CN116376119B - Milk product freshness intelligent label with high sensitivity and low swelling property as well as preparation method and application thereof - Google Patents

Milk product freshness intelligent label with high sensitivity and low swelling property as well as preparation method and application thereof Download PDF

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CN116376119B
CN116376119B CN202310436915.6A CN202310436915A CN116376119B CN 116376119 B CN116376119 B CN 116376119B CN 202310436915 A CN202310436915 A CN 202310436915A CN 116376119 B CN116376119 B CN 116376119B
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starch
anthocyanin
freshness
high sensitivity
dairy
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CN116376119A (en
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陈龙
王允
缪铭
田耀旗
赵建伟
徐振林
孟嫚
邱超
龙杰
金征宇
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Jiangnan University
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L3/00Compositions of starch, amylose or amylopectin or of their derivatives or degradation products
    • C08L3/02Starch; Degradation products thereof, e.g. dextrin
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/75Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
    • G01N21/77Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator
    • G01N21/78Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator producing a change of colour
    • G01N21/80Indicating pH value
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02WCLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W90/00Enabling technologies or technologies with a potential or indirect contribution to greenhouse gas [GHG] emissions mitigation
    • Y02W90/10Bio-packaging, e.g. packing containers made from renewable resources or bio-plastics

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  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
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Abstract

The invention discloses a dairy product freshness intelligent label with high sensitivity and low swelling property, and a preparation method and application thereof, and belongs to the technical field of food packaging. Based on the color development characteristic of anthocyanin along with pH change and the combination characteristic of phytic acid, starch and protein, the invention adopts starch, glycerol, anthocyanin, isolated soy protein and phytic acid as raw materials, firstly, the starch and the glycerol are mixed and heated for plasticizing and pasting and are mixed with the anthocyanin, and secondly, the phytic acid is used for crosslinking the starch and the isolated soy protein to form stable label forming liquid, and finally, the intelligent label with high color development sensitivity and strong stability of dairy products in an emulsion state is prepared. The preparation method is simple, green, pollution-free and low in energy consumption, the prepared freshness intelligent label senses the freshness change of the dairy product obviously, has strong stability in emulsion, good swelling property and solubility, and has wide application prospect in the field of food packaging.

Description

Milk product freshness intelligent label with high sensitivity and low swelling property as well as preparation method and application thereof
Technical Field
The invention relates to a dairy product freshness intelligent label with high sensitivity and low swelling property, and a preparation method and application thereof, and belongs to the technical field of food packaging.
Background
Food spoilage due to microbial contamination is a serious problem with current food safety. The intelligent label is a novel packaging material, has a sensing function, can identify pH change caused by a spoilage marker generated when food in the package is spoiled, displays color change, further displays the freshness of the food, predicts the quality change and displays the shelf life of the food.
In order to prepare such a smart label, a dye having a sensing function is often simply mixed with a conventional packaging material. The existing labels are mostly used for detecting vegetables and meat products with lower water content, and for foods (such as dairy products) with higher water content, the problems of label base material dissolution, label structure damage, dye leakage, stability reduction, label fading and the like often occur, so that the application of the intelligent labels in foods with high water content is limited; in the prior art, the hydrophobicity of the label material is enhanced to enable the label to have certain resistance to moisture, but the water vapor transmittance of the label can be reduced, the swelling property of the label material is not improved, and the stability in high-moisture foods cannot be improved.
Therefore, development of a dairy product freshness intelligent label with high sensitivity and low swelling property is needed, which has important economic value and social significance for detecting the freshness of the dairy product and solving the problem of food safety and quality.
Disclosure of Invention
The invention aims to solve the technical problems that the existing dairy product intelligent label is poor in stability and cannot have high sensitivity and low swelling characteristics.
Therefore, the invention provides a dairy product freshness intelligent label with high sensitivity and low swelling property, and a preparation method and application thereof; the intelligent label with the dairy product freshness and high sensitivity and low swelling property is prepared by adopting a method of crosslinking and curtain coating drying of soy protein isolate and phytic acid, and the method is simple, green, pollution-free and low in energy consumption; compared with the original starch-based label, the intelligent label prepared by the invention can be combined with milk protein to form a hydrophobin layer when contacting with milk, the swelling and dissolving characteristics are further improved, the stability of the label is improved, and the intelligent label has good sensing performance.
The first object of the invention is to provide a method for preparing a dairy freshness intelligent label with high sensitivity and low swelling, which comprises the following steps:
(1) Mixing starch, glycerol, soy protein isolate with phytic acid solution and dispersing in water for gelatinization;
(2) Cooling the starch mixed solution obtained after gelatinization in the step (1), then adding anthocyanin, uniformly stirring, regulating the pH value of the mixed solution to be neutral, and removing bubbles to obtain a mixture;
(3) Pouring the mixture obtained in the step (2) into a polytetrafluoroethylene flat plate by adopting a tape casting method, and drying and balancing the humidity to obtain the product.
In one embodiment, the starch of step (1) is one or more of high amylose starch, waxy corn starch, or common corn starch.
In one embodiment, the anthocyanin in step (2) is one or more of blueberry anthocyanin, roselle anthocyanin, grape anthocyanin, mulberry anthocyanin, black bean anthocyanin and purple potato anthocyanin.
In one embodiment, the mass ratio of the glycerol to the starch in the step (1) is 1-2:3-5, and the mass ratio of the phytic acid solution to the starch is 1-40:100; the mass ratio of the isolated soy protein to the starch is 0.5-2:3.
In one embodiment, the mass ratio of anthocyanin to starch in step (2) is 0.25-12:100.
In one embodiment, the bubble removal in the step (2) is performed by using ultrasound, the ultrasound power is 120-300W, and the ultrasound time is 1-10 min.
In one embodiment, the gelatinization in step (1) is carried out at a temperature of 80 to 90℃for a period of 30 to 50 minutes.
In one embodiment, the pH value adjustment range of step (2) is from 6.5 to 7.5.
In one embodiment, the temperature of the drying in step (3) is 30-60 ℃ and the time is 4-48 hours.
In one embodiment, the equilibrium temperature in step (3) is 20-35 ℃, the equilibrium relative humidity is 50-55%, and the equilibrium time is 24-48 hours.
The second object of the invention is to provide a dairy product freshness intelligent label with high sensitivity and low swelling property, which is prepared by the method.
A third object of the present invention is to provide a packaging material, a wearable material and a degradable material comprising the above-mentioned dairy freshness smart label with both high sensitivity and low swelling.
A fourth object of the present invention is to provide a use of the above-mentioned smart label for freshness of dairy products with high sensitivity and low swelling property in the field of food, pharmaceutical or agricultural products.
In one embodiment, the food product comprises any one of a dairy product, a meat product, an aquatic product.
A fifth object of the present invention is to provide a method for detecting freshness of dairy products, which comprises using the smart label for freshness of dairy products with high sensitivity and low swelling property as a detection matrix, and determining freshness of dairy products according to color change of the label.
The beneficial effects of the invention are that
(1) The invention prepares the dairy product freshness intelligent label with high sensitivity and low swelling property based on the color development characteristic of anthocyanin along with pH change and the combination characteristic of phytic acid, starch and protein, wherein the phytic acid can crosslink starch and soybean protein, improve the continuity and uniformity of starch, capture starch hydroxyl, reduce the swelling capacity of starch, combine with protein in dairy product, precipitate and separate out, and form protein hydrophobic layer on the surface of the label, thereby protecting the intelligent label and improving the stability thereof;
(2) The intelligent label prepared by the method is complete and continuous, has reduced swelling performance and good sensing performance, can effectively display the freshness of the dairy product and the shelf life of the dairy product, and can be used in the field of food packaging.
Drawings
FIG. 1 is a diagram of a process for preparing a smart label for freshness of dairy products with both high sensitivity and low swelling characteristics according to example 1 of the present invention;
FIG. 2 is a schematic view showing the solubility of anthocyanin-free labels prepared in example 1 and comparative examples 1 to 5 according to the present invention after immersion in water;
FIG. 3 is a schematic view showing the solubility of the dairy freshness intelligent labels with both high sensitivity and low swelling characteristics prepared in example 1 and comparative examples 1 to 5 according to the present invention after being soaked in water;
fig. 4 is a graph of response color chart of the smart label with high sensitivity and low characteristic for freshness of dairy products prepared in example 1 of the present invention under different pH conditions.
Detailed Description
The present invention is further described below with reference to examples, which are not intended to limit the invention in any way. Unless specifically stated otherwise, the reagents, methods and apparatus employed in the present invention are those conventional in the art.
The starch and the citric acid related by the invention are purchased from chemical reagent limited company of national medicine group; blueberry anthocyanin (5% -25%), 50% phytic acid solution are purchased from Shanghai Michelin Biochemical technology Co., ltd; glycerol (99.5%), carboxymethyl starch, carboxymethyl cellulose, sodium trimetaphosphate were purchased from beijing enokic technologies limited; isolated soy proteins were purchased from source foliar organisms.
The invention relates to a measuring method:
1. label chromogenic capability assay
Solutions of ph=2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12 were prepared, respectively, the test sample specification was 10mm×10mm, the samples were immersed in solutions of different pH for 30min, the color change of the samples was recorded using a camera, and the photo data was converted into CIE L using ImageJ software * a * b * Color value, L * Representing brightness, from 0 (black) to 100 (white); a, a * Representing green (-a) * ) To red (+a) * );b * Representing blue (-b) *) To yellow (+b) * ). Calculate the Total Color Difference (TCD) using the equation:
wherein the initial color parameter is expressed asAnd->
2. Determination of moisture transmittance of tag
Cutting the label subjected to humidity balancing into a round shape with the radius of 13-15 mm, tightly sealing the mouth of a 50mL centrifuge tube, and pre-loading 3g of anhydrous CaCl in the tube 2 After sealing, the tube was weighed and placed in an environment of 100% humidity, and the mass change was recorded every 24 hours. After sealing, the treatment group containing milk is covered by 1mL of fresh milk dropwise on the label so as to simulate the scene in the dairy product. The label moisture transmittance (WVP) was calculated using the equation:
wherein: Δm (g) is the weight gain of the centrifuge tube; h (m) is the thickness of the thin label; s (m) 2 ) Is the corresponding area of the inner diameter of the centrifuge tube; ΔP (2339 Pa,20 ℃) is the moisture vapor pressure; t(s) is time.
3. Label thickness measurement
The thickness (μm) of the five spots on the label was randomly extracted and measured with an electronic digital display micrometer.
4. Determination of tag moisture content, swelling ratio, solubility:
the tag was placed in an oven at 105℃and weighed to m 1 Then dried for 24 hours and then weighed to m 2 . The dry labels were then immersed in 20mL deionized water for 24 hours, then removed, and the surface wiped off to swell to give mass m 3 . Finally, the expanded sample is put into a baking oven at 105 ℃ to be dried for 24 hours 4 . The tag moisture content MC, swelling ratio SI and solubility WS were calculated according to the following formulas:
example 1
A method for preparing a dairy freshness intelligent label with high sensitivity and low swelling property, comprising the following steps:
(1) 3g of starch, 2g of glycerol, 1g of soy protein isolate and 0.1g of 50% phytic acid solution are mixed and dispersed in 100mL of deionized water and continuously stirred; stirring for 1h at 90 ℃ in a water bath kettle to carry out gelatinization;
(2) Placing the gelatinized starch mixed solution in the step (1) at room temperature (25 ℃) for stirring and cooling, then adding 0.1g of blueberry anthocyanin, mixing and stirring for 5min until the mixture is uniformly stirred, adjusting the pH value of the mixed solution to 7.0, and then placing the mixed solution under 100W ultrasonic power for ultrasonic treatment for 5min to remove bubbles, thus obtaining a mixture;
(3) Pouring 30g of the mixture obtained in the step (2) into a polytetrafluoroethylene flat plate by adopting a tape casting method, and placing the flat plate in a 50 ℃ oven for 8 hours for drying; and (5) removing and performing humidity balance for 24 hours under 50% of humidity to obtain the dairy product freshness intelligent label with high sensitivity and low swelling property.
Comparative example 1
A method for preparing a dairy freshness intelligent label with high sensitivity and low swelling property, comprising the following steps:
(1) 3g of starch, 1g of glycerol, 0.5g of citric acid and 0.1g of 50% phytic acid solution are mixed and dispersed in 100mL of deionized water and continuously stirred; stirring for 1h at 90 ℃ in a water bath kettle to carry out gelatinization;
(2) Placing the gelatinized starch mixed solution in the step (2) at room temperature (25 ℃) for stirring and cooling, then adding 0.1g of blueberry anthocyanin, mixing and stirring for 5min until the mixture is uniformly stirred, adjusting the pH value of the mixed solution to 7.0, and then placing the mixed solution under 100W ultrasonic power for ultrasonic treatment for 5min to remove bubbles, thus obtaining a mixture;
(3) Pouring 30g of the mixture obtained in the step (2) into a polytetrafluoroethylene flat plate by adopting a tape casting method, and placing the flat plate in a 50 ℃ oven for 8 hours for drying; and (5) removing and performing humidity balance for 24 hours under 50% of humidity to obtain the dairy product freshness intelligent label with high sensitivity and low swelling property.
Comparative example 2
(1) 3g of starch, 1g of glycerol and 0.1g of 50% phytic acid solution are mixed and dispersed in 100mL of deionized water and continuously stirred; stirring for 1h at 90 ℃ in a water bath kettle to carry out gelatinization;
(2) Placing the gelatinized starch mixed solution in the step (2) at room temperature (25 ℃) for stirring and cooling, then adding 0.1g of blueberry anthocyanin, mixing and stirring for 5min until the mixture is uniformly stirred, adjusting the pH value of the mixed solution to 7.0, and then placing the mixed solution under 100W ultrasonic power for ultrasonic treatment for 5min to remove bubbles, thus obtaining a mixture;
(3) Pouring 30g of the mixture obtained in the step (2) into a polytetrafluoroethylene flat plate by adopting a tape casting method, and placing the flat plate in a 50 ℃ oven for 8 hours for drying; and (5) removing and performing humidity balance for 24 hours under 50% of humidity to obtain the dairy product freshness intelligent label with high sensitivity and low swelling property.
Comparative example 3
(1) 1.5g of starch, 1.5g of carboxymethyl starch, 1g of glycerol and 0.1g of 50% phytic acid solution are mixed and dispersed in 100mL of deionized water and continuously stirred; stirring for 1h at 90 ℃ in a water bath kettle to carry out gelatinization;
(2) Placing the gelatinized starch mixed solution in the step (2) at room temperature (25 ℃) for stirring and cooling, then adding 0.1g of blueberry anthocyanin, mixing and stirring for 5min until the mixture is uniformly stirred, adjusting the pH value of the mixed solution to 7.0, and then placing the mixed solution under 100W ultrasonic power for ultrasonic treatment for 5min to remove bubbles, thus obtaining a mixture;
(3) Pouring 30g of the mixture obtained in the step (2) into a polytetrafluoroethylene flat plate by adopting a tape casting method, and placing the flat plate in a 50 ℃ oven for 8 hours for drying; and (5) removing and performing humidity balance for 24 hours under 50% of humidity to obtain the dairy product freshness intelligent label with high sensitivity and low swelling property.
Comparative example 4
(1) 1.5g of starch, 1.5g of carboxymethyl cellulose, 1g of glycerol and 0.1g of 50% phytic acid solution are mixed and dispersed in 100mL of deionized water and continuously stirred; stirring for 1h at 90 ℃ in a water bath kettle to carry out gelatinization;
(2) Placing the gelatinized starch mixed solution in the step (2) at room temperature (25 ℃) for stirring and cooling, then adding 0.1g of blueberry anthocyanin, mixing and stirring for 5min until the mixture is uniformly stirred, adjusting the pH value of the mixed solution to 7.0, and then placing the mixed solution under 100W ultrasonic power for ultrasonic treatment for 5min to remove bubbles, thus obtaining a mixture;
(3) Pouring 30g of the mixture obtained in the step (2) into a polytetrafluoroethylene flat plate by adopting a tape casting method, and placing the flat plate in a 50 ℃ oven for 8 hours for drying; and (5) removing and performing humidity balance for 24 hours under 50% of humidity to obtain the dairy product freshness intelligent label with high sensitivity and low swelling property.
Comparative example 5
(1) 3g of starch, 1g of sodium trimetaphosphate, 1g of glycerol and 0.1g of 50% phytic acid solution are mixed and dispersed in 100mL of deionized water and continuously stirred; stirring for 1h at 90 ℃ in a water bath kettle to carry out gelatinization;
(2) Placing the gelatinized starch mixed solution in the step (2) at room temperature (25 ℃) for stirring and cooling, then adding 0.1g of blueberry anthocyanin, mixing and stirring for 5min until the mixture is uniformly stirred, adjusting the pH value of the mixed solution to 7.0, and then placing the mixed solution under 100W ultrasonic power for ultrasonic treatment for 5min to remove bubbles, thus obtaining a mixture;
(3) Pouring 30g of the mixture obtained in the step (2) into a polytetrafluoroethylene flat plate by adopting a tape casting method, and placing the flat plate in a 50 ℃ oven for 8 hours for drying; and (5) removing and performing humidity balance for 24 hours under 50% of humidity to obtain the dairy product freshness intelligent label with high sensitivity and low swelling property.
Results Performance test
1. The freshness intelligent labels prepared in example 1 and comparative examples 1 to 5 were put into water to perform swelling property measurement, and the results are shown in fig. 2 and 3;
FIG. 2 is a schematic illustration of a dairy product smart label prepared by directly casting a gelatinized starch solution mixture without adding blueberry anthocyanin in example 1 and comparative examples 1-5; FIG. 3 is a dairy product smart label prepared in example 1 and comparative examples 1-5; as can be seen from fig. 2 and 3, the embodiment 1 still maintains the complete structure and less pigment leakage within 1h after soaking in water; the comparative examples 1 and 2 show cracks and breaks under soaking, and the pigment leakage is obvious although the whole structure is still relatively intact, and the pigment is almost colorless after soaking for 1 h; comparative examples 3 to 5 show remarkable phenomena of water swelling, structural disintegration and dissolution, indicating that it cannot be applied to the detection of freshness of dairy products.
2. The smart labels prepared in example 1 and comparative examples 1 and 2 were subjected to performance measurement, and the results are shown in table 1;
TABLE 1 Label thickness, moisture content, swelling Rate, solubility, moisture Transmission Rate for different treatment groups
From the data in table 1, the addition of milk results in a significant increase in the moisture content of the tag, which indicates that the moisture content of the fresh milk partially penetrates the tag matrix, indicating that the tag still has the ability to contact and detect the quality of the dairy component; after milk is added, the swelling rate of the labels prepared in the example 1 and the comparative example 1 is obviously reduced, which shows that phytic acid is combined with milk protein and forms a protein hydrophobic layer, so that a large amount of water infiltration during soaking is prevented; however, pure starch is difficult to maintain the structure under the condition of water soaking, and the water vapor transmittance can not be measured stably; the addition of soy protein isolate in example 1 reduced the solubility of the tag during soaking, better maintained the tag morphology, and exhibited lower water vapor transmission rates. The addition of citric acid in comparative example 1, while also reducing the water vapor transmission rate, did not have a remarkable effect on the swelling and dissolution properties of the soy protein isolate.
3. The smart labels prepared in example 1 were subjected to sensing property measurement, and the results are shown in table 2;
as can be seen from Table 2, the labels produced color response ΔE > 5 at pH change, indicating that the labels prepared in example 1 only had good response to pH.
Table 2 sensing performance response data for smart tags

Claims (9)

1. A method for preparing a dairy product freshness intelligent label with high sensitivity and low swelling property, which is characterized by comprising the following steps:
(1) Mixing starch, glycerol, soy protein isolate with phytic acid solution and dispersing in water for gelatinization; the mass ratio of the glycerol to the starch is 1-2:3-5, and the mass ratio of the phytic acid solution to the starch is 1-40:100; the mass ratio of the isolated soy protein to the starch is 0.5-2:3; (2) Cooling the starch mixed solution obtained after gelatinization in the step (1), then adding anthocyanin, uniformly stirring, adjusting the pH value range of the mixed solution to be 6.5-7.5, and removing bubbles to obtain a mixture;
(3) Pouring the mixture obtained in the step (2) into a polytetrafluoroethylene flat plate by adopting a tape casting method, and drying and balancing the humidity to obtain the product.
2. The method according to claim 1, wherein the anthocyanin in step (2) is one or more of blueberry anthocyanin, roselle anthocyanin, grape anthocyanin, mulberry anthocyanin, black bean anthocyanin and purple potato anthocyanin.
3. The method of claim 1, wherein the starch in step (1) is one or more of high amylose starch, waxy corn starch, or common corn starch.
4. The method according to claim 1, wherein the temperature of the drying in the step (3) is 30-60 ℃ for 4-48 hours.
5. The method according to claim 1, wherein the equilibrium temperature in step (3) is 20 to 35 ℃, the equilibrium relative humidity is 50 to 55%, and the equilibrium time is 24 to 48 hours.
6. A dairy freshness smart label with both high sensitivity and low swelling properties prepared by the method of any one of claims 1 to 5.
7. Packaging material, wearable material and degradable material comprising the dairy freshness smart label of claim 6 having both high sensitivity and low swelling properties.
8. The use of a dairy freshness intelligent label having both high sensitivity and low swelling properties as claimed in claim 6 in the field of food, pharmaceutical or agricultural products.
9. A method for detecting freshness of dairy products, comprising using the smart dairy product freshness detection tag having both high sensitivity and low swelling property as a detection matrix according to claim 6, and determining freshness of dairy products according to color change of the tag.
CN202310436915.6A 2023-04-21 2023-04-21 Milk product freshness intelligent label with high sensitivity and low swelling property as well as preparation method and application thereof Active CN116376119B (en)

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