CN114113063A - Preparation method and application of fish freshness indication colorimetric array - Google Patents
Preparation method and application of fish freshness indication colorimetric array Download PDFInfo
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- VFLDPWHFBUODDF-FCXRPNKRSA-N curcumin Chemical compound C1=C(O)C(OC)=CC(\C=C\C(=O)CC(=O)\C=C\C=2C=C(OC)C(O)=CC=2)=C1 VFLDPWHFBUODDF-FCXRPNKRSA-N 0.000 claims abstract description 28
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- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/75—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
- G01N21/77—Systems 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
- G01N21/78—Systems 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
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- C—CHEMISTRY; METALLURGY
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2489/00—Characterised by the use of proteins; Derivatives thereof
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- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/75—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
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Abstract
The invention discloses a preparation method and application of a fish freshness indication colorimetric array, wherein carboxymethyl cellulose (1.0g/100ml-2.0/100ml based on deionized water) powder is dissolved in deionized water at 85-95 ℃, the mixture is fully stirred for 50-60min, and glycerin is added to obtain a carboxymethyl cellulose solution for later use; dissolving natural pigment to obtain an indicating dye; when the carboxymethyl cellulose solution is cooled to 35-45 ℃, adding an indicating dye into the carboxymethyl cellulose solution to obtain a film-forming solution, degassing, and pouring the film-forming solution into a polystyrene culture dish to obtain a completely gelled indicator film; the invention has the beneficial effects that: firstly, the colorimetric array contains troponin to improve the capacity of the indicating layer to adsorb gas; the colorimetric array can be used for realizing real-time, nondestructive and convenient detection on the freshness of meat; and thirdly, the used pigments are anthocyanin, curcumin and beet red which are all natural plant extracts, and the polymers for preparing the colorimetric array are all food-grade and are safe and edible.
Description
Technical Field
The invention relates to the technical field of food detection, in particular to a preparation method and application of a fish freshness indication colorimetric array based on natural pigments.
Background
The traditional method for detecting the freshness and quality of the aquatic products mainly comprises sensory detection, physicochemical analysis, microbial detection and the like, has higher accuracy, but also has the defects of damage, long time consumption, complex procedure and the like. It is a great need to develop a convenient, fast and low cost method to assess freshness. A food freshness indicator is a packaging system (or portion of a package) that can constantly monitor the freshness status of food based on metabolites associated with food spoilage. The fish meat condition is monitored in real time and informed to a consumer, and particularly, the information data of the freshness of the fish meat can be directly observed by naked eyes, which is a problem to be solved in the fish meat storage process.
Currently, aquatic products have used chemical indicators to monitor their freshness. Wherein colorimetric indicators such as pH sensitive dyes provide visual information to the consumer of the packaged food product. However, such indicators present potential safety hazards and are not ideal materials for packaging in food. In addition, most of the existing presentation forms of the freshness indication cards exist in a single form, and are also deficient in terms of accuracy. Therefore, a nondestructive, easy-to-operate, low-cost, safe and accurate colorimetric array is developed to be used as an online monitoring index of fish freshness.
Disclosure of Invention
In order to solve the technical problems, the invention aims to provide a method for preparing a colorimetric array for monitoring freshness change in refrigerated fish transportation.
In order to achieve the purpose, the invention provides the following technical scheme: comprises the following steps of (a) carrying out,
dissolving carboxymethyl cellulose (1.0g/100ml-2.0/100ml based on deionized water) powder in deionized water at 85-95 deg.C, stirring for 50-60min, and adding glycerol to obtain carboxymethyl cellulose solution; dissolving natural pigment to obtain an indicating dye; when the carboxymethyl cellulose solution is cooled to 35-45 ℃, adding an indicating dye into the carboxymethyl cellulose solution to obtain a film-forming solution, degassing, and pouring the film-forming solution into a polystyrene culture dish to obtain a completely gelled indicator film;
dissolving starch in 90-100 deg.C deionized water, stirring for 25-35min, and adding glycerol; adding myogenin into starch solution, and performing ultrasonic treatment by an ultrasonic processor to obtain a film forming solution;
and degassing the film forming solution, pouring the film forming solution onto a completely gelled indicator film, and drying to obtain the natural pigment-based freshness indication colorimetric array.
Preferably, the natural pigment is anthocyanin, curcumin and beet red mixture or anthocyanin or curcumin or beet red, and the concentration of the indicator solution of the indicator dye is 40-60 mg/ml.
Preferably, when the natural pigment is a mixture of anthocyanin, curcumin and beet red, the mass ratio of anthocyanin, curcumin and beet red is 1:1: 1.
preferably, the drying conditions are 24 hours at 45 ℃.
Preferably, the specific weight proportion relationship of each raw material in the colorimetric array is as follows: carboxymethyl cellulose, natural pigment, starch, myogenin ═ 6:0.16:2:1, wherein the concentration of the myogenic protein is 2% -6%.
Preferably, the carboxymethyl cellulose powder is dissolved in deionized water at 85-95 ℃ and fully stirred for 50-60min, and the cooling temperature of the carboxymethyl cellulose solution is 35-45 ℃.
Preferably, the starch is dissolved in deionized water at 90-100 ℃ and stirred for 25-35 min.
The invention also comprises an application of the fish freshness indication colorimetric array, which comprises the fish freshness indication colorimetric array prepared by the preparation method of the fish freshness indication colorimetric array based on the natural pigment, and the application of the fish freshness indication colorimetric array is used for indicating the fish freshness.
The invention has the beneficial effects that: firstly, the colorimetric array contains troponin to improve the capacity of the indicating layer to adsorb gas; the colorimetric array can be used for realizing real-time, nondestructive and convenient detection on the freshness of meat; and thirdly, the used pigments are anthocyanin, curcumin and beet red which are all natural plant extracts, and the polymers for preparing the colorimetric array are all food-grade and are safe and edible.
Drawings
FIG. 1 is an exploded view of the structure of a fish freshness indication colorimetric array according to the present invention;
FIG. 2 is a graph of the sensitivity response of a fish freshness indication colorimetric array of the present invention to ammonia gas;
FIG. 3 is an application example of a fish freshness indication colorimetric array in accordance with the present invention to cod.
Detailed Description
The following detailed description of the present invention is provided in conjunction with the accompanying drawings, but it should be understood that the scope of the present invention is not limited to the specific embodiments. It should be noted that the experimental methods used in the following examples are all conventional methods unless otherwise specified; materials, reagents and the like used in the following examples are commercially available unless otherwise specified.
The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially. In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below.
Example 1
In recent years, aquatic foods have a great role as a nutrient source for maintaining human health, and the demand is increasing year by year. Generally, the freshness of fish meat refers to whether or not a physical or chemical change has occurred in fresh fish and the degree of change. The fresh fish and aquatic products are extremely easy to rot in the storage and transportation process, certain economic loss is caused, the requirement on the freshness of the fresh fish and aquatic products is higher and higher along with the improvement of the living standard of people, and the research on strengthening the comprehensive evaluation system of the freshness of the fish and aquatic products has important social and economic benefits.
The embodiment provides a preparation method of a fish freshness indication colorimetric array based on natural pigments, which comprises the following specific actual preparation processes:
selecting raw materials: anthocyanins (ATH), Curcumin (CUR), beet red (BET), carboxymethylcellulose (CMC), starch (S), Myogenin (MP), glycerol.
The preparation method of the colorimetric array comprises the following steps:
(1) CMC-ATH-CUR indicates the preparation of membranes.
6g of carboxymethyl cellulose (CMC) powder was dissolved in 500mL of deionized water at 90 ℃ and stirred well for 60 min. Glycerol (30% of the dry matter (carboxymethylcellulose powder)) was added as a plasticizer to obtain a carboxymethylcellulose solution. 0.16g of anthocyanin-curcumin (ATH-CUR, 1: 1) was dissolved in 47.5% ethanol to obtain an indicator solution. When the carboxymethyl cellulose solution was cooled to 40 ℃, the indicator solution was added thereto to obtain a deposition solution containing 40mg/mL of a natural pigment. After degassing, 40mL of the film-forming solution was poured into a polystyrene petri dish with a diameter of 10cm, resulting in a fully gelled indicator film, designated CMC-ATH-CUR.
(2) CMC-ATH-BET indicates the preparation of the membrane.
6g of carboxymethyl cellulose (CMC) powder was dissolved in 500mL of deionized water at 90 ℃ and stirred well for 60 min. Glycerol (30% of the dry matter (carboxymethylcellulose powder)) was added as a plasticizer to obtain a carboxymethylcellulose solution. 0.16g of anthocyanin-beet red (ATH-BET, 1: 1) was dissolved in 40ml of deionized water to obtain an indicator solution. When the carboxymethyl cellulose solution was cooled to 40 ℃, the indicator solution was added thereto to obtain a deposition solution containing 40mg/mL of a natural pigment. After degassing, 40mL of the film-forming solution was poured into a polystyrene petri dish with a diameter of 10cm, resulting in a fully gelled indicator film, named CMC-ATH-BET.
(3) CMC-CUR-BET indicates the preparation of membranes.
6g of carboxymethyl cellulose (CMC) powder was dissolved in 500mL of deionized water at 90 ℃ and stirred well for 60 min. Glycerol (30% of the dry matter (carboxymethylcellulose powder)) was added as a plasticizer to obtain a carboxymethylcellulose solution. 0.16g of curcumin-beet red (CUR-BET, 1: 1) was dissolved in 47.5% ethanol to obtain an indicator solution. When the carboxymethyl cellulose solution was cooled to 40 ℃, the indicator solution was added thereto to obtain a deposition solution containing 40mg/mL of a natural pigment. After degassing, 40mL of the film-forming solution was poured into a polystyrene petri dish with a diameter of 10cm, resulting in a fully gelled indicator film, named CMC-CUR-BET.
(4) CMC-ATH indicates the preparation of the film.
6g of carboxymethyl cellulose (CMC) powder was dissolved in 500mL of deionized water at 90 ℃ and stirred well for 60 min. Glycerol (30% of the dry matter (carboxymethylcellulose powder)) was added as a plasticizer to obtain a carboxymethylcellulose solution. 0.16g of Anthocyanidin (ATH) was dissolved in 40mL of deionized water to give an indicator solution. When the carboxymethyl cellulose solution was cooled to 40 ℃, the indicator solution was added thereto to obtain a deposition solution containing 40mg/mL of a natural pigment. After degassing, 40mL of the film-forming solution was poured into a polystyrene petri dish with a diameter of 10cm, resulting in a fully gelled indicator film, designated CMC-ATH.
(5) CMC-CUR indicates the preparation of membranes.
6g of carboxymethyl cellulose (CMC) powder was dissolved in 500mL of deionized water at 90 ℃ and stirred well for 60 min. Glycerol (30% of the dry matter (carboxymethylcellulose powder)) was added as a plasticizer to obtain a carboxymethylcellulose solution. 0.16g Curcumin (CUR) was dissolved in 95% ethanol to give an indicator solution. When the carboxymethyl cellulose solution was cooled to 40 ℃, the indicator solution was added thereto to obtain a deposition solution containing 40mg/mL of a natural pigment. After degassing, 40mL of the film-forming solution was poured into a polystyrene petri dish with a diameter of 10cm, resulting in a fully gelled indicator film, designated CMC-CUR.
(6) CMC-BET indicates the preparation of a film.
6g of carboxymethyl cellulose (CMC) powder was dissolved in 500mL of deionized water at 90 ℃ and stirred well for 60 min. Glycerol (30% of the dry matter (carboxymethylcellulose powder)) was added as a plasticizer to obtain a carboxymethylcellulose solution. 0.16g of beet red (BET) was dissolved in 40mL of deionized water to provide an indicator solution. When the carboxymethyl cellulose solution was cooled to 40 ℃, the indicator solution was added thereto to obtain a deposition solution containing 40mg/mL of a natural pigment. After degassing, 40mL of the film-forming solution was poured into a polystyrene petri dish with a diameter of 10cm, resulting in a fully gelled indicator film, designated CMC-BET.
(7) And (3) preparing a film forming solution.
Dissolving starch in 90-100 deg.C deionized water, stirring for 25-35min, and adding glycerol; adding myogenin into starch solution, and performing ultrasonic treatment by ultrasonic processor to obtain membrane forming solution.
(8) And (4) preparing a colorimetric array.
Degassing the film-forming emulsion, pouring the degassed film-forming emulsion onto a completely gelled indicator film (CMC-ATH-CUR, CMC-ATH-BET, CMC-CUR-BET, CMC-ATH, CMC-CUR, CMC-BET), and drying the prepared film at 45 deg.C for 24 hours to obtain the colorimetric array. Referring to the schematic diagram of fig. 1, which is an explosion diagram of the structure of the fish freshness indication colorimetric array of the present embodiment, wherein the reference numbers are:
1-CMC-ATH-CUR indicator membrane, 2-CMC-ATH-BET indicator membrane, 3-CMC-CUR-BET indicator membrane, 4-CMC-ATH indicator membrane, 5-CMC-CUR indicator membrane, 6-CMC-BET indicator membrane, and 7-myogenin-containing starch adsorption gas layer.
Example 2
The colorimetric array of instruction flesh of fish new freshness that this embodiment provided pastes it in the packing, carries out real-time detection to the new freshness according to its colour change, can discern flesh of fish new freshness.
The colorimetric array was prepared as in example 1.
Adding 90mL of ammonia water with the concentration of 8mol/L into a 100mL beaker, fixing a colorimetric array (8cm multiplied by 5cm) in a culture medium, reversely covering a bottle mouth, collecting image information of a label at room temperature, extracting an RGB value of the label by using a Photoshop2018 color sampler for 21min, and calculating the sensitivity, wherein the calculation formula is as follows:
wherein R is0、G0、B0Is a value of 0 min.
The results are shown in FIG. 2, where the sensitivity of the colorimetric array is different as the ammonia reaction time increases, and the sensitivity of the composite indicator is higher than that of the single indicator.
Fresh cod samples were placed in a clear plastic display box and then wrapped with a sterilized polyester/polypropylene film, with the indicator colorimetric array directly covering the top of the box. As shown in fig. 3, the sample was stored at a temperature of 25 ℃ for 12h, and color change of the colorimetric array was observed, wherein:
the color of the CMC-ATH-CURPH sensate coating changes from a khaki color to a greenish-black color depending on the freshness of the cod;
the color of the CMC-ATH-BET pH sensitive agent coating changes from purple red to deep blue depending on cod freshness;
the color of the CMC-CUR-BET pH-sensitive agent coating changes from orange-red to pale-green depending on cod freshness;
the color of the CMC-ATH pH sensitive agent coating changes from light purple to blue-green according to the freshness of the cod;
the color of the CMC-CurPh sensitive agent coating changes from yellow to bright red according to the freshness of the cod;
the color of the CMC-BET pH-sensitive agent coating changes from pink to pale yellow depending on cod freshness.
In the figure 3, the colorimetric array has obvious color change, and the freshness of the cod can be visually judged.
It should be understood that the present invention is described by way of embodiments, and the embodiments are only provided for enabling technical solutions proposed by the claims of the present invention to achieve clear and complete descriptions, that is, explanations of the claims, so that when judging whether the technical solutions described in the present specification are sufficiently disclosed, the core meanings of the solutions defined by the claims should be fully considered, and other technical problems that are irrelevant to the solution of the core technical problems proposed by the embodiments are necessarily present in the description, and the corresponding technical features and technical solutions are not referred to in the present embodiment, but belong to unnecessary technical features, so that reference may be made to implicit disclosures, and those skilled in the art can fully combine the prior art with the common general knowledge to achieve the purposes, and therefore, no detailed description is necessary.
It should be noted that the above-mentioned embodiments are only for illustrating the technical solutions of the present invention and not for limiting, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions may be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention, which should be covered by the claims of the present invention.
Claims (8)
1. A preparation method of a fish freshness indication colorimetric array based on natural pigments is characterized by comprising the following steps: comprises the following steps of (a) carrying out,
dissolving carboxymethyl cellulose powder in deionized water, fully stirring, adding glycerol to obtain a carboxymethyl cellulose solution, dissolving a natural pigment to obtain an indicating dye, adding the indicating dye into the cooled carboxymethyl cellulose solution to obtain a first membrane forming solution, and pouring the degassed first membrane forming solution into a polystyrene culture dish to obtain a completely gelled indicator membrane;
dissolving starch in deionized water and stirring, adding glycerol to obtain a starch solution, adding myogenin into the starch solution, and performing ultrasonic treatment to obtain a second membrane forming solution;
and after degassing the second film forming solution, pouring the second film forming solution onto the indicator film, and drying to obtain the natural pigment-based freshness indication colorimetric array.
2. The method for preparing a natural pigment-based fish freshness-indicating colorimetric array according to claim 1, wherein: the natural pigment is anthocyanin and curcumin mixture or anthocyanin or curcumin, and the solution concentration of the indicating dye is 40-60 mg/ml.
3. The method for preparing a natural pigment-based fish freshness-indicating colorimetric array according to claim 1, wherein: when the natural pigment is a mixture of anthocyanin, curcumin and beet red, the mass ratio of the anthocyanin, the curcumin and the beet red is 1:1: 1.
4. The method for preparing a natural pigment-based fish freshness-indicating colorimetric array according to claim 1, wherein: the drying conditions were 24 hours at 45 ℃.
5. The method for preparing a natural pigment-based fish freshness-indicating colorimetric array according to claim 1, wherein: the specific weight ratio of each raw material in the colorimetric array is that the carboxymethyl cellulose, the natural pigment, the starch and the myogenic protein are 6:0.16:2:1, wherein the concentration of the myogenic protein is 2-6%.
6. The method for preparing a natural pigment-based fish freshness-indicating colorimetric array according to claim 1, wherein: the carboxymethyl cellulose powder is dissolved in deionized water at 85-95 ℃ and fully stirred for 50-60min, and the cooling temperature of the carboxymethyl cellulose solution is 35-45 ℃.
7. The method for preparing a natural pigment-based fish freshness-indicating colorimetric array according to claim 1, wherein: dissolving the starch in deionized water at 90-100 deg.C, and stirring for 25-35 min.
8. The application of the fish freshness indication colorimetric array is characterized in that: the fish freshness indication colorimetric array prepared by the preparation method of the natural pigment based fish freshness indication colorimetric array according to claims 1 to 7 is applied to indication of fish freshness.
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| CN115368637A (en) * | 2022-08-11 | 2022-11-22 | 桂林理工大学 | High-performance multifunctional carboxymethyl cellulose-based composite material and preparation method and application thereof |
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