CN110987920B - Preparation method and application of gold nano-colloid type time temperature indicator - Google Patents

Preparation method and application of gold nano-colloid type time temperature indicator Download PDF

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CN110987920B
CN110987920B CN201911338452.XA CN201911338452A CN110987920B CN 110987920 B CN110987920 B CN 110987920B CN 201911338452 A CN201911338452 A CN 201911338452A CN 110987920 B CN110987920 B CN 110987920B
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temperature indicator
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time temperature
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钱静
张李璇
许高垒
焦宇
邓黎明
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Jiangnan University
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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
    • G—PHYSICS
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    • G01K—MEASURING TEMPERATURE; MEASURING QUANTITY OF HEAT; THERMALLY-SENSITIVE ELEMENTS NOT OTHERWISE PROVIDED FOR
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    • G—PHYSICS
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    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
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    • 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
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Abstract

The invention relates to a preparation method and application of a gold nano-colloid type time temperature indicator, belonging to the technical field of detection. Mixing, heating and stirring a gelatin solution and a chloroauric acid tetrahydrate solution, and independently packaging the mixed solution to obtain the gold nano-colloid type time temperature indicator. Before the use, the product is stored at a low temperature below 0 ℃. The gold nanometer colloid type time temperature indicator indicates time and temperature history through color change, and can be applied to shelf life prediction of food sensitive to temperature and time. The gold nano material is adopted, so that the color change of the time temperature indicator is more obvious; its color change is irreversible. The preparation process is simple and easy to prepare; the invention also provides a mathematical model between the color service life and the preparation parameters of the gold nanometer colloid type time temperature indicator, which is convenient for practical application.

Description

Preparation method and application of gold nano-colloid type time temperature indicator
Technical Field
The invention relates to a preparation method and application of a gold nano-colloid type time temperature indicator, in particular to an indicator capable of indicating the elapsed time and temperature of a product, and belongs to the technical field of detection.
Background
With the development of economy, the living standard of people is continuously improved, and the requirements of people on the quality and safety of food are also continuously improved. The environment experienced by different products is different and therefore the shelf life printed on the packaging bag does not truly reflect the quality of each individual food product. The quality change of the food is mainly influenced by time and temperature, and the time temperature indicator can effectively indicate the quality change of the food to predict the shelf life of the food because the time temperature indicator can display the time and the temperature which are passed by the time temperature indicator through the change of color.
The existing time temperature indicator has the phenomenon that the color change is not obvious or reversible. The gold nano material has unique optical characteristics, and the time temperature indicator prepared from the gold nano material can generate excellent color effect. However, most of the existing time temperature indicators are liquid type, which puts high requirements on the sealing performance of the outer package of the indicator, so that the development of a gel type time temperature indicator has application value.
Disclosure of Invention
The invention aims to overcome the defects and provides a preparation method and application of a gold nano-colloid type time temperature indicator, which has obvious and irreversible color change and can effectively indicate the change of time and temperature.
According to the technical scheme, the preparation method of the gold nano-colloid type time temperature indicator comprises the steps of mixing, heating and stirring a gelatin solution and a chloroauric acid tetrahydrate solution, and independently packaging the mixed solution to obtain the gold nano-colloid type time temperature indicator. Before the use, the product is stored at a low temperature below 0 ℃.
Further, the gelatin solution preparation process is as follows: dissolving gelatin in pure water, and stirring at the speed of 450-550r/min at the temperature of 88-92 ℃ for 25-35min to obtain a gelatin solution with the concentration of 83-150 g/L;
the concentration of the chloroauric acid tetrahydrate solution is less than 30g/L, and the chloroauric acid tetrahydrate solution is prepared by pure water;
when mixing, the volume ratio of the gelatin solution to the chloroauric acid tetrahydrate solution is 1: 1. during the mixing, the mixture is stirred for 5-15min at the speed of 450-550r/min at the temperature of 88-92 ℃.
Further, when the concentration of the gelatin solution is more than 83g/L, the prepared nano time temperature indicator is in a colloid state when cooled to room temperature.
Further, the individual package is an individual package having sealability.
Further, the amount of the individual package is 0.1 to 1.2 mL.
The application of the gold nanometer colloid type time temperature indicator is applied to the shelf life prediction of food; the time and temperature course is indicated by the color change of the gold nanometer colloid type time and temperature indicator.
Further, the color change means that the color changes from transparent pale yellow to deep red.
Further, the user selects the appropriate dosage according to the needs of the user.
According to the invention, gelatin is used as a reducing agent and a stabilizing agent at the same time, and the gold nanoparticles can be effectively agglomerated by increasing the using amount of the gelatin, so that the colloidal time temperature indicator is prevented from generating gold color, the gold color influences the judgment of naked eyes on other colors, and the visual effect of the time temperature indicator is influenced;
the increase of the gelatin dosage can change the state of the time temperature indicator from liquid to colloid, and reduce the requirement of the time temperature indicator on the sealing performance of the container;
the invention has the beneficial effects that: the gold nano material is adopted, so that the color change of the time temperature indicator is more obvious; its color change is irreversible. The preparation process is simple and easy to prepare; the invention also provides a mathematical model between the color service life and the preparation parameters of the gold nanometer colloid type time temperature indicator, which is convenient for practical application.
Drawings
FIG. 1 is a graph showing the change of absorbance with time at 25 ℃ of the time temperature indicator prepared in example 1.
FIG. 2 is a graph showing the time-temperature indicator prepared in example 1 showing the change of absorbance with time at different temperatures for 600 hours.
FIG. 3 is a graph showing the time-temperature indicator prepared in example 1, showing the time-dependent change in absorbance at different temperatures.
FIG. 4 is a curve fitted to the nano-type time temperature indicator prepared in example 1 for activation energy calculation.
Detailed Description
Example 1
(1) Preparation of gelatin solution: 116.667g of gelatin is taken, 1L of pure water is added, and the mixture is stirred at the speed of 500r/min for 30 minutes at the temperature of 90 ℃ to completely dissolve the gelatin, so that 116.67g/L of gelatin solution can be obtained;
(2) preparing a chloroauric acid tetrahydrate solution: 1.458g of chloroauric acid tetrahydrate is taken, 1L of pure water is added, and the chloroauric acid tetrahydrate solution with the concentration of 1.458g/L is obtained after the mixture is fully shaken up.
(3) Preparing a gold nano-colloid type time temperature indicator: 50mL of chloroauric acid tetrahydrate solution was slowly poured into 50mL of gelatin solution, and the mixture was stirred with heating at 90 ℃ at a rate of 500r/min for 10 minutes. And (3) putting 1.2mL of the mixed solution into a disposable micro plastic cuvette with the volume of 1.5mL to obtain the time temperature indicator.
3 identical nanometer time temperature indicators were manufactured according to the above manufacturing method, and a climatic chamber (RQH-350 type, Shanghai, right instruments Co., Ltd.) was used to perform constant temperature tests at 15 deg.C, 20 deg.C, and 25 deg.C, respectively, and the absorbance of the time temperature indicator was measured at specific time intervals. The instrument required for measuring the absorbance was a UV-1800 UV-visible spectrophotometer (Shimadzu Denko, Japan).
The time temperature indicator absorbance trend with time is shown in fig. 1. As can be seen from fig. 1, the absorbance of the time temperature indicator increases with time because gold ions are reduced to gold atoms, and the gold atoms are continuously aggregated to form gold nanoparticles. As time goes by, the concentration of gold nanoparticles in the indicator becomes greater and its measured absorbance becomes greater. When the concentration of gold nanoparticles in the indicator no longer changes, the absorbance value of the indicator remains unchanged, at which point the indicator reaches its color change endpoint. The time corresponding to the color change end point is the color life of the indicator.
The time temperature indicator absorbance trend with temperature is shown in fig. 2. Over the same time, the higher the temperature at which the indicator is exposed, the greater the concentration of gold nanoparticles generated in the indicator, and the greater its absorbance. The initial color of the time temperature indicator is transparent light yellow, when the absorbance is more than 0.3, the time temperature indicator appears light pink, and the color changes remarkably with the time and finally turns dark red. When the indicator reaches the end point of its color change, its actual color and absorbance no longer change.
As can be seen from FIG. 3, the absorbance of the nano-type time temperature indicator is in a good exponential relationship with time, so that the reaction rates k at different temperatures can be obtained by fitting, and the fitting results are shown in Table 1.
TABLE 1 exponential fitting results of absorbance-time of nano-type time temperature indicator at different temperatures
Temperature, K Reaction rate k Coefficient of correlation R2
288.15(15℃) 0.001092 0.997
293.15(20℃) 0.001956 0.999
298.15(25℃) 0.003567 0.998
Since the correlation coefficient of the absorbance-time fitting curve is greater than 0.9, the logarithm lnk of the reaction rate k at different temperatures and the reciprocal 1/T of the temperature are subjected to linear fitting, and the fitting result is shown in FIG. 4. According to the arrhenius formula:
lnk＝lnk0-EA/RT
the activation energy of the time temperature indicator can be obtained from the slope of the lnk-1/T fit line, i.e., the activation energy Ea is 83.73 KJ/mol.
Example 2
The gold nanogel-type time temperature indicator prepared in example 1 was used to indicate a product within 25KJ/mol of its activation energy. Example 1 the nano-type time temperature indicator prepared can be used to indicate products such as pork, mutton, cream, etc., which are deteriorated due to oxidation of lipid or loss of nutrition.
And when the absorbance value of the time temperature indicator is not changed any more, the indicator reaches a color change end point, and the time corresponding to the color change end point is the color life of the indicator. The color life of the gold-nanogel-type time temperature indicator with different preparation parameters is shown in table 2.
TABLE 2 color Life of gold Nanogel-type time temperature indicators with different preparation parameters
Figure BDA0002331601980000031
Figure BDA0002331601980000041
By fitting the relationship between the color life and the preparation parameters of the gold-nano-colloid type time temperature indicator, a mathematical model between the preparation parameters and the color life of the gold-nano-colloid type time temperature indicator can be obtained as follows (R)2＝0.99695)：
z＝20.27361-0.30359x+0.16403y+0.00244x2+0.00168y2-0.00329xy
Wherein z is indicates a color lifetime (d); x is the gelatin solution concentration before mixing (g/L); y is the gold precursor solution concentration (g/L) before mixing. According to the model, the color life corresponding to the indicators with different preparation parameters can be conveniently and rapidly calculated.

Claims (7)

1. A preparation method of a gold nanometer colloid type time temperature indicator is characterized by comprising the following steps: mixing, heating and stirring a gelatin solution and a chloroauric acid tetrahydrate solution to obtain a mixed solution; independently packaging the mixed solution to obtain a gold nano-colloid type time temperature indicator; before formal use, the product is stored at a low temperature below 0 ℃;
the preparation process of the gelatin solution is as follows: dissolving gelatin in pure water, and stirring at the speed of 450-550r/min at the temperature of 88-92 ℃ for 25-35min to obtain a gelatin solution with the concentration of 83-150 g/L; the concentration of the chloroauric acid tetrahydrate solution is less than 30 g/L; when mixing, the volume ratio of the gelatin solution to the chloroauric acid tetrahydrate solution is 1: 1.
2. the method for preparing a gold nanogel type time temperature indicator according to claim 1, wherein the method comprises the following steps: during the mixing, the mixture is stirred for 5-15min at the speed of 450-550r/min at the temperature of 88-92 ℃.
3. The method for preparing a gold nanogel type time temperature indicator according to claim 1, wherein the method comprises the following steps: when the concentration of the gelatin solution is more than 83g/L, the prepared gold nanometer colloid type time temperature indicator is in a colloid state when cooled to room temperature.
4. The method for preparing a gold nanogel type time temperature indicator according to claim 1, wherein the method comprises the following steps: the independent package is an independent package with sealing performance.
5. The method for preparing a gold nanogel type time temperature indicator according to claim 4, wherein the method comprises the following steps: the amount of the independent package is 0.1-1.2 mL.
6. The use of gold nanogel-type time temperature indicators prepared according to the method of claim 1, wherein: applying it to the shelf life prediction of foods that are more temperature and time sensitive; the time and temperature course is indicated by the color change of the gold nanometer colloid type time and temperature indicator.
7. The use of claim 6, wherein: the color change means that the color changes from transparent pale yellow to deep red.
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