and the like, grinding the mixture to a fineness of less than 20 mu m, and processing the mixture by a high-pressure homogenizer, wherein the dietary fiber is subjected to a series of modification treatments, so that the particle size of the dietary fiber can be reduced, the dietary fiber particles are uniformly dispersed and stabilized, the content of water-soluble dietary fiber is increased, the content of the prepared 3D printing material for food is high, the surface of the dietary fiber is subjected to water-soluble treatment to further improve the taste, the taste can be improved in the preparation of a finished food product by 3D printing, the absorption of a human body is facilitated, the labor difficulty and intensity of operators are reduced, the maintenance cost of a 3D printer is reduced, and different auxiliary materials are added, the food with different tastes is made, the method is suitable for various 3D printers, and the materials with various tastes can be rapidly printed in a short time, so that the printing efficiency is improved. The 3D printing material takes starch and low acyl gellan gum as gelling agents, is favorable for re-melting, can be quickly gelled at room temperature, can ensure smooth discharging during 3D printing, and can improve the stability of the printing material by applying plant extracts, so that the printed candy can be stored for a long time, and the phenomenon of sand return is avoided. Experiments show that the printing material provided by the invention can be smoothly printed, the obtained product has good sensory evaluation, and no sand return or melting phenomenon is caused after the product is placed at room temperature for 60 days. Octopus and the like (2016) disclose a longan rice flour 3D printing food material (publication number: CN106213154A), which belongs to the field of 3D printing materials and comprises the following raw materials in parts by weight: 60-70 parts of rice flour, 5-8 parts of longan extract, 8-10 parts of water, 8-10 parts of fresh milk, 8-10 parts of buckwheat flour, 3-5 parts of vegetable oil, 2-3 parts of honey, 2-3 parts of xylitol, 2-3 parts of salt, 2-3 parts of maltodextrin, 2-3 parts of dietary fiber, 1-2 parts of emulsifier and 0.1-0.2 part of essence. The invention adopts low-sugar and low-fat raw materials, does not contain chemical additives, has no pollution and is healthier. The longan contains a large amount of trace elements beneficial to human health, and has the main functions of soothing the nerves, treating insomnia and the like. By adopting 3D printing, diversified, personalized and automatic production of products can be realized, and the types of 3D printed food materials are enriched. The nano rice flour can meet the process requirements of 3D printing; the selenium-rich rice flour is adopted to supplement selenium element required by human body, and the requirements of different consumers are met. Zhang Yunju et al (2017) disclose an ice cream 3D printer, an ice cream 3D printing method and a product thereof (publication number: CN 106578317A). This ice cream 3D printer is including printing platform, X to drive arrangement, Y to drive arrangement, Z to drive arrangement, spout material system, protection casing and master control set. The ice cream 3D printing method comprises the following steps: 1) printing a base layer consisting of contour lines and ice cream powder; 2) print a plurality of basic units of piling up step by step, and then obtain the ice cream that 3D printed. The technical scheme provided by the invention can solve the technical problems of long time consumption and high cost of 3D food printing at the present stage. The ice cream 3D printer provided by the invention has the advantages of novel structural design and high automation degree, and can meet the requirements of consumers on the diversification of ice cream food models; the technical scheme provided by the invention solves the problem that one ice cream is printed in several minutes by using the method for printing the ice cream coat, and greatly reduces the printing cost. The above inventions are mainly related to the proportioning of different materials for 3D printing and the production and manufacturing of machines. Different from the inventions, the invention mainly relates to a method for realizing color-changing 4D printing by catalyzing 3D printing through blueberry anthocyanin.
Lingweifu (2016) provides a preparation method of a color-changing rose tea (publication number: CN107772019A), comprising the steps of cleaning and crushing a substance rich in anthocyanin such as lycium ruthenicum, blueberries or mulberries, pouring alcohol into the crushed substance, stirring, filtering, settling, discarding residues, centrifuging, heating and concentrating, centrifuging again, adding alcohol to obtain a coloring liquid, naturally coloring the rose subjected to microwave drying and treating the rose by trypsin, and rapidly drying the colored rose by open wave drying. The beneficial effects are as follows: the finished color-changing rose tea is rich in anthocyanin, can be quickly precipitated in the brewing process to color tea water, can realize the change process from dark purple-light purple-dark red-light red-grass green to colorless, and has the advantages of simple operation, strong ornamental value and high nutrition and health care functions. Chengweili (2018) invented a color-changeable functional beverage and its preparation method (publication number: CN 108236027A). The color-changeable functional beverage takes anthocyanin embedded powder and lycopene embedded powder as main raw materials, the color of the beverage can be effectively changed by utilizing the embedding effect of microcapsules, when the beverage is in a static state, the pigment is adsorbed or embedded due to the adsorption of porous starch and the embedding of lactalbumin, so that the beverage is clear and transparent, but when the beverage is shaken forcibly, the embedded pigment and the adsorbed pigment are released due to the action of external force, so that the beverage presents gorgeous green and red, is very attractive, and can also attract the attention of children and teenagers. Meanwhile, the anthocyanin and the lycopene have excellent antioxidant activity, can improve the immunity of a human body and delay aging, and also have certain prevention and treatment effects on cancers and tumors, so that the beverage disclosed by the invention not only can attract customers, but also has a health-care effect. The invention discloses a Huang-rong (2015) color-changing beverage and a processing method thereof (publication No. CN104957702A), wherein the color-changing beverage comprises the following raw materials in parts by weight: 130-160 parts of anthocyanin vegetable juice, 5-8 parts of miracle fruit, 30-45 parts of lemon juice, 6-10 parts of pine pollen, 1-5 parts of agar and 12-17 parts of sugarcane juice. The preparation method of the color-changing beverage comprises the following steps: pretreating raw materials, stirring and pulping, spraying and granulating, drying, packaging and obtaining a finished product. The product of the invention has rich nutrition, can supplement various vitamins and amino acids necessary for human body, especially the existence of anthocyanin can delay senility and improve immunity, and is especially suitable for breakfast and afternoon tea to supplement energy for eating. The color-changing characteristic of the food makes the food interesting and romantic, meets the increasing material culture needs of people, and especially meets the aesthetic taste of young people. Although the inventions relate to the field of fruit and vegetable anthocyanin and color-changing food, the main realization mode is to realize the color change of the beverage by microcapsules or adsorption and elution modes. Different from the inventions, the color change related in the method is the color change generated by the anthocyanin diffusing between two materials printed by the double-nozzle 3D printing under different environmental pH conditions, belongs to the 4D printing category of the autonomous color change realized by the blueberry anthocyanin catalysis based on the 3D printing, and has different color change principles.
The invention discloses a color-changeable tea product (publication number: CN105053364A) which is prepared from the following components in parts by mass: 100 parts of tea making plants; 0.01 to 3.33 portions of natural pigment; 0.5 to 25.0 portions of edible alkaline additive; wherein the natural pigment is at least one of litmus and anthocyanin. When drinking, the color of the tea can be changed by dripping a certain amount of edible acidic liquid such as lemon juice or other edible alkaline substances into the tea. The prepared color-changeable tea product has good taste, rich color change and certain health-care function. Also discloses a preparation method of the tea product, which is simple and has low processing cost and can increase the additional value of tea-making plants. Different from the invention, the color change in the method is realized based on the 3D printing of the double-nozzle jelly.
Zhang 24924m et al (2018) disclose a method for 3D printing a two-color sandwich snack by using concentrated fruit pulp (publication number: CN108477540A), which is mainly used for 3D printing of gel food, relates to a food processing technology and belongs to the field of novel food processing. The method comprises the steps of respectively and fully mixing two raw materials, homogenizing, preserving heat, cooling and charging the raw materials, and then carrying out 3D printing by using a double-nozzle printer according to a pre-made double-color sandwich 3D printing model. According to the food printing machine, double-nozzle 3D printing is adopted, different models are designed, materials can be printed to have sandwich effects of different space shapes and different quantities, so that food has richer taste and visual effects, and diversified, personalized and automatic production of products is realized. Different from the 3D printing method of the double-color dessert, the method mainly relates to a method for realizing color-changing 4D printing by using a double-nozzle 3D printing method of the blueberry anthocyanin-rich jelly and the lemon thick paste jelly and catalyzing through anthocyanin.
Disclosure of Invention
The method is a 4D food printing method for realizing color change through anthocyanin catalysis on the basis of 3D food printing, and the food idea and variety of 3D printing can be enriched.
The technical scheme of the invention is as follows:
a method for realizing 4D printing of color jelly by utilizing spontaneous color change of blueberry anthocyanin specifically comprises the following steps:
(1) extracting blueberry anthocyanin in vacuum by ultrasonic wave cooperation:
a. selecting fresh and high-quality blueberry fresh fruits, weighing, and placing in a refrigerator at the temperature of 80 ℃ below zero for freezing and moderating;
b. preparing an anthocyanin extracting agent from hydrochloric acid and ethanol;
c. mixing the frozen fresh blueberry fruits with an anthocyanin extracting agent according to the weight ratio of 1: mixing at a mass ratio of 20;
d. placing the extracted mixed solution in a low-speed homogenizing machine for homogenizing for 25-35 s, transferring the homogenized mixed solution into a vacuum bottle, and pumping air in the bottle by using a vacuum pump to ensure that the air pressure in the bottle is maintained at 0.07-0.09 MPa for 10min so as to remove oxygen in the extracted solution;
e. placing a vacuum bottle connected with a vacuum pump in an ultrasonic bath at 50-53.5 ℃ and maintaining the air pressure at 0.07-0.09 MPa, and extracting for 25-30 min;
f. filtering the extracting solution, adjusting the pH value to 7.0-7.2, and freeze-drying to obtain anthocyanin powder;
(2) preparing a color carrier layer material:
g. mixing: adding the anthocyanin powder extracted from the blueberries in the step (1), potato starch, pectin, essence and purified water into a mixer and uniformly mixing;
h. homogenizing: feeding the mixed material obtained in the step g into a homogenizer, and homogenizing under 3.0-3.5 MPa for 10-15 min to ensure that the particle size of the homogenized material is less than 20 mu m;
i. and (3) gelation: preserving the heat of the material obtained in the step h at 53.5 ℃ for 15-20 min;
j. and (3) cooling: cooling the color layer carrying material obtained in the step i to normal temperature for later use;
(3) preparing a color control layer material:
k. mixing: mixing lemon concentrated juice and NaCO3Adding pectin and potato starch into a mixer and uniformly mixing;
l, homogenizing: d, feeding the material mixed in the step k into a homogenizer, and homogenizing under 3.0-3.5 MPa for 10-15 min to ensure that the particle size of the homogenized material is less than 20 mu m;
m, gelation: keeping the temperature of the material obtained in the step (l) at 53.5 ℃ for 15-20 min;
n, cooling: cooling the color control layer material obtained in the step m to normal temperature for later use;
(4) filling materials: filling the color carrying layer and the color control layer materials prepared in the steps (2) and (3) into two printing material cylinders respectively, and placing the printing material cylinders into a vacuum cavity with the vacuum degree of 0.07-0.09 MPa for degassing to remove air bubbles in the material cylinders;
(5) printing: the method comprises the steps of adopting a double-nozzle 3D printer, carrying out double-material 3D printing and laying according to a pre-established double-color 3D printing model, alternately laying multiple layers of color carrying layers with different anthocyanin concentrations and color control layer materials with different pH values through the double-nozzle layer by layer, and finally forming the 3D-shaped colored jelly.
In the step b, the matching ratio of the anthocyanin extracting agent is 0.01 percent of HCl and 70 percent of ethanol aqueous solution.
In the step e, the parameters of the ultrasonic generating device during ultrasonic bath are 20-25 kHz and 2W/g.
In the step f, the freeze drying conditions are as follows: and drying for 20-24 h at the cold trap temperature of-80 ℃ and the pressure of 220 Pa.
In the step g, the raw material formula comprises the following components in parts by weight: 1-2 parts of anthocyanin powder, 100-150 parts of potato starch, 10-20 parts of pectin, 0.1-0.2 part of essence and 100 parts of purified water;
in the step k, the raw material formula comprises the following components in parts by weight: lemon concentrated juice 100 parts, NaCO30-7 parts of pectin, 10-20 parts of potato starch and 75-125 parts of potato starch;
the starch formed after the potato starch is gelatinized has good gel property and high transparency; pectin provides elasticity and texture properties to the jelly; the lemon concentrated juice and the lemon essential oil can provide the flavor and the taste for the jelly; NaCO3The pH value of the jelly with the color control layer can be adjusted to control the color change. The essence is white lemon essential oil.
The color-carrying layer material has the viscosity of 1500-8000 Pa.s, the elastic modulus of 1800-3200 Pa, the viscous modulus of 300-500 Pa and the pH value of 5.1-5.2. The color at which the color support layer is formed is expressed in standard Lab as: l66.85 ± 2.44, a 67.44 ± 2.62, b-34.61 ± 3.65, magenta.
The material viscosity of the color control layer is 4300-10000 Pa.s, the elastic modulus is 2600-9200 Pa, the viscous modulus is 320-1000 Pa, and the pH value is 2.4-11.2. The final color change is adjusted by adjusting the pH value of the color control layer. The color of the jelly formed by the final color change is expressed according to the standard Lab value as follows: l59.44 ± 2.76, a 67.59 ± 8.81, b 36.66 ± 12.86, and red at pH 2.4; l50.43 ± 4.50, a 59.66 ± 12.43, b-38.70 ± 6.87, at pH 7, purple; l27.83 ± 4.19, a 17.60 ± 6.98, b-31.04 ± 12.26, pH 11.2, blue.
In the step (5), the printing speed is 20-25 mm/s, and the extrusion speed is 25-30 mm3S; when the bottom layer and the shell are printed, the printing speed is 50% of the normal speed; the relative positions of the head 2 and the head 1 were set to 62.5mm in X and-0.5 mm in Y. Double-nozzle 3D printer nozzleThe head diameter was 0.85 mm.
The invention has the beneficial effects that:
1. the method uses ultrasonic wave to cooperate with vacuum to extract the anthocyanin in the blueberry fruits, so that the anthocyanin extraction efficiency can be improved while the oxidation of the anthocyanin is reduced;
2. the anthocyanin extracted from the blueberry has good oxidation resistance and bright color;
3. the invention relates to a food 4D color-changing printing method which is realized on the basis of double-nozzle printing and laying;
4. different jelly materials laid by 3D can spontaneously migrate and stimulate each other to realize color change;
5. by using NaCO3Adjusting the pH value of the color control layer to finally realize color control;
6. multiple layers of different color-carrying layers and color-controlling layer materials are laid through the double nozzles to be alternated layer by layer, and finally, multicolor change is realized, so that the jelly can change multiple colors simultaneously.
7. The gelatinization temperature of the material is 50-53.5 ℃, and sufficient gelatinization of potato starch and less anthocyanin loss can be ensured at the temperature.
Detailed Description
The following is a further description of the invention with reference to specific examples.
Example 1: method for realizing color jelly 4D printing by blueberry anthocyanin spontaneously changing color (Dual-color)
Selecting fresh and high-quality blueberry fresh fruits, weighing, and placing in a refrigerator at the temperature of 80 ℃ below zero for freezing and moderating. 0.01% hydrochloric acid and 70% ethanol are prepared into aqueous solution as anthocyanin extracting agent. Mixing the frozen fresh blueberry fruits with an extracting agent according to the weight ratio of 1: mixing at a mass ratio of 20, homogenizing in a low-speed homogenizer for 25s, transferring to a vacuum bottle, and pumping air in the bottle by using a vacuum pump to maintain the air pressure in the bottle at 0.07MPa for 10min to remove oxygen in the extractive solution. Placing the vacuum bottle connected with vacuum pump in ultrasonic bath at 53.5 deg.C, 20kHz and 2W/g, maintaining air pressure at 0.07MPa, and extracting for 25 min. Filtering the extractive solution, adjusting pH to 7, and freeze drying at-80 deg.C under 220Pa for 20 hr.
Weighing 100 parts of potato starch, 1 part of the extracted blueberry anthocyanin powder, 20 parts of pectin, 100 parts of purified water and 0.1 part of white lemon essential oil, and adding into a mixer to mix uniformly; and (3) feeding the mixed material into a homogenizer, and homogenizing for 10min at 3.0-3.5 MPa to ensure that the particle size of the homogenized material is less than 20 mu m. And (3) preserving the temperature of the homogenized material at 53.5 ℃ for 15min, and cooling to room temperature to prepare the color layer carrying material. The color support layer formed had a pH of 5.1 and a light magenta color (L × 68.58, a × 69.30, b × 32.03).
Weighing 75 parts of potato starch, 20 parts of pectin and 100 parts of lemon concentrated juice, and adding into a mixer for uniformly mixing; feeding the mixed material into a homogenizer, homogenizing at 3.0MPa for 10min to make the particle diameter of the homogenized material less than 20 μm. And (3) preserving the temperature of the homogenized material at 53.5 ℃ for 15min, and cooling to room temperature to prepare a first color control layer material, wherein the pH value is 2.4. Adding 4 parts of NaCO on the basis of the first part of the color control layer material3To form a second color control layer material, wherein the pH is 7.
The three materials are respectively loaded into a printing material cylinder, and are placed into a vacuum cavity with the vacuum degree of 0.07MPa after being uniformly filled to degas and remove air bubbles in the material cylinder. A nozzle with a diameter of 0.85mm was selected for printing, the printing speed was set at 20mm/s, and the extrusion rate was set at 25mm3S; the relative position of the head 2 and the head 1 was set to 62.5mm and-0.5 mm. The printing speed is set to 50% of the normal printing speed when printing the product housing. The sprayer 1 prints color carrying layer materials, the sprayer 2 prints and alternately prints two color control layer materials, and a pre-designed multilayer 3D model is alternately printed, laid and molded according to color carrying layer-first color control layer (pH is 2.4) -color carrying layer-second color control layer (pH is 7) and the like. The printed jelly can realize two color changes of reddish (L ═ 61.39, a ═ 73.81, b ═ 45.76) and purplish (L ═ 53.61, a ═ 68.45, b ═ 33.85) at 2 min.
Example 2: method for realizing color jelly 4D printing by blueberry anthocyanin spontaneously changing color (three colors)
Selecting fresh and high-quality blueberry fresh fruits, weighing, and placing in a refrigerator at the temperature of 80 ℃ below zero for freezing and moderating. 0.01% hydrochloric acid and 70% ethanol are prepared into aqueous solution as anthocyanin extracting agent. Mixing the frozen fresh blueberry fruits with an extracting agent according to the weight ratio of 1: mixing at a mass ratio of 20, homogenizing in a low-speed homogenizer for 35s, transferring to a vacuum bottle, and pumping air in the bottle by using a vacuum pump to maintain the air pressure in the bottle at 0.09MPa for 10min to remove oxygen in the extractive solution. Placing the vacuum bottle connected with vacuum pump in ultrasonic bath at 52 deg.C and 20kHz and 2W/g, maintaining air pressure at 0.09MPa, and extracting for 30 min. Filtering the extractive solution, adjusting pH to 7.2, and freeze drying at-80 deg.C under 220Pa for 20 hr.
Weighing 150 parts of potato starch, 10 parts of pectin, 2 parts of the extracted blueberry anthocyanin powder, 100 parts of purified water and 0.2 part of white lemon essential oil, and adding into a mixer to mix uniformly; and (3) feeding the mixed material into a homogenizer, and homogenizing for 15min under 3.5MPa to ensure that the particle size of the homogenized material particles is less than 20 microns. And (3) preserving the temperature of the homogenized material at 53.5 ℃ for 20min, and cooling to room temperature to prepare the color layer carrying material. The color support layer had a pH of 5.2 and a magenta color (L65.12, a 65.59, b-37.19) upon formation.
Mixing 100 parts of potato starch, 10 parts of pectin and 4 parts of NaCO3Weighing 100 parts of lemon concentrated juice, and adding into a mixer for uniformly mixing; and (3) feeding the mixed material into a homogenizer, and homogenizing for 15min under 3.5MPa to ensure that the particle size of the homogenized material particles is less than 20 microns. Keeping the homogenized material at 53.5 deg.C for 20min, cooling to room temperature to obtain a first color control layer material with pH of 2.4; adding 4 parts of NaCO on the basis of the first part of the color control layer material3Preparing a second part of the color control layer material with the pH value of 7; adding 7 parts of NaCO on the basis of the first part of the color control layer material3And preparing a third color control layer material with the pH value of 11.2.
Respectively loading 4 materials into a printing material cylinder, uniformly filling, placing into a vacuum cavity with the vacuum degree of 0.09MPa, degassing, and removing bubbles in the material cylinder. A nozzle with a diameter of 0.85mm was selected for printing, the printing speed was set at 25mm/s, and the extrusion rate was set at 30mm3S; the method comprises the steps that a sprayer 1 prints color carrying layer materials, a sprayer 2 prints and alternately prints two color control layer materials, a multi-layer 3D model which is designed in advance is alternately printed and laid according to color carrying layers, a first color control layer (pH is 2.4), a color carrying layer, a second color control layer (pH is 7), a color carrying layer and a third color control layer (pH is 11.2) and the likeAnd (5) molding. The printed jelly can realize three color changes of red (L ═ 57.48, a ═ 61.36, b ═ 27.56), purple (L ═ 47.25, a ═ 50.87, b ═ 43.56), blue (L ═ 24.86, a ═ 12.67, b ═ 39.71) at 2 min.
Example 3: method for realizing color jelly 4D printing by blueberry anthocyanin spontaneously changing color (six colors)
Selecting fresh and high-quality blueberry fresh fruits, weighing, and placing in a refrigerator at the temperature of 80 ℃ below zero for freezing and moderating. 0.01% hydrochloric acid and 70% ethanol are prepared into aqueous solution as anthocyanin extracting agent. Mixing the frozen fresh blueberry fruits with an extracting agent according to the weight ratio of 1: mixing at a mass ratio of 20, homogenizing in a low-speed homogenizer for 25-35 s, transferring to a vacuum bottle, and pumping air in the bottle by using a vacuum pump to maintain the air pressure in the bottle at 0.08MPa for 10min to remove oxygen in the extracting solution. Placing the vacuum bottle connected with vacuum pump in ultrasonic bath at 50 deg.C, 20kHz and 2W/g, maintaining air pressure at 0.08MPa, and extracting for 25 min. Filtering the extractive solution, adjusting pH to 7, and freeze drying at-80 deg.C under 220Pa for 24 hr.
Weighing 125 parts of potato starch, 15 parts of pectin, 1 part of the extracted blueberry anthocyanin powder, 100 parts of purified water and 0.2 part of white lemon essential oil, and adding into a mixer to mix uniformly; and (3) feeding the mixed material into a homogenizer, and homogenizing for 15min under 3.5MPa to ensure that the particle size of the homogenized material particles is less than 20 microns. And (3) preserving the temperature of the homogenized material at 53.5 ℃ for 20min, and cooling to room temperature to prepare a first color-carrying layer material. The first color support layer formed at pH 5.1, light magenta (L × 68.58, a × 69.30, b × 32.03); adding 1 part of the above extracted blueberry anthocyanidin powder on the basis of the first color layer carrying material to prepare a second color layer carrying material, wherein the pH value is 5.2 when the layer is formed, and the color is mauve (L is 65.12, a is 65.59, and b is-37.19).
Weighing 125 parts of potato starch, 15 parts of pectin and 100 parts of lemon concentrated juice, and adding into a mixer for uniformly mixing; and (3) feeding the mixed material into a homogenizer, and homogenizing for 15min under 3.5MPa to ensure that the particle size of the homogenized material particles is less than 20 microns. Keeping the homogenized material at 53.5 deg.C for 20min, cooling to room temperature to obtain a first color control layer material with pH of 2.4; on the basis of the first color control layer material4 parts of NaCO are added3Preparing a second part of the color control layer material with the pH value of 7; adding 7 parts of NaCO on the basis of the first part of the color control layer material3And preparing a third color control layer material with the pH value of 11.2.
Respectively loading 5 materials into a printing material cylinder, uniformly filling, placing into a vacuum cavity with the vacuum degree of 0.08MPa, degassing and removing bubbles in the material cylinder. A nozzle with a diameter of 0.85mm was selected for printing, the printing speed was set at 20mm/s, and the extrusion rate was set at 30mm3S; the relative position of the head 2 and the head 1 was set to 62.5mm and-0.5 mm. The printing speed is set to 50% of the normal printing speed when printing the product housing. And (3) alternately printing different color carrying layers and color control layers on the pre-designed multilayer 3D model, and laying and molding. The printed jelly can realize six color changes of red (L ═ 61.39, a ═ 73.81, b ═ 45.76), purple (L ═ 53.61, a ═ 68.45, b ═ 33.85), blue (L ═ 30.79, a ═ 22.53, b ═ 22.369), red (L ═ 57.48, a ═ 61.36, b ═ 27.56), purple (L ═ 47.25, a ═ 50.87, b ═ 43.56), blue (L ═ 24.86, a ═ 12.67, b ═ 39.71) at 2 min.

Claims (5)

1. A method for realizing color jelly 4D printing by utilizing blueberry anthocyanin to change color spontaneously is characterized by comprising the following steps:
(1) extracting blueberry anthocyanin in vacuum by ultrasonic wave cooperation:
a. selecting fresh and high-quality blueberry fresh fruits, weighing, and placing in a refrigerator at the temperature of 80 ℃ below zero for freezing and moderating;
b. preparing an anthocyanin extracting agent from hydrochloric acid and ethanol;
c. mixing the frozen fresh blueberry fruits with an anthocyanin extracting agent according to the weight ratio of 1: mixing at a mass ratio of 20;
d. placing the extracted mixed solution in a low-speed homogenizing machine for homogenizing for 25-35 s, transferring the homogenized mixed solution into a vacuum bottle, and pumping air in the bottle by using a vacuum pump to ensure that the air pressure in the bottle is maintained at 0.07-0.09 MPa for 10min so as to remove oxygen in the extracted solution;
e. placing a vacuum bottle connected with a vacuum pump in an ultrasonic bath at 50-53.5 ℃ and maintaining the air pressure at 0.07-0.09 MPa, and extracting for 25-30 min;
f. filtering the extracting solution, adjusting the pH value to 7.0-7.2, and freeze-drying to obtain anthocyanin powder;
(2) preparing a color carrier layer material:
g. mixing: adding the anthocyanin powder extracted from the blueberries in the step (1), potato starch, pectin, essence and purified water into a mixer and uniformly mixing;
h. homogenizing: feeding the mixed material obtained in the step g into a homogenizer, and homogenizing under 3.0-3.5 MPa for 10-15 min to ensure that the particle size of the homogenized material is less than 20 mu m;
i. and (3) gelation: preserving the heat of the material obtained in the step h at 53.5 ℃ for 15-20 min;
j. and (3) cooling: cooling the color layer carrying material obtained in the step i to normal temperature for later use;
(3) preparing a color control layer material:
k. mixing: mixing lemon concentrated juice and Na2CO3Adding pectin and potato starch into a mixer and uniformly mixing;
l, homogenizing: d, feeding the material mixed in the step k into a homogenizer, and homogenizing under 3.0-3.5 MPa for 10-15 min to ensure that the particle size of the homogenized material is less than 20 mu m;
m, gelation: keeping the temperature of the material obtained in the step (l) at 53.5 ℃ for 15-20 min;
n, cooling: cooling the color control layer material obtained in the step m to normal temperature for later use;
(4) filling materials: filling the color carrying layer and the color control layer materials prepared in the steps (2) and (3) into two printing material cylinders respectively, and placing the printing material cylinders into a vacuum cavity with the vacuum degree of 0.07-0.09 MPa for degassing to remove air bubbles in the material cylinders;
(5) printing: adopting a double-nozzle 3D printer, carrying out double-material 3D printing and laying according to a pre-established double-color 3D printing model, and alternately laying a plurality of color carrying layers with different anthocyanin concentrations and color control layer materials with different pH values through the double-nozzle layer by layer to finally form the 3D-shaped colored jelly;
the material viscosity of the color-carrying layer is 1500-8000 Pa.s, the elastic modulus is 1800-3200 Pa, the viscosity modulus is 300-500 Pa, and the pH value is 5.1-5.2; carrierThe color at which the color layer is formed is expressed in standard Lab as:L*=66.85±2.44，a*=67.44±2.62，b-34.61 ± 3.65, magenta;
the material viscosity of the color control layer is 4300-10000 Pa.s, the elastic modulus is 2600-9200 Pa, the viscous modulus is 320-1000 Pa, and the pH value is 2.4-11.2; adjusting the pH value of the color control layer to adjust the change of the final color; the color of the jelly formed by the final color change is expressed according to the standard Lab value as follows:L*=59.44±2.76，a*=67.59±8.81，b=36.66 ± 12.86, red at pH = 2.4; L*=50.43±4.50，a*=59.66±12.43，b-38.70 ± 6.87, purple at pH = 7; L*=27.83±4.19，a*=17.60±6.98，b-31.04 ± 12.26, blue at pH = 11.2.
2. The method for realizing 4D color printing of the jelly by utilizing the spontaneous color change of the blueberry anthocyanin according to claim 1, wherein in the step b, the matching ratio of the anthocyanin extracting agent is 0.01% of HCl and 70% of ethanol in water; in the step e, the parameters of the ultrasonic generating device during ultrasonic bath are 20-25 kHz and 2W/g; in the step f, the freeze drying conditions are as follows: and drying for 20-24 h at the cold trap temperature of-80 ℃ and the pressure of 220 Pa.
3. The method for realizing 4D printing of the color jelly by utilizing spontaneous color change of the blueberry anthocyanin is characterized in that in the step g, the raw material formula comprises the following components in parts by weight: 1-2 parts of anthocyanin powder, 100-150 parts of potato starch, 10-20 parts of pectin, 0.1-0.2 part of essence and 100 parts of purified water; in the step k, the raw material formula comprises the following components in parts by weight: lemon concentrated juice 100 parts, Na2CO3 0-7 parts of pectin, 10-20 parts of potato starch and 75-125 parts of potato starch.
4. The method for realizing 4D printing of color jelly by utilizing spontaneous color change of blueberry anthocyanin according to claim 1 or 2, wherein in the step (5), the printing speed is 20-25 mm/s, and the extrusion speed is 25-30 mm3S; in printingWhen the bottom layer and the shell are used, the printing speed is 50% of the normal speed; the relative positions of the spray head 2 and the spray head 1 are set to be X =62.5 mm and Y = -0.5 mm; the diameter of the double-nozzle 3D printer nozzle is 0.85 mm.
5. The method for realizing 4D printing of color jelly by utilizing spontaneous color change of blueberry anthocyanin, as claimed in claim 3, wherein in the step (5), the printing speed is 20-25 mm/s, and the extrusion speed is 25-30 mm3S; when the bottom layer and the shell are printed, the printing speed is 50% of the normal speed; the relative positions of the spray head 2 and the spray head 1 are set to be X =62.5 mm and Y = -0.5 mm; the diameter of the double-nozzle 3D printer nozzle is 0.85 mm.
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