CN115171515A - Label reflecting food freshness and method for detecting food freshness - Google Patents

Label reflecting food freshness and method for detecting food freshness Download PDF

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CN115171515A
CN115171515A CN202210797399.5A CN202210797399A CN115171515A CN 115171515 A CN115171515 A CN 115171515A CN 202210797399 A CN202210797399 A CN 202210797399A CN 115171515 A CN115171515 A CN 115171515A
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label
food
copper
freshness
solution
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孙大文
张文洋
马骥
成军虎
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South China University of Technology SCUT
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    • GPHYSICS
    • G09EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
    • G09FDISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
    • G09F3/00Labels, tag tickets, or similar identification or indication means; Seals; Postage or like stamps
    • G09F3/02Forms or constructions
    • GPHYSICS
    • G09EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
    • G09FDISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
    • G09F3/00Labels, tag tickets, or similar identification or indication means; Seals; Postage or like stamps
    • G09F3/02Forms or constructions
    • G09F3/0291Labels or tickets undergoing a change under particular conditions, e.g. heat, radiation, passage of time
    • GPHYSICS
    • G09EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
    • G09FDISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
    • G09F3/00Labels, tag tickets, or similar identification or indication means; Seals; Postage or like stamps
    • G09F3/02Forms or constructions
    • G09F2003/0283Forms or constructions food-compatible or edible

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Abstract

The invention discloses a label reflecting food freshness and a method for detecting food freshness, wherein the label is obtained by soaking a paper substrate material into a copper nanocluster solution, taking out and drying the paper substrate material; area S (cm) of the label 2 )=35X 1 ‑10X 2 ‑20X 3 2 +5X 4 + e; wherein X 1 Is food mass (kg), X 2 Is the volume (L) and X of the packaging box 3 Concentration of copper nanocluster solution (mM), X 4 Is the pH of the copper nanocluster solution and e is a constant factor for a particular food product. The freshness label can optimize products according to different types and different qualities of the products, and more importantly, the freshness label can react with volatile amine substances generated by food decay to generate observable signals, so that the accurate monitoring of the food quality is realized.

Description

Label reflecting food freshness and method for detecting food freshness
Technical Field
The invention relates to the technical field of food detection, in particular to a label reflecting food freshness and a method for detecting food freshness.
Background
The freshness of food is an important factor that determines the price of the product, affects the consumer's willingness to purchase, and the consumer's health. However, the freshness of packaged food can be affected by the packaging, shipping and storage conditions of the food.
At present, the judgment of food freshness by consumers is mostly based on the production date and the quality guarantee period on food packages. However, the actual shelf life of food is influenced by storage and transportation environmental conditions, and the shelf life on the label is often different from the actual shelf life. The intelligent label which can be chemically reacted with food odor components to directly indicate the change of food quality in real time can provide scientific basis for the real quality of food in shelf life.
During the storage of the food, the protein is affected by microorganisms, enzymes, chemical actions and the like, and is hydrolyzed to generate volatile amine substances. The detection mechanism of the food intelligent label is that the food intelligent label and volatile amine substances such as ammonia, dimethylamine, biogenic amine and the like generated by the decomposition of protein under the external action are subjected to chemical reaction, so that an observable signal is generated.
Most of the current common food freshness indicator labels are pH type food freshness indicator labels, which indirectly judge the freshness of food through the action of volatile acidic and alkaline substances generated by food spoilage and pH sensitive materials. The labels usually adopt artificial synthetic dyes and natural pigments as pH value indicating materials, and the main problems in development and application are as follows: (1) The synthetic pigment has safety risk and is not recommended to be directly acted on food packaging; (2) Natural pigments are highly susceptible to oxidation and often exhibit a delay in indication due to insufficient sensitivity in application.
Disclosure of Invention
The invention aims to provide a label reflecting food freshness and a method for detecting food freshness, which can judge whether food is putrefactive or not by detecting whether fluorescence emission exists on the label.
The purpose of the invention is realized by the following technical scheme:
a label reflecting food freshness is prepared by soaking paper substrate material in copper nanocluster (GSH-CuNCs) solution, taking out, and drying to obtain label;
the area of the label (namely the area of the paper base material) is in a certain numerical relationship with the quality of the specific food, the volume of the packaging box, the concentration of the copper nanocluster (GSH-CuNCs) solution and the pH value, so that the freshness of the specific food can be objectively and accurately reflected;
area S (cm) of the label 2 )=35X 1 -10X 2 -20X 3 2 +5X 4 +e;
Wherein X 1 Is food mass (kg), X 2 Is the volume (L) of the packing box, X 3 Concentration of copper nanocluster solution (mM), X 4 Is the pH of the copper nanocluster solution, e is a constant factor for a particular food;
the e-values for several common food products are:
beef: 0.82; pork: 1.22; mutton: 1.51; shrimp: 3.47; shellfish: 2.42; fresh water fish: 2.88; sea fish: 3.58.
the copper nanoclusters (GSH-CuNCs), which are related in the prior art, such as CN 104458050A and CN 111570820B;
preferably, the copper nanocluster solution is prepared by the following steps:
adding 10-25 parts of glutathione into ultrapure water, adding 5 parts of copper source, stirring uniformly, and adjusting the pH value to 4-7; centrifuging after ultrasonic treatment, and redissolving the obtained precipitate in ethanol solution to obtain a copper nanocluster solution; the parts are parts by weight;
the glutathione is preferably reduced glutathione;
the copper source is more than one of copper nitrate, copper sulfate or copper chloride;
the centrifugal speed is preferably 6000rpm;
the centrifugation is preferably carried out for 10 minutes;
the concentration of the ethanol solution is 70-95% (vol%).
The paper substrate material is prepared from more than one of plant fiber, natural sponge, low-density polyether, reed fiber, polyvinyl alcohol or polyester.
The drying is preferably carried out at 40 ℃.
A method for detecting freshness of food comprises placing the above label together with food, detecting whether the label of food has fluorescence emission, and if no fluorescence emission exists, indicating that the food is putrefactive.
In the food label, the copper nanoclusters (GSH-CuNCs) can specifically react with volatile amine substances in food, and the fluorescence signal intensity of the GSH-CuNCs is in inverse proportion to the content of the volatile amine substances in a food spoilage system. The main action mechanism is as follows:
1. the GSH-CuNCs related in the invention contain a functional group capable of specifically reacting with volatile amine substances, and the functional group is a carboxylic acid group.
2. The GSH-CuNCs related in the invention can generate ligand exchange effect with volatile amine substances, so that part of glutathione as a ligand is dropped from the surface of the GSH-CuNCs, and the newly formed copper nanocluster taking the amine substances as the ligand has no fluorescence emission capability, so that a charge transfer mechanism in the system is changed, and the fluorescence signal of the GSH-CuNCs is promoted to be reduced until the fluorescence signal is completely quenched.
Compared with the prior art, the invention has the following advantages and effects:
1. the freshness food label provided by the invention is made of green and safe raw materials, so that the risk caused by using toxic reagents in the synthesis process is avoided. In addition, the preparation method and the process of the label are simple, and the defects of complicated steps, complex structure and the like of some methods are overcome.
2. The freshness label can optimize products according to different types and different qualities of the products, and more importantly, the freshness label can react with volatile amine substances generated by food decay to generate observable signals, so that the accurate monitoring of the food quality is realized.
Drawings
FIG. 1 is a least squares regression plot established in example 3.
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but the embodiments of the present invention are not limited thereto.
Example 1
Taking the content of volatile basic nitrogen (TVB-N) in the food as the quality index of whether the food is putrefactive or not to obtain various types of foodSpoilage Point (T) of food f )
The experiment was carried out at ambient temperature (25. + -. 5 ℃ C.). The spoilage point was determined according to the index threshold specified by the relevant standard, and is shown in table 1 for various foods:
TABLE 1 spoilage Point of various foods
Figure BDA0003736235130000041
Example 2
A label reflecting freshness of food is prepared by the following steps:
1) 10-25 parts (parts by weight; the same as below) reduced glutathione is added into ultrapure water;
2) Adding 5 parts of copper nitrate into the solution obtained in the step 1;
3) The mixed solution obtained in the step 2 is stirred for 20 minutes at room temperature, and then the pH value is adjusted to 4-7;
4) Carrying out ultrasonic treatment on the solution obtained in the step 3 for 20 minutes;
5) Centrifuging the solution obtained in the step 4 for 10 minutes;
6) Re-dissolving the precipitate obtained in the step 5 in ethanol with the volume fraction of 90% to obtain GSH-CuNCs aggregates;
7) And (3) soaking a paper base material (Youyijia cosmetic cotton, type 1/2 water-saving) in the solution obtained in the step (6) for 1 minute, taking out, and drying at 40 ℃ to obtain the label reflecting the freshness of the food.
Example 3
To test the accuracy of the prepared labels, the food labels obtained in example 2 were cut into different sizes, salmon were selected as experimental samples (six groups of 20 parallel samples each), and the specific experimental parameters are shown in table 2.
TABLE 2 Salmon freshness monitoring
Figure BDA0003736235130000051
Establishing a numerical relationship between the area of the label and the food quality, the volume of the packaging box, the concentration of the copper nanocluster (GSH-CuNCs) solution and the pH value by means of partial least squares regression analysis (figure 1) according to the data obtained from the table;
area S (cm) of the label 2 )=35.2X 1 –10.4X 2 –19.6X 3 2 +4.9X 4 +3.58,(R 2 =95.3);
Wherein, X 1 Is food mass (kg), X 2 Is the volume (L) and X of the packaging box 3 Concentration of copper nanocluster solution (mM), X 4 Is the pH of the copper nanocluster solution;
according to the obtained area formula, X is selected 1 :0.1,X 2 :1,X 3 :0.75,X 4 :6, as an experimental group, the area of the food label in cut-out example 2 was 12cm 2 . The control group had an area of 10cm 2 The label of (1). Actually measuring the complete quenching time of the fluorescence emission of the labels of the experimental group and the control group, wherein the complete quenching time is 22.5h and 20h respectively; the complete quenching time of the fluorescence emission of the experimental group tag, which can reflect food freshness, is very close to the spoilage point of salmon compared to the control group. The fluorescence emission complete quenching time of the control group label is greatly different from the decay point of salmon, and the freshness of food cannot be objectively reflected.
Example 4
To test the accuracy of the prepared labels, the food labels obtained in example 2 were cut into different sizes, beef was selected as the experimental sample (six groups of 20 parallel samples each), and the specific experimental parameters are shown in table 3.
TABLE 3 beef freshness monitoring
Figure BDA0003736235130000061
According to the data obtained by the table, a numerical relation between the area of the label and the food quality, the volume of the packaging box, the concentration of a copper nanocluster (GSH-CuNCs) solution and the pH value is established by means of partial least squares regression analysis;
area S (cm) of the label 2 )=35.8X 1 –10.1X 2 –20.2X 3 2 +4.6X 4 +0.82,(R 2 =91.8);
Wherein, X 1 Is food mass (kg), X 2 Is the volume (L) and X of the packaging box 3 Concentration of copper nanocluster solution (mM), X 4 Is the pH of the copper nanocluster solution;
selecting X according to the obtained area formula 1 :0.15,X 2 :1,X 3 :0.8,X 4 :5, as an experimental group, the area of the food label in cut-out example 2 was 5.05cm 2 . The control group had an area of 6cm 2 The label of (1). Actually measuring the complete quenching time of the fluorescence emission of the labels of the experimental group and the control group, wherein the complete quenching time is 15h and 17h respectively; the complete quenching time of the fluorescence emission of the experimental group tag is very close to the spoilage point of beef, which can reflect food freshness, compared to the control group. The difference between the complete quenching time of fluorescence emission of the control group label and the spoilage point of beef is large, and the freshness of food cannot be objectively reflected.
Example 5
To test the accuracy of the labels prepared, the food labels from example 2 were cut into different sizes, and shrimp were selected as experimental samples (six groups of 20 parallel samples) with specific experimental parameters as shown in table 4.
TABLE 4 freshness monitoring of metapenaeus ensis
Figure BDA0003736235130000071
According to the data obtained by the table, a numerical relation between the area of the label and the food quality, the volume of the packaging box, the concentration of a copper nanocluster (GSH-CuNCs) solution and the pH value is established by means of partial least squares regression analysis;
area S (cm) of the label 2 )=35.1X 1 –9.6X 2 –20.3X 3 2 +5.3X 4 +3.47,(R 2 =93.7);
Wherein, the first and the second end of the pipe are connected with each other,X 1 is food mass (kg), X 2 Is the volume (L) and X of the packaging box 3 Concentration of copper nanocluster solution (mM), X 4 Is the pH of the copper nanocluster solution;
selecting X according to the obtained area formula 1 :0.07,X 2 :1,X 3 :0.8,X 4 :5, as an experimental group, the area of the food label in cut-out example 2 was 5cm 2 . The control group had an area of 8cm 2 The label of (1). Actually measuring the complete quenching time of the fluorescence emission of the labels of the experimental group and the control group, wherein the complete quenching time is 11h and 16h respectively; the complete quenching time of the fluorescence emission of the experimental group tag compared to the control group was very close to the spoilage point of metapenaeus ensis, which can reflect food freshness. The time for complete quenching of fluorescence emission of the control group tag is greatly different from the decay point of metapenaeus ensis, and the freshness of food cannot be objectively reflected.
Example 6
The food labels obtained in example 2 were cut to have areas of 20, 16, 12, 9, 6 and 4cm, respectively 2 The food mass is 0.05-0.15kg, the volume of the food packaging box is 0.5-1L, and the pH value of the GSH-CuNCs in the example 2 is controlled to be 2-6. The concentration of the GSH-CuCNs is adjusted according to the size of the experimental intelligent label and the pH of the GSH-CuNCs, and the concentration range is 0.01-0.75 mM.
Three area equations were obtained in examples 3-5, respectively: s (cm) 2 )=35.2X 1 –10.4X 2 –19.6X 3 2 +4.9X 4 +3.58,S(cm 2 )=35.8X 1 –10.1X 2 –20.2X 3 2 +4.6X 4 +0.82, and S (cm) 2 )=35.1X 1 –9.6X 2 –20.3X 3 2 +5.3X 4 +3.47. The coefficient values of the variables in the three groups of formulas are relatively close, and the coefficients are unified to obtain S =35X 1 -10X 2 -20X 3 2 +5X 4 + e; the result of the formula after the system is unified has acceptable effect although the monitoring capability of the formula still has acceptable effect;
wherein S is the area (cm) 2 ),X 1 Is food mass (kg), X 2 Is the volume (L) and X of the packaging box 3 Concentration of GSH-CuNCs aggregates (mM), X 4 The pH value of the GSH-CuNCs aggregate is shown, and the e value is a constant value;
e is at 35X 1 -10X 2 -20X 3 2 +5X 4 On the premise of fixation, three groups of X are set 1 、X 2 、X 3 、X 4 After the value of (A), three groups of intelligent tags with the same area (S) are prepared, the intelligent tags are monitored for 23 hours at 25 ℃, the difference value between the measured TVB-N value and the critical value of the TVB-N in the national standard is obtained, and the correction constant e for different foods is obtained by combining the actual change condition of the color of the tags on the basis of the difference value.
The e-values for several foods were:
beef: 0.82 (R) 2 = 91.8); pork: 1.22 (R) 2 = 94.1); mutton: 1.51 (R) 2 = 92.4); shrimp: 3.47 (R) 2 = 93.7); shellfish: 2.42 (R) 2 = 92.6); fresh water fish: 2.88 (R) 2 = 91.4); sea fish: 3.58 (R) 2 =95.3)。
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.

Claims (10)

1. A label reflecting freshness of a food, comprising: soaking the paper substrate material into the copper nanocluster solution, taking out and drying to obtain a label;
area S (cm) of the label 2 )=35X 1 -10X 2 -20X 3 2 +5X 4 +e;
Wherein, X 1 Is food mass (kg), X 2 Is the volume (L) and X of the packaging box 3 Concentration of copper nanocluster solution (mM), X 4 Is the pH of the copper nanocluster solution and e is a constant factor for a particular food product.
2. The label of claim 1, wherein: the e-values for several common food products are:
beef: 0.82; pork: 1.22; mutton: 1.51; shrimp: 3.47; shellfish: 2.42; fresh water fish: 2.88; sea fish: 3.58.
3. the label of claim 1, wherein: the copper nanocluster solution is prepared by the following steps:
adding 10-25 parts of glutathione into ultrapure water, adding 5 parts of copper source, uniformly stirring, and adjusting the pH value to 4-7; centrifuging after ultrasonic treatment, and redissolving the obtained precipitate in an ethanol solution to obtain a copper nanocluster solution; the parts are parts by weight.
4. The label of claim 3, wherein: the glutathione is reduced glutathione.
5. The label of claim 3, wherein: the copper source is more than one of copper nitrate, copper sulfate or copper chloride.
6. The tag of claim 3, wherein: the centrifugation is carried out at the rotating speed of 6000rpm for 10 minutes.
7. The label of claim 3, wherein: the concentration of the ethanol solution is 70-95% (vol%).
8. The label of claim 1, wherein: the paper substrate material is prepared from more than one of plant fiber, natural sponge, low-density polyether, reed fiber, polyvinyl alcohol or polyester.
9. The label of claim 1, wherein: the drying is carried out at 40 ℃.
10. A method for detecting freshness of a food product, comprising the steps of: placing the label of any of claims 1-9 with a food product, and detecting the presence or absence of fluorescent emission from the food product label, wherein the absence of fluorescent emission indicates that the food product is spoiled.
CN202210797399.5A 2022-07-08 2022-07-08 Label reflecting food freshness and method for detecting food freshness Pending CN115171515A (en)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109115758A (en) * 2018-08-22 2019-01-01 广西大学 A kind of preparation method and applications of freshness indicator type intelligent label
CN109975283A (en) * 2019-04-10 2019-07-05 内蒙古农业大学 Visual indicating label of a kind of identification Meat and preparation method thereof and application
CN110057805A (en) * 2019-06-24 2019-07-26 烟台大学 A kind of method of atriphos fluorescence detection aquatic products freshness
CN112649426A (en) * 2020-11-30 2021-04-13 华南理工大学 Preparation method and application of 3D printing freshness monitoring and freshness keeping integrated label
CN113293216A (en) * 2021-02-07 2021-08-24 中国检验检疫科学研究院 Identification method for animal-derived components in salmonidae products based on high-throughput sequencing

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109115758A (en) * 2018-08-22 2019-01-01 广西大学 A kind of preparation method and applications of freshness indicator type intelligent label
CN109975283A (en) * 2019-04-10 2019-07-05 内蒙古农业大学 Visual indicating label of a kind of identification Meat and preparation method thereof and application
CN110057805A (en) * 2019-06-24 2019-07-26 烟台大学 A kind of method of atriphos fluorescence detection aquatic products freshness
CN112649426A (en) * 2020-11-30 2021-04-13 华南理工大学 Preparation method and application of 3D printing freshness monitoring and freshness keeping integrated label
CN113293216A (en) * 2021-02-07 2021-08-24 中国检验检疫科学研究院 Identification method for animal-derived components in salmonidae products based on high-throughput sequencing

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