CN110618116B - Preparation method and application of intelligent indication label for visually detecting freshness of meat - Google Patents

Preparation method and application of intelligent indication label for visually detecting freshness of meat Download PDF

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CN110618116B
CN110618116B CN201910800122.1A CN201910800122A CN110618116B CN 110618116 B CN110618116 B CN 110618116B CN 201910800122 A CN201910800122 A CN 201910800122A CN 110618116 B CN110618116 B CN 110618116B
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freshness
meat
label
indicator
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CN110618116A (en
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邹小波
胡雪桃
石吉勇
李艳肖
李文亭
徐艺伟
李亚惠
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Jiangsu University
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    • G01N21/6428Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
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    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
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    • 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
    • G01N21/62Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/63Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
    • G01N21/64Fluorescence; Phosphorescence
    • G01N21/6428Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
    • G01N2021/6439Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes" with indicators, stains, dyes, tags, labels, marks

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Abstract

The invention relates to the field of food detection, in particular to a preparation method and application of an intelligent indicating label for meat freshness; the method comprises the following steps: firstly, preparing fluorescent carbon quantum dots, dissolving the fluorescent carbon quantum dots and bromothymol blue in ethanol, and adjusting the pH value to obtain a freshness indicator; then, mixing the chitosan solution, the polyvinyl alcohol solution and the freshness indicator, carrying out ultrasonic defoaming and drying to form an indicating film, and wrapping the indicating film by using a low-density polyethylene film to obtain an intelligent freshness indicating label; after the tags and the meat coexist, recording visible light color pictures of the tags on different storage days to form a visible light color colorimetric card, and recording fluorescence color pictures to form a fluorescence color colorimetric card; the color of the label changes after the meat to be detected and the label coexist, and the visual detection of the freshness of the meat is realized through the color comparison of the color comparison card; the label prepared by the invention is safe and environment-friendly, and the fluorescent nano material is combined with the traditional color indicator to enrich the color signal of the indicating label and make the determination result more accurate.

Description

Preparation method and application of intelligent indication label for visually detecting freshness of meat
Technical Field
The invention relates to the field of food detection, in particular to a preparation method and application of an intelligent indication label for meat freshness.
Background
With the improvement of the awareness of food safety, people pay more and more attention to the quality and safety of meat. Due to the incomplete cold chain system, meat is influenced by conditions such as external environment, microorganisms and the like in the processes of storage, transportation, processing and sale, and the meat contains rich nutrient components, so that the microorganisms in the meat are easy to grow and reproduce, the sensory quality and the physicochemical quality of the meat are changed under the enzymolysis effect of the meat and the decomposition effect of the microorganisms, and finally the freshness of the meat is reduced. If the rotten pork is not detected in time, the health of people is seriously damaged. Therefore, how to track and detect the freshness of meat is a very important and urgent task.
The freshness of the meat is evaluated mainly according to the sensory characteristics of the meat, the nature and the content of decomposition products, the amount of microorganisms and the like, and established detection methods comprise a sensory analysis method and a physicochemical analysis method. Although the sensory analysis method does not need instruments and equipment, the detection result completely depends on the subjective judgment and experience of an inspector, and the analysis result has subjectivity and sidedness. The physical and chemical analysis method mainly comprises the steps of measuring physical properties (pH value, viscosity, conductivity and the like) and chemical properties (ammonia gas, volatile basic nitrogen (TVB-N), microorganisms and the like) of meat, such as the content of the volatile basic nitrogen (TVB-N) detected by a Kjeldahl method, the quantity of spoilage microorganisms detected by a microbiological method and the like. Although the physicochemical analysis method can accurately determine the freshness of the meat, the method has the disadvantages of complicated operation process, long pretreatment time, sample damage and incapability of realizing rapid and nondestructive detection of the freshness of the meat.
The meat freshness indicating label utilizes acid-base indicator dyes (such as bromocresol blue, methyl red, bromocresol green and the like) to react with volatile components generated by meat to change the color of the indicating label, so that the freshness of meat products is detected. This freshness indicator label has the function that need not to destroy meat and its packing and can detect meat quality and freshness, and the consumer only needs to observe the fresh degree of meat in the indicator label colour just knows the packing. However, the existing freshness indicating label can only realize freshness detection according to visible light color change, but the detection label has low sensitivity and high detection limit. Therefore, it is necessary to prepare a visible light/fluorescence dual-signal indicator of freshness and an intelligent indicating label, so as to realize visible light/fluorescence visual detection of the freshness of meat.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention develops the intelligent indicating label for the freshness of the meat, and the intelligent indicating label can visually track and monitor the freshness change condition of the meat in the processes of transportation, storage, processing and sale in real time and can ensure the quality and safety of the meat when being eaten by consumers. The method comprises the steps of firstly preparing a visible light/fluorescent meat freshness indicator, then preparing a green and safe intelligent freshness indicating label, establishing visible light colors and fluorescent color colorimetric cards with different freshness degrees by using the prepared intelligent indicating label, and finally judging the freshness degree of the meat by comparing the colors of the intelligent indicating label and the colorimetric card in the actual meat. The invention can realize real-time, visual and rapid monitoring of freshness of meat in the processes of transportation, storage, processing and sale, and can overcome the defects of complex operation, long time consumption, sample damage and the like of the traditional detection method.
In order to achieve the above object, the present invention specifically comprises the following steps:
step 1, preparing a freshness indicator; firstly, adding sucrose into water to obtain a sucrose aqueous solution, then adding the sucrose aqueous solution into ethanol, carrying out heating reaction under a vacuum condition, and after the reaction, centrifuging, filtering, and carrying out vacuum freeze drying to obtain the fluorescent carbon quantum dots; then, dissolving bromothymol blue and fluorescent carbon quantum dots in ethanol to obtain a bromothymol blue-carbon quantum dot indicator, and adjusting the pH value to obtain the visible light/fluorescent meat freshness indicator;
step 2, preparing an intelligent freshness indication label; firstly, adding chitosan into an acetic acid aqueous solution to obtain a chitosan solution; then mixing the chitosan solution, the polyvinyl alcohol solution and the meat freshness indicator prepared in the step 1, uniformly stirring to obtain a mixed solution, adjusting the pH value of the mixed solution, and performing ultrasonic defoaming and drying to form a freshness indicating film; wrapping the obtained indicating film with a low-density polyethylene film to obtain an intelligent freshness indicating label;
preferably, the mass concentration of the sucrose aqueous solution in the step 1 is 20-40%; the volume ratio of the sucrose aqueous solution to the ethanol is 3: 5 to 15.
Preferably, the heating reaction in the step 1 is carried out at the temperature of 150-300 ℃ for 12-36 h.
Preferably, the fluorescence emission peak of the fluorescent carbon quantum dot in the step 1 is 450-480 nm, blue fluorescence is displayed, and the fluorescent carbon quantum dot has excellent fluorescence characteristics.
Preferably, in the bromothymol blue-carbon quantum dot indicator in the step 1, the dosage ratio of bromothymol blue to carbon quantum dots to ethanol is 0.1-1 mg: 1-2 mg: 10-20 mL.
Preferably, the pH value is adjusted to 6.0-7.6 by hydrochloric acid or sodium hydroxide in the step 1.
Preferably, the dosage ratio of the chitosan to the acetic acid aqueous solution in the step 2 is 1-2 g: 50-100 mL; the volume concentration of the acetic acid aqueous solution is 1-5% (v/v).
Preferably, the concentration of the polyvinyl alcohol solution in the step 2 is 10-50 mg/mL.
Preferably, in the step 2, the dosage ratio of the chitosan solution, the polyvinyl alcohol solution and the meat freshness indicator is 5-10 mL: 5-10 mL: 1-5 mL.
Preferably, the pH value of the mixed solution is adjusted to 6.0-7.6 by hydrochloric acid or sodium hydroxide in the step 2.
Preferably, the drying temperature in the step 2 is 40-60 ℃ and the time is 10-30 h.
The detection of the freshness of the meat slices to be prepared by the intelligent freshness indicating label comprises the following steps:
s1, manufacturing a meat freshness intelligent indication colorimetric card; sticking the prepared intelligent freshness indication label in a fresh meat packaging bag, and storing the prepared intelligent freshness indication label and fresh meat in the same space for m days, wherein m is a positive integer;
detecting volatile basic total nitrogen (TVB-N) stored for different time by a national standard method (Kjeldahl nitrogen determination method), judging the freshness of the meat, and when the TVB-N value is more than 15mg/100g, indicating that the meat is an stale product, and recording the storage days as N days, wherein N is a positive integer less than or equal to m; at the moment, the meat stored for 1-n-1 days is a fresh product, and the meat stored for n-m days is an unrifted product;
observing the visible light color change of the indicating label in the storage process, and regularly recording the visible light pictures of the freshness intelligent indicating label at different storage time; meanwhile, a handheld ultraviolet lamp is used for irradiating the intelligent freshness indicating label, fluorescent pictures of the intelligent indicating label changing along with preservation time are recorded, visible light color pictures are arranged from small to large according to preservation days and are sequentially recorded as V1, V2 … …, Vn … … and Vm, and a visible light color colorimetric card for intelligently indicating freshness is formed; arranging the fluorescent color pictures from small to large according to preservation days, and sequentially marking as F1, F2 … …, Fn … … and Fm to form a fluorescent color colorimetric card for intelligently indicating freshness;
s2, visually detecting the freshness of the meat;
sticking the intelligent freshness indicating label prepared in the step (2) in a packaging bag of a meat sample, and storing the meat sample in the same space for storage to obtain a visible light color picture and a fluorescent color picture of the intelligent freshness indicating label in the packaging bag; and comparing the observed visible light color picture and the observed fluorescence color picture with the visible light color colorimetric card and the fluorescence color colorimetric card obtained in the step S1 respectively, and realizing the visual detection of the freshness of the meat through color comparison.
Preferably, in step S1, V1 is an indicator tag visible light picture stored for 1 day, V2 is an indicator tag visible light picture stored for 2 days, … … and Vn are indicator tag visible light pictures stored for n days, and … … and Vm are indicator tag visible light pictures stored for m days; the visible light color colorimetric card consists of V1, V2 … …, Vn … … and Vm.
Preferably, in step S1, the F1 is an indicator label fluorescent picture stored for 1 day, the F2 is an indicator label fluorescent picture stored for 2 days, … …, Fn is an indicator label fluorescent picture stored for n days, … …, Fm is an indicator label fluoresceable picture stored for m days; the fluorescent color colorimetric card consists of F1, F2 … …, Fn … … and Fm.
Compared with the prior art, the invention has the beneficial effects that:
(1) the invention firstly prepares a visible light/fluorescence double-signal indicator (bromothymol blue-carbon quantum dot indicator), the indicator generates the change of visible light color and fluorescence color by reacting with volatile components generated by meat decay, and the monitoring of the freshness of meat products can be realized by utilizing the change of the visible light color and the fluorescence color; compared with a single visible light indicator, the indicator also has fluorescence indicating property, the fluorescence indicating signal changes sensitively, the freshness of the meat can be accurately detected, and the detection limit is low.
(2) The intelligent indicating label prepared by the invention is synthesized by polyvinyl alcohol and chitosan, and can be placed in a food package to realize the intelligent indicating label of meat freshness; compared with other intelligent indicating labels, the indicating label is non-toxic, low in cost, high in stability, good in film forming property, antibacterial property and biocompatibility, is an excellent degradable green material, and accords with the sustainable development trend in food processing.
(3) The method for visually detecting the freshness of the meat, which is established by the invention, can effectively judge fresh or stale meat according to the change of visible light color and fluorescent color of the indication label in the processes of transportation, storage, processing and sale of the meat, and can realize real-time and rapid monitoring of the meat; the fluorescent nano material is combined with the traditional color indicator, so that the color signals of the indicating label are richer, and the measuring result is more accurate; the freshness of the meat can be judged by naked eyes, an expensive detection instrument is not needed, the detection cost is low, and the operation is simple and convenient.
Drawings
Fig. 1 (a) is a uv-vis spectrum curve and a fluorescence spectrum curve of the carbon quantum dot and bromothymol blue-carbon quantum dot indicator in example 1; (b) the middle left picture is a visible light picture of the carbon quantum dots, and the right picture is a fluorescence picture of the carbon quantum dots; (c) the middle left picture is a visible light picture of the bromothymol blue-carbon quantum dot indicator, and the right picture is a fluorescence picture of the bromothymol blue-carbon quantum dot indicator;
in fig. 2, (a) is a visible light picture of the smart indicator prepared in example 1 under visible light, and (b) is a fluorescent picture of the smart indicator prepared in example 1 under ultraviolet light.
FIG. 3 is a visible light picture and a fluorescent picture of the freshness intelligent indicator label prepared in example 1 and after meat storage; (a) the visual light pictures of the intelligent freshness indication label for 1 day, 3 days, 5 days, 7 days, 10 days, 15 days and 20 days of pork storage are respectively displayed from left to right; the figure (b) is a fluorescent picture of the intelligent freshness indication label for 1, 3, 5, 7, 10, 15 and 20 days of pork storage from left to right.
Fig. 4 (a) is a visible light picture of the intelligent freshness indicator label in example 1 after coexistence of 3 types of pork to be detected; (b) the fluorescent pictures of the intelligent freshness indicating label in example 1 and 3 pork to be detected coexisted are shown.
Detailed Description
The invention is described in more detail below with reference to the figures and examples, but the scope of the invention is not limited thereto.
Example 1:
step 1, preparing a freshness indicator;
mixing 3mL of sucrose solution (with the concentration of 30% (m/v)) and 10mL of organic solvent ethanol, uniformly stirring, then pouring into a polytetrafluoroethylene reaction kettle, and placing in an oven for reaction at 180 ℃ for 24 hours; cooling to room temperature, filtering the reaction solution through 0.22 μm filter paper, centrifuging at 15000rpm for 20min, removing impurities, and freeze-drying in vacuum to obtain fluorescent carbon quantum dots; and finally, dissolving 0.5mg of bromothymol blue and 1mg of fluorescent carbon quantum dots in 15mL of ethanol solvent, adjusting the pH value to 6.0, and uniformly mixing and stirring to obtain the bromothymol blue-carbon quantum dot indicator.
As shown in figure 1, the fluorescent carbon quantum dot has a fluorescence emission peak of 450nm, shows blue fluorescence under ultraviolet light, and has excellent fluorescence characteristics; the maximum absorption peak of the bromothymol blue-carbon quantum dot indicator is 460nm, and the bromothymol blue-carbon quantum dot indicator is yellow under visible light; the maximum fluorescence emission peak is 450nm, the indicator shows weak blue fluorescence under ultraviolet light, the fluorescence emitted by the carbon quantum dots is absorbed by bromothymol blue to quench the fluorescence of the carbon quantum dots, and a fluorescence resonance energy transfer phenomenon occurs between the carbon quantum dots and the bromothymol blue; the ultraviolet absorption spectrum (maximum absorption peak at 460nm) of bromothymol blue almost overlaps with the fluorescence emission spectrum (maximum emission peak at 450nm) of the carbon quantum dot (as shown in figure 1 a), demonstrating that fluorescence resonance energy transfer can occur between the two.
Step 2, preparing an intelligent freshness indication label;
a chitosan solution was prepared by dissolving 1.5g of Chitosan (CS) in an aqueous acetic acid solution (1% (v/v)), and 1.5g of polyvinyl alcohol (PVA) was dissolved in distilled water and stirred in a water bath at 85 ℃ for 4h to prepare a 15mg/mL polyvinyl alcohol solution. When the PVA solution was cooled to room temperature, the chitosan solution, polyvinyl alcohol solution, and bromothymol blue-carbon quantum dot indicator solution were mixed at a ratio of 1: 1: mixing at 0.3 volume ratio, stirring, adjusting pH to 6.0, ultrasonically defoaming, pouring into a culture dish with diameter of 6cm, and drying in an oven at 50 deg.C for 20 hr to obtain a freshness indicating membrane. Tightly wrapping the obtained freshness indicating film with a low-density polyethylene film to obtain an intelligent indicating label;
as shown in fig. 2, (a) is a visible light picture of the smart indicator prepared in example 1 under visible light, and (b) is a fluorescent picture of the smart indicator prepared in example 1 under ultraviolet light; the obtained intelligent indicating label can change the pH value of the intelligent indicating label for gases such as TVB-N, carbon dioxide, hydrogen sulfide and the like generated in the meat spoilage process, so that the visible light color of bromothymol blue is changed, and the fluorescence intensity of the carbon quantum dots is changed, so that the intelligent indicating label can generate visible light and fluorescence double-signal response to the freshness of the meat.
Detecting the freshness of the pork;
s1, manufacturing a freshness intelligent indication colorimetric card;
packaging fresh pork, sticking an indication label in a meat packaging bag, placing the meat in a refrigerator at 4 ℃ for storage, measuring the TVB-N content of the pork on different days by using a Kjeldahl method, and finding that the TVB-N value of the pork in a storage period of 1-5 days is less than 15mg/100g, wherein the pork is fresh; when the storage period is more than or equal to 7 days, the TVB-N value is more than 15mg/100g, and the pork is not fresh.
Moreover, the change of the visible light color of the indicating label is observed every day, and a visible light color picture of the indicating label changing along with the preservation time is recorded by using the smart phone; irradiating the freshness indication label by using a handheld ultraviolet lamp, and recording a fluorescent picture of the indication label along with the change of preservation time by using a smart phone; when the storage days of the pork are respectively 1, 3, 5, 7, 10, 15 and 20 days, collecting and arranging visible light color pictures from small to large according to the storage days, sequentially recording the visible light color pictures as V1, V3, V5, V7, V10, V15 and V20, and arranging the visible light color pictures from small to large according to the storage days to form a freshness indication visible light color colorimetric card; arranging the fluorescent color pictures from small to large according to the preservation days, and sequentially marking the fluorescent color pictures as F1, F3, F5, F7, F10, F15 and F20 to form the fluorescent color colorimetric card for intelligently indicating freshness.
As shown in fig. 3, (a) is a visible light picture of the intelligent freshness indication label for 1, 3, 5, 7, 10, 15 and 20 days for the storage of pork meat from left to right, respectively; as can be seen from the attached drawing (a), the visible light color of the indicating label changes from yellow to blue along with the increase of the storage days, which shows that after the pork is gradually rotten, the volatile gas reacts with the bromothymol blue in the intelligent indicating label to change the bromothymol blue into blue. Under visible light, when the label shows yellow or light green, the pork is a fresh product, and the TVB-N value is less than 15mg/100 g; when the label shows dark green or blue, the TVB-N value is more than 15mg/100g, and the pork is not fresh.
The picture (b) is a fluorescent picture of the intelligent freshness indication label for 1, 3, 5, 7, 10, 15 and 20 days of pork storage from left to right; as can be seen from the graph (b), the fluorescence color of the indicator label gradually becomes stronger with the increase of the storage days, which shows that when the pork is gradually rotten, the fluorescence resonance energy transfer phenomenon of bromothymol blue and the carbon quantum dots is weakened, and the fluorescence of the carbon quantum dots is recovered; under an ultraviolet lamp, when the label shows black or bluish fluorescence, the TVB-N value is less than 15mg/100g, and the pork is an unrifted product; when the label shows blue or deep blue fluorescence, the TVB-N value is more than 15mg/100g, and the pork is not fresh product.
S2, visually detecting the freshness of the pork;
selecting 3 pork samples with different degrees of freshness, placing the prepared freshness indication label on the inner side of the package of the 3 pork samples with different degrees of freshness, clearly observing the change condition of the visible light color of the intelligent indication label along with the degree of freshness of the meat from the outside of the package, and obtaining visible light color pictures of the 3 pork samples, as shown in the graph (a) of fig. 4; comparing the obtained 3 pork sample visible light color pictures with the visible light color colorimetric card prepared in the step 3, finding that the 1 st meat and the pictures with the storage period of 1 day in the visible light color colorimetric card are similar in color, preliminarily judging that the storage period of the meat is 1 day, the TVB-N value is less than 15mg/100g, and the meat is a fresh product; the 2 nd meat is found to be similar to the color of the picture with the storage period of 5 days and 7 days in the visible light color comparison card, the storage period of the meat can be judged to be 5-7 days, the TVB-N value can be less than 15mg/100g and possibly more than 15mg/100g, and the freshness of the pork can not be accurately judged because the meat is between the critical points of freshness and freshness; the color of the graph is similar when the storage period in the 3 rd meat visible light picture visible light color colorimetric card is 15 days, the storage period of the meat can be judged to be 15 days, the TVB-N value is more than or equal to 15mg/100g, and the meat is an unrifted product;
the intelligent indicating label is irradiated by the handheld ultraviolet lamp, the change of the fluorescence color of the indicating label is observed, and a fluorescence color picture of 3 pork is obtained, as shown in the picture (b) of fig. 4, and is combined with the fluorescence picture for further detection. Comparing the fluorescent color picture with the fluorescent color colorimetric card, finding that the color of the 1 st meat fluorescent picture is similar to that of the picture with the storage period of 1 day in the fluorescent color colorimetric card, judging that the storage period of the meat is 1 day, the TVB-N value is less than 15mg/100g, and the meat is a fresh product; the 2 nd meat fluorescent picture is similar to the picture with the storage period of 7 days in the fluorescent color colorimetric card in color, the storage period of the meat can be judged to be 7 days, the TVB-N value is more than 15mg/100g, and the meat is an stale product; the 3 rd meat fluorescent picture is similar to the picture with the storage period of 15 days in the fluorescent color colorimetric card in color, the storage period of the meat can be judged to be 15 days, the TVB-N value is more than or equal to 15mg/100g, and the meat is an unrifted product;
therefore, the freshness of the pork can be quickly and accurately detected. The detection of the freshness of the meat can be realized by utilizing the visible light color picture, but the sensitivity is not high, the freshness of the meat at the critical point of freshness and freshness cannot be accurately judged, and the freshness of the meat at each stage can be accurately judged by utilizing the fluorescent color picture.
Description of the drawings: the above embodiments are only used to illustrate the present invention and do not limit the technical solutions described in the present invention; thus, although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted; all such modifications and variations that do not depart from the spirit and scope of the invention are intended to be included within the scope of the appended claims.

Claims (10)

1. A preparation method of an intelligent indication label for visually detecting freshness of meat is characterized by comprising the following steps:
step 1, preparing a freshness indicator; firstly, adding sucrose into water to obtain a sucrose aqueous solution, then adding the sucrose aqueous solution into ethanol, carrying out heating reaction under a vacuum condition, and after the reaction, centrifuging, filtering, and carrying out vacuum freeze drying to obtain the fluorescent carbon quantum dots; then, dissolving bromothymol blue and fluorescent carbon quantum dots in ethanol to obtain a bromothymol blue-carbon quantum dot indicator, and adjusting the pH value to 6.0-7.6 to obtain a visible light/fluorescent meat freshness indicator; the indicator not only shows a visible light/fluorescence double signal, but also can generate a fluorescence resonance energy transfer quenching phenomenon, wherein the carbon quantum dots are fluorescence donors, and bromothymol blue is a fluorescence acceptor;
the optimal emission wavelength of the fluorescent carbon quantum dots is 450-480 nm, blue fluorescence is displayed, and the fluorescent carbon quantum dots have a fluorescent characteristic; the maximum absorption peak of the bromothymol blue-carbon quantum dot indicator is 460nm, and the bromothymol blue-carbon quantum dot indicator is yellow under visible light; the maximum fluorescence emission peak is 450nm, and the indicator shows blue fluorescence under ultraviolet light;
step 2, preparing an intelligent freshness indication label; firstly, adding chitosan into an acetic acid aqueous solution to obtain a chitosan solution; then mixing the chitosan solution, the polyvinyl alcohol solution and the meat freshness indicator prepared in the step 1, uniformly stirring to obtain a mixed solution, adjusting the pH value of the mixed solution to 6.0-7.6, and performing ultrasonic defoaming and drying to form a freshness indicating film; wrapping the obtained indicating film with a low-density polyethylene film to obtain an intelligent freshness indicating label; as the freshness of the meat decreases, the freshness indicating label has a visible/fluorescent color change.
2. The preparation method of the intelligent indicator label for visually detecting the freshness of the meat according to claim 1, wherein the mass concentration of the sucrose aqueous solution in the step 1 is 20-40%; the volume ratio of the sucrose aqueous solution to the ethanol is 3: 5-15; the heating reaction temperature is 150-300 ℃, and the time is 12-36 h.
3. The preparation method of the intelligent indicator label for visually detecting meat freshness according to claim 1, wherein in the step 1, the dosage ratio of bromothymol blue to carbon quantum dots to ethanol in the bromothymol blue-carbon quantum dot indicator is 0.1-1 mg: 1-2 mg: 10-20 mL.
4. The method for preparing the intelligent indicator label for visually detecting the freshness of the meat according to claim 1, wherein the pH value is adjusted to 6.0-7.6 by hydrochloric acid or sodium hydroxide in step 1.
5. The preparation method of the intelligent indicator label for visually detecting the freshness of the meat according to claim 1, wherein the dosage ratio of the chitosan to the acetic acid aqueous solution in the step 2 is 1-2 g: 50-100 mL; the volume concentration of the acetic acid aqueous solution is 1-5%; the concentration of the polyvinyl alcohol solution is 10-50 mg/mL.
6. The preparation method of the intelligent indicator label for visually detecting the freshness of the meat according to claim 1, wherein the dosage ratio of the chitosan solution, the polyvinyl alcohol solution and the meat freshness indicator in the step 2 is 5-10 mL: 5-10 mL: 1-5 mL.
7. The preparation method of the intelligent indicator label for visually detecting the freshness of the meat according to claim 1, wherein the pH value of the mixed solution in the step 2 is adjusted to 6.0-7.6 by hydrochloric acid or sodium hydroxide; the drying temperature is 40-60 ℃, and the time is 10-30 h.
8. The method for detecting the freshness of the meat by using the intelligent freshness indicating label prepared by the method according to any one of claims 1 to 7, which is characterized by comprising the following steps:
(1) sticking the freshness intelligent indication label in a fresh meat packaging bag, and storing the freshness intelligent indication label and fresh meat in the same space for m days, wherein m is a positive integer;
detecting the TVB-N values of the meat stored for different time by a Kjeldahl method to be used as a basis for judging the freshness of the meat; when the TVB-N value is more than 15mg/100g, the meat is not fresh, the storage days at the moment are recorded as N days, wherein N is a positive integer less than or equal to m; namely, the meat with the storage period of 1-n-1 days is a fresh product, and the meat with the storage period of n-m days is an unrifted product;
observing the visible light color change of the indicating label in the storage process, regularly recording visible light pictures of the freshness intelligent indicating label in different storage time, simultaneously irradiating the freshness intelligent indicating label by using a handheld ultraviolet lamp, and recording a fluorescent picture of the intelligent indicating label changing along with the storage time; arranging the visible light color pictures from small to large according to preservation days, and sequentially marking as V1, V2 … …, Vn … … and Vm to form a visible light color colorimetric card for intelligently indicating freshness; arranging the fluorescent color pictures from small to large according to preservation days, and sequentially marking as F1, F2 … …, Fn … … and Fm to form a fluorescent color colorimetric card for intelligently indicating freshness;
(2) sticking the prepared intelligent freshness indicating label in a packaging bag of a meat sample to be detected, storing the meat sample to be detected in the same space, and obtaining a visible light color picture and a fluorescent color picture of the intelligent freshness indicating label in the packaging bag; and (3) comparing the observed visible light color picture and the observed fluorescence color picture with the visible light color colorimetric card and the fluorescence color colorimetric card obtained in the step (1) respectively, and realizing the visual detection of the freshness of the meat through color comparison.
9. The use according to claim 8, wherein in step (1) the V1 is an indicator tag visible light picture stored for 1 day, V2 is an indicator tag visible light picture stored for 2 days, … …, Vn are indicator tag visible light pictures stored for n days, … …, Vm are indicator tag visible light pictures stored for m days; the visible light color colorimetric card consists of V1, V2 … …, Vn … … and Vm.
10. Use according to claim 8, wherein in step (1) the F1 is an indicator label fluorescence picture for 1 day of storage, F2 is an indicator label fluorescence picture for 2 days of storage, … …, Fn is an indicator label fluorescence picture for n days of storage, … …, Fm is an indicator label fluoresceable picture for m days of storage; the fluorescent color colorimetric card consists of F1, F2 … …, Fn … … and Fm.
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