CN115598118B

CN115598118B - Colorimetric sensing reagent, intelligent label, colorimetric method and application

Info

Publication number: CN115598118B
Application number: CN202211392135.8A
Authority: CN
Inventors: 刘一丁; 何怡
Original assignee: Southwest Petroleum University
Current assignee: Southwest Petroleum University
Priority date: 2022-11-08
Filing date: 2022-11-08
Publication date: 2023-05-23
Anticipated expiration: 2042-11-08
Also published as: CN115598118A

Abstract

In order to solve the technical problem that the existing intelligent label is difficult to provide finer experience information and difficult to be utilized by intermediate links, the embodiment of the invention provides a colorimetric sensing reagent, an intelligent label, a colorimetric method and application, wherein the method comprises the following steps: a first reagent comprising a first gold nanoparticle solution and an unaged liquid polymer, the first gold nanoparticle solution being for reacting with the unaged liquid polymer in an oxygen-free closed environment; a second reagent comprising a second gold nanoparticle solution and a first aging-treated polymer solution; the second gold nanoparticle solution is used for reacting with the polymer solution subjected to the first aging treatment in an oxygen-free closed environment; a third reagent comprising a third gold nanoparticle solution and a second aging-treated polymer solution; the third gold nanoparticle solution is used for reacting with the polymer solution of the second aging treatment in an environment communicated with the outside. The embodiment of the invention realizes the functions of time labels, temperature labels and sealing labels.

Description

Colorimetric sensing reagent, intelligent label, colorimetric method and application

Technical Field

The invention relates to the field of colorimetric sensing for optical property application of surface plasma nano materials, and discloses a colorimetric sensing reagent, an intelligent label, a colorimetric method and application.

Background

The food and medicine easy to deteriorate are easily affected by the decomposition of effective components, microorganism reproduction or oxidation, and have strict requirements on environmental temperature, sealing state, etc. in the process of logistics and storage. If the food or drug is once exposed to high temperatures or storage conditions are poor, it is not necessarily shelf-stable even during shelf life. The quality guarantee period is very inaccurate in measuring the duration and internal state of foods or medicines, and the harm of eating deteriorated foods or medicines to human bodies is difficult to measure in the continuous accumulation. Currently, some technologies are dedicated to solving the problem of monitoring easily-degraded foods and medicines, and some achievements are achieved, while smart tags are favored by researchers because of their convenience, and smart tags with single time, temperature, pH and other indication functions have been subjected to staged research and are partially put into the market.

But still have some of its disadvantages, specifically as follows:

1. most of the existing intelligent tags are single-function intelligent tags. Because of the single function, monitoring is often required in conjunction with instrument monitoring or multiple labels for particularly sensitive foods and drugs, increasing monitoring costs and steps, and because of limitations in the number of instruments, efficiency, cost, etc., full coverage of sample monitoring is difficult to achieve in this case.

2. Most of the existing intelligent labels are regulated and controlled based on chemical reactions in a certain type of single equilibrium state to realize different application ranges, but the regulation and control direction of one type of reactions is unidirectional and the regulation and control range is limited, when various scenes are required to be applied, various different types of reactions are required to be searched for design, various proper reactions are not easy to design and convenient functions such as color development are met, research and use cost is increased, and therefore the application range of the labels is limited.

Meanwhile, the current reaction mostly ranges the monitoring of food from the manufacturer to the consumer, and aims to allow the consumer to judge whether the food is edible or not through a simple color state, which is very simple and convenient from the consumer perspective. The principle is that environmental changes affect chemical reactions so that the speed of unidirectional color change is accelerated to obtain different color states, finer experience information is difficult to provide, and the method is difficult to be used by intermediate links. When the middle link encounters a problem, a large amount of manpower and material resources and even precise instruments are required to be consumed for investigation, and the problem is difficult to be optimized and solved simply and quickly from the source.

Disclosure of Invention

In order to solve the technical problem that the existing intelligent label is difficult to provide finer experience information and difficult to utilize for intermediate links, the embodiment of the invention provides a colorimetric sensing reagent, an intelligent label, a colorimetric method and application.

The embodiment of the invention is realized by the following technical scheme:

in a first aspect, embodiments of the present invention provide a colorimetric sensing reagent comprising:

a first reagent comprising a first gold nanoparticle solution and an unaged liquid polymer, the first gold nanoparticle solution being for reacting with the unaged liquid polymer in an oxygen-free closed environment;

a second reagent comprising a second gold nanoparticle solution and a first aging-treated polymer solution; the second gold nanoparticle solution is used for reacting with the polymer solution subjected to the first aging treatment in an oxygen-free closed environment;

a third reagent comprising a third gold nanoparticle solution and a second aging-treated polymer solution; the third gold nanoparticle solution is used for reacting with the second aging-treated polymer solution in an environment communicated with the outside;

the concentrations of the first gold nanoparticle solution, the second gold nanoparticle solution and the third gold nanoparticle solution are consistent;

The concentration of the first aging treatment polymer solution is consistent with that of the second aging treatment polymer solution;

the aging time of the first aging treatment polymer solution and the second aging treatment polymer solution are consistent.

Further, the polymer used in the first reagent, the second reagent and the third reagent is polyethylene glycol.

Further, the gold nanoparticles in the first gold nanoparticle solution, the second gold nanoparticle solution and the third gold nanoparticle solution are gold nanoparticles coated by bis (p-sulfonylphenyl) phenylphosphinated dipotassium dihydrate; the preparation method of the gold nanoparticle coated by the di-potassium bis (p-sulfonylphenyl) phenylphosphinate dihydrate comprises the following steps:

preparing gold nanoparticles by adopting a sodium citrate reduction method;

and carrying out ligand exchange on the gold nanoparticles to obtain the gold nanoparticles coated with the di-potassium bis (p-sulfonylphenyl) phenylphosphinate dihydrate.

In a second aspect, embodiments of the present invention provide a colorimetric method of colorimetric sensing reagents, comprising:

reacting the first gold nanoparticle solution with an unaged liquid polymer in an oxygen-free closed environment to obtain a first reagent;

reacting the second gold nanoparticle solution with the polymer solution subjected to the first aging treatment in an oxygen-free closed environment to obtain a second reagent;

Reacting the third gold nanoparticle solution with the second aging-treated polymer solution in an environment communicated with the outside to obtain a third reagent;

placing the first reagent, the second reagent and the third reagent into the environment where the object to be colorimetrically monitored is located;

and colorizing the color of the first reagent, the color of the second reagent and the color of the third reagent in a pairwise combination manner so as to realize the functions of time labels, temperature labels and sealing labels.

Further, the color of the first reagent, the color of the second reagent and the color of the third reagent are combined in pairs for colorimetry so as to realize the functions of a time tag, a temperature tag and a sealing tag; comprising the following steps:

colorimetry is carried out on the color combination of the first reagent and the color combination of the second reagent so as to realize a time tag function and a temperature tag function;

the color of the second reagent and the color of the third reagent are combined and colorized to realize the sealing label function.

Further, the color of the first reagent and the color of the second reagent are combined and colorimetrically used for realizing a time tag function and a temperature tag function; comprising the following steps:

comparing the color of the first reagent with the color generation time length of the second reagent to realize the time tag function by comparing the time length with the standard time length of the object to be colorimetrically monitored;

Comparing whether the time length is greater than the standard time length of the article to be colorimetrically monitored to realize the temperature label function, if so, judging that the article to be colorimetrically monitored has the condition that the temperature in the time length is less than the temperature in the standard time length; if not, judging that the object to be colorimetrically monitored has the condition that the temperature in the time length is greater than the temperature in the standard time length.

Further, colorimetrizing the combination of the color of the second reagent and the color of the third reagent to achieve the sealing label function comprises:

comparing the color of the second reagent with the color of the third reagent, and if the color of the second reagent is different from the color of the third reagent, judging that the environment where the object to be colorimetrically monitored is positioned is in a non-sealing state; and if the color of the second reagent is the same as that of the third reagent, judging that the environment where the object to be colorimetrically monitored is positioned is in a sealed state.

In a third aspect, an embodiment of the present invention provides a colorimetric sensing smart tag based on the colorimetric sensing reagent, including:

the first color matching device comprises a first closed reaction container and a second color matching device, wherein the first closed reaction container is used for containing liquid polymer which is not aged and a first openable glass tubule; a first glass tubule for holding a first gold nanoparticle solution;

A second colorimetric device comprising a second closed-type reaction vessel for holding the first aging-treated polymer solution and an openable second glass tubule; a second glass tubule for holding a second gold nanoparticle solution;

a third colorimetric device comprising an openable reaction vessel comprising a lid and a container body for holding a second aging-treated polymer solution and an openable third glass tubule; the opening of the container body is sealed by an air-selective permeable membrane; and a third glass tubule for holding a third gold nanoparticle solution.

Further, the colorimetric sensing smart tag further comprises:

the colorimetric container is used for accommodating the first colorimetric device, the second colorimetric device and the third colorimetric device;

the color recognition graph is arranged outside the colorimetric container;

the time indicator label is arranged on the outer side of the colorimetric container;

the temperature indicator label is arranged on the outer side of the colorimetric container; and

and the sealing indicator label is arranged outside the colorimetric container.

In a fourth aspect, embodiments of the present invention provide for the use of the colorimetric sensing reagent for smart labels.

Compared with the prior art, the embodiment of the invention has the following advantages and beneficial effects:

According to the colorimetric sensing reagent, the intelligent label, the colorimetric method and the application, a first gold nanoparticle solution of a first reagent reacts with an unaged liquid polymer in an oxygen-free closed environment; the second gold nanoparticle solution of the second reagent reacts with the polymer solution of the first aging treatment in an oxygen-free closed environment; the third gold nanoparticle solution of the third reagent reacts with the polymer solution of the second aging treatment in the environment communicated with the outside, and the functions of a time tag, a temperature tag and a sealing tag are realized through the combined colorimetry of the first reagent, the second reagent and the first reagent, so that the technical problem that the existing intelligent tag is difficult to provide finer experience information and is difficult to be utilized by an intermediate link is solved.

Drawings

In order to more clearly illustrate the technical solutions of the exemplary embodiments of the present invention, the drawings that are needed in the examples will be briefly described below, it being understood that the following drawings only illustrate some examples of the present invention and therefore should not be considered as limiting the scope, and that other related drawings may be obtained from these drawings without inventive effort for a person skilled in the art.

Fig. 1 is a schematic view of a visible light absorption wavelength range corresponding to a color change in a transient assembly process.

FIG. 2 is a schematic diagram of the effect of temperature on transient assembly.

Fig. 3 is a schematic diagram of the effect of humidity on transient assembly.

FIG. 4 is a schematic diagram showing the effect of aging on transient assembly.

FIG. 5 is a schematic diagram showing the effect of different oxygen levels on transient assembly.

Fig. 6 is a schematic structural diagram of the first color matching device.

Fig. 7 is a schematic structural view of a second colorimetric device.

Fig. 8 is a schematic structural view of a third colorimetric device.

Fig. 9 is a schematic structural view of the cuvette.

FIG. 10 is a schematic representation of the basic structural units comprised by the polymer.

In the drawings, the reference numerals and corresponding part names:

1-closed plastic shell, 2-liquid polymer, 3-gold nanoparticle solution, 4-glass tubule, 5-aging polymer solution, 6-openable plastic shell, 7-color mark, 8-time indication label, 9-color combination and corresponding time mark, 10-temperature indication label, 11-sealing indication label, 12-air selective transmission film.

Detailed Description

For the purpose of making apparent the objects, technical solutions and advantages of the present invention, the present invention will be further described in detail with reference to the following examples and the accompanying drawings, wherein the exemplary embodiments of the present invention and the descriptions thereof are for illustrating the present invention only and are not to be construed as limiting the present invention.

In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention. However, it will be apparent to one of ordinary skill in the art that: no such specific details are necessary to practice the invention. In other instances, well-known structures, circuits, materials, or methods have not been described in detail in order not to obscure the invention.

Throughout the specification, references to "one embodiment," "an embodiment," "one example," or "an example" mean: a particular feature, structure, or characteristic described in connection with the embodiment or example is included within at least one embodiment of the invention. Thus, the appearances of the phrases "in one embodiment," "in an example," or "in an example" in various places throughout this specification are not necessarily all referring to the same embodiment or example. Furthermore, the particular features, structures, or characteristics may be combined in any suitable combination and/or sub-combination in one or more embodiments or examples. Moreover, those of ordinary skill in the art will appreciate that the illustrations provided herein are for illustrative purposes and that the illustrations are not necessarily drawn to scale. The term "and/or" as used herein includes any and all combinations of one or more of the associated listed items.

In the description of the present invention, the terms "front", "rear", "left", "right", "upper", "lower", "vertical", "horizontal", "high", "low", "inner", "outer", etc. indicate orientations or positional relationships based on the orientations or positional relationships shown in the drawings, merely to facilitate description of the present invention and simplify description, and do not indicate or imply that the devices or elements referred to must have a specific orientation, be configured and operated in a specific orientation, and therefore should not be construed as limiting the scope of the present invention.

Examples

In order to solve the technical problem that the existing intelligent label is difficult to provide finer experience information and difficult to be utilized by an intermediate link, in a first aspect, an embodiment of the present invention provides a colorimetric sensing reagent, which includes:

The specific principle is as follows: for the second reagent and the third reagent, the reaction mechanism of the colorimetric sensing reagent is different from that of other intelligent labels, the other intelligent labels are one-way reactions, one equilibrium state is reached to the other, the reaction constructs a self-regulating dynamic assembly system based on chemical driving, a competitive cascade reaction of specific sites is formed on an assembly module (namely gold nano particles) and a chemical driving design (namely polymers such as polyethylene glycol), namely the first driving provided by sodium citrate (adsorption action, electrostatic action caused by polyethylene glycol after adsorbing polyethylene glycol) and the second driving provided by BSPP (BSPP and aged polyethylene glycol are subjected to oxidation reaction, so that the nano particles are disassembled) because the two driving compete with each other but the assembly speed is higher than the disassembly speed, thereby realizing a transient assembly process and reversible color change. The first reagent uses unaged polymer solution on the basis of not changing the design of the nano particles, so that the second drive is weaker, transient assembly can not be realized, and the first reagent is a durable assembly structure.

In the embodiment of the invention, the first gold nanoparticle solution of the first reagent reacts with the liquid polymer which is not subjected to aging treatment in an oxygen-free closed environment; the second gold nanoparticle solution of the second reagent reacts with the polymer solution of the first aging treatment in an oxygen-free closed environment; the third gold nanoparticle solution of the third reagent reacts with the polymer solution of the second aging treatment in the environment communicated with the outside, and the functions of a time tag, a temperature tag and a sealing tag are realized through the combined colorimetry of the first reagent, the second reagent and the first reagent, so that the technical problem that the existing intelligent tag is difficult to provide finer experience information and is difficult to be utilized by an intermediate link is solved.

Alternatively, the polyethylene glycol is polyethylene glycol 200, polyethylene glycol 300, polyethylene glycol 400 or polyethylene glycol 600 (different polyethylene glycol molecular weights), preferably polyethylene glycol 200.

The invention researches and screens the influence of substances with similar structures on the transient assembly process of the first reagent, the second reagent and the third reagent. Table 1 will be described in detail.

TABLE 1

As can be seen from the above table, the volume of alcohol and water is 3: under the condition of 1, the triethylene glycol, the tetraethylene glycol and the polyethylene glycol 200-600 can realize the transient assembly effect, and the transient assembly effect of the polyethylene glycol 200 is optimal from the viewpoint of the transient assembly time, so the polyethylene glycol 200 is selected.

In addition, it can be seen from the above table that the polymer having the structure shown in fig. 10 after aging can realize the transient assembly process.

Polyethylene glycol polymers are commercially available high purity polymers. The volume ratio of the water to the water is from 2:1 to 6:1, even the PEG ratio may be higher. The concentration of gold nanoparticles is 1x10 ^-4 mol/L to 5x10 ^-4 The concentration of gold nanoparticles can be higher in mol/L. The optimal condition is that the volume ratio of gold nano particles to water is 4:1, at this time, the gold nanoparticle concentration is 3x10 ^-4 mol/L。

The difference in the reaction product of aged polyethylene glycol compared to unaged polyethylene glycol is the peroxide of polyethylene glycol.

Further, the polymer solution for the first aging treatment and the polymer solution for the second aging treatment are the same polyethylene glycol solution, the conditions for the aging treatment are 90 ℃ treatment, and the treatment time is optimal for 12 hours. The solvent corresponds to the liquid polymer which has not been aged.

Preparing gold nanoparticles by adopting a sodium citrate reduction method;

The gold nanoparticle is prepared by a classical sodium citrate reduction method, and the gold nanoparticle is subjected to ligand exchange to obtain the gold nanoparticle coated with bis (p-sulfonylphenyl) phenylphosphinated dipotassium dihydrate.

Optionally, the specific preparation method comprises:

negatively charged gold nanoparticles are synthesized by classical citrate reduction followed by ligand exchange procedures. The method comprises the following steps: HAuCl was stirred at 800-1200rpm ₄ ·3H ₂ O(19-25mL，1g mL ^-1 ) The aqueous solution was added to boiling deionized water (95 mL) followed by the addition of trisodium citrate aqueous solution (5 mL,1wt% to 1.5 wt%). Boiling for 20-30 min, and gradually changing the color of the solution from colorless to dark red. After cooling to room temperature, the solution was combined with an aqueous solution of bis (p-sulfonylphenyl) phenylphosphonate dipotassium dihydrate (BSPP) (0.1-0.5 mL,40mg mL ^-1 ) Mixing, stirring for 4-12h, centrifuging, washing with deionized water for 1-2 times, and dispersing in 10mL of water to obtain gold nanoparticle solution.

Specifically, when the gold nanoparticles are gold nanoparticles coated by bis (p-sulfonylphenyl) phenylphosphonate dipotassium dihydrate, the first gold nanoparticle solution reacts with the unaged liquid polymer in an oxygen-free closed environment, and the color of the reacted product is t ₁ A change in color from red, violet, deep violet to blue occurs over a time range that is unidirectional and is tunable by having a temperature dependence.

Specifically, when the gold nanoparticles are gold nanoparticles coated by bis (p-sulfonylphenyl) phenylphosphonate dipotassium dihydrate, the second gold nanoparticle solution is used for reacting with the polymer solution subjected to the first aging treatment in an oxygen-free closed environment, and the color of the reacted product can be at t in the same oxygen-free closed environment as the first reagent ₁ The time frame achieves a color change from red, violet, deep violet to blue in synchronization with the first reagent and, unlike the first reagent, the second reagent reverses the direction of the color change of the product after turning blue, at t ₁ To t ₂ The color change gradually goes from blue, deep violet, purple back to red over time.

Thus, since the first and second reagents are at t ₁ The synchronicity within the reagent and the multistable character of the second reagent in the absence of additional stimulus may function as a time stamp based on the combined color change.

The reaction of the first, second and third reagents is a transient assembly process in which various equilibrium state color changes are involved. Reference is made to figures 1-5.

From time t ₀ -t ₁ The colors are from red, purple, deep purple to blue (t ₁ ) From time t ₁ -t ₂ The color is changed from blue, deep purple, purple to red (t ₂ ) From t of FIG. 1 ₀ 、t ₁ And t ₂ The wavelength of the corresponding color is known from the corresponding absorption spectrum.

The inventors studied the impact on the transient assembly process under different conditions. Conditions studied included temperature, humidity, degree of polymer aging and oxygen content.

Referring to FIG. 2, the relationship between reaction time and ratio (A650 nm/A522 nm) at temperatures of 30℃2a,40℃2b,50

℃

2c and 60℃2d was studied in FIG. 2. In the absorption spectrum, 650nm is the plasmon coupling band and 522nm represents a single isotropic surface plasmon band. The ratio can represent the assembly state of transient assembly, and the increasing ratio represents that gold nanoparticles in the reagent are in the assembly process, and the corresponding color changes to red-purple-dark purple-blue. The gradual decrease in the ratio indicates that the gold nanoparticles in the reagent are in the process of disassembly, and the corresponding color changes to blue-deep purple-red.

As can be seen from fig. 2, the lower the temperature, the longer the reaction time, i.e. the time for the assembly and disassembly of the transient assembly becomes longer.

Referring to FIG. 3, the relationship between reaction time and Ritio (A650 nm/A522 nm) at different humidity levels (i.e., at different volume ratios of PEG200 and water) was studied in FIG. 3. Different humidity conditions include PEG200: h ₂ O＝4:1 3a,PEG200：H ₂ O＝5:1 3b,PEG200：H ₂ O＝6:1 3c,PEG200：H ₂ O＝3:1 3d,PEG200：H ₂ O=2:1:3e. As can be seen from fig. 3, PEG200: h ₂ The higher the ratio of O, the shorter the reaction time, the higher the assembly degree in the transient assembly process, the faster the disassembly and assembly speed, and when the volume ratio is 6:1 and 5:1, the reaction time is 30min, the ratio (A650nm/A522 nm) is maximized, and at a reaction time of 60min, the ratio (A650 nm/A522 nm) is maximized at a volume ratio of 4:1, 3:1, 2:1.

Referring to FIG. 4, FIG. 4 shows the relationship between reaction time and ratio (A650 nm/A522 nm) for various aging times of PEG200, including 0h 4a, 2h 4b, 4h 4c, 6h4d, 8h4e, 10.5h 4f and 12h 4g. As can be seen from fig. 4, the longer the aging time, the more thorough the disassembly process of transient assembly is reflected on the color change, and the more the color change process is, the cycle of color change can be realized. At 0h aging time, the ratio (A650 nm/A522 nm) was stable after 60min, indicating that it did not undergo a process of disassembly, and from the perspective of color change, it had a unidirectional change, i.e., a change in red-violet-deep violet-blue, which remained blue after 60 min. As can be seen from 8h, 10.5h and 12h, the aging within the range can realize the round-trip process of color change, and the whole transient assembly process time is shortened along with the increase of the aging time.

Referring to FIG. 5, FIG. 5 shows the relationship between reaction time and ratio (A650 nm/A522 nm) for various oxygen contents. The different oxidation levels include a small amount of oxygen 5a and a large amount of oxygen 5b, and as can be seen from FIG. 5, the more the amount of oxygen is, the more easily oxidized, and the faster the maximum value of the ratio (A650 nm/A522 nm) decreases, the faster the color change from the viewpoint of color change.

Based on the conclusion of the above study, the colorimetric sensing reagent of the embodiment of the invention can realize the functions of a time tag, a temperature tag and a sealing tag.

The first reagent is represented by A, the second reagent is represented by B, the third reagent is represented by C, a represents red, B represents purple, C represents deep purple, and d represents blue. The color combination of AB can be represented by a combination of letters, thereby corresponding to a period of time. The process is simple and convenient, for example aa indicates that the first reagent is red and the second reagent is red, i.e. the time indicated by the first reagent and the second reagent is t ₁ In, the article to be colorimetrically monitored is illustrated at t ₁ The front section in the time indicates that the object to be colorimetrically monitored is fresh and can be used, and the object to be colorimetrically monitored is close to the production date; similarly, dd is at t ₁ The end of the time belongs toIn the middle stage of the shelf life of the article, the product should be used quickly; da indicates that the item is in a temporary state and is recommended to be unused.

The length of time that the progress of the ABC reaction has elapsed can be determined by color combining and comparing the length of time to a standard length of time for the item to be colorimetrically monitored. If the factory time is taken as a starting point and the time of colorimetric is taken as an end point, the standard time length is obtained. The ABC reaction is faster in reaction progress when the temperature is higher, and slower in reaction progress when the temperature is lower, so that the speed of the ABC reaction progress can be reflected according to comparison of the time length of the ABC reaction progress and the standard time length, and the temperature change of an article to be colorimetrically monitored in the standard time length can be deduced.

Specifically, whether the time length is greater than the standard time length of the article to be colorimetrically monitored is compared to realize the temperature label function, and if so, the condition that the temperature of the article to be colorimetrically monitored is less than the temperature of the standard time length is judged; if not, judging that the object to be colorimetrically monitored has the condition that the temperature in the time length is greater than the temperature in the standard time length.

B and C are the same reaction conditions and the sensitivity to temperature is the same, except that B is a closed condition, and C is not a complete closed state, and gas can pass through the upper part, so if the package is damaged, oxygen enters, the color change process of C can be quickened, the colors of B and C can be different, and therefore whether the package is damaged or not can be judged, and whether oxygen enters or not can be judged.

Therefore, the colorimetric sensing reagent provided by the embodiment of the invention can realize the functions of a time tag, a temperature tag and a sealing tag through the combination of ABC. Therefore, the reaction system of the chemically-driven transient assembly reaction system designed by using the gold nanoparticle material coated by the bis (p-sulfonylphenyl) phenylphosphinated dipotassium salt dihydrate can meet the multi-dimensional intelligent label function, is distinguished from the traditional single-reaction single-dimensional intelligent label function, and realizes the maximization of resources.

s1, reacting a first gold nanoparticle solution with an unaged liquid polymer in an oxygen-free closed environment to obtain a first reagent;

s2, reacting the second gold nanoparticle solution with the polymer solution subjected to the first aging treatment in an oxygen-free closed environment to obtain a second reagent;

s3, reacting the third gold nanoparticle solution with the polymer solution subjected to the second aging treatment in an environment communicated with the outside to obtain a third reagent;

steps S1-S3 may be performed simultaneously or separately.

S4, placing the first reagent, the second reagent and the third reagent into an environment where the object to be colorimetrically monitored is located;

Such as placing the first, second and third reagents into the packaging of the packaged food or pharmaceutical product or attaching them to the packaging surface as required for the label function. The time label and the temperature label can be used and are attached to the outside of the package.

S5, colorizing the color of the first reagent, the color of the second reagent and the color of the third reagent in a two-by-two combination manner so as to realize the functions of time labels, temperature labels and sealing labels.

The functions of the time tag, the temperature tag and the sealing tag can be realized by checking the combination of the color of the first reagent, the color of the second reagent and the color of the third reagent, so that the information of the temperature environment, the transferring time, the damage of the sealing and the like of the food or medicine from delivery to transferring can be obtained.

Further, S5, the color of the first reagent, the color of the second reagent and the color of the third reagent are combined in pairs for colorimetry so as to realize the functions of a time tag, a temperature tag and a sealing tag; comprising the following steps:

s51, combining and colorizing the color of the first reagent and the color of the second reagent to realize a time tag function and a temperature tag function;

s52, colorimetry is carried out on the color combination of the second reagent and the color combination of the third reagent so as to realize the sealing label function.

Further, S51, combining colors of the first reagent and the second reagent to realize a time tag function and a temperature tag function; comprising the following steps:

s511, comparing the color of the first reagent with the color generation time length of the second reagent, and realizing a time tag function by comparing the time length with the standard time length of the object to be monitored colorimetrically;

s512, comparing whether the time length is greater than the standard time length of the object to be colorimetrically monitored to realize the temperature label function, if so, judging that the object to be colorimetrically monitored has the condition that the temperature in the time length is less than the temperature in the standard time length; if not, judging that the object to be colorimetrically monitored has the condition that the temperature in the time length is greater than the temperature in the standard time length.

When the colorimetric sensor reagent is enclosed in a package together with the article to be colorimetrically monitored at the time of production, if the reading time according to the colorimetric sensor reagent is smaller than the time calculated according to the package production date at this time, it is known that there is a process in which the temperature is higher than the storage condition in this time range. If the above-mentioned reading time is greater than the calculated time based on the package production date, it is known that there is a process in which the temperature is lower than the storage condition within this time range. Since the color change process is segmented finely and definitely, a specific section of the temperature change can be known by a plurality of observations.

Further, s52, colorizing the color combination of the second reagent and the color combination of the third reagent to realize the sealing label function includes:

s521, comparing the color of the second reagent with the color of the third reagent, and if the color of the second reagent is different from the color of the third reagent, judging that the environment where the object to be colorimetrically monitored is located is in a non-sealing state; and if the color of the second reagent is the same as that of the third reagent, judging that the environment where the object to be colorimetrically monitored is positioned is in a sealed state.

The second reagent and the third reagent are identical in reaction condition and same in sensitivity to temperature, except that the second reagent is in a closed condition, and the third reagent is not in a completely closed state, and a film hole which can pass through gas but cannot pass through liquid is formed above the second reagent, so that if the package is damaged, oxygen enters, the color change process of the third reagent is accelerated, and the colors of the second reagent and the third reagent are different, so that judgment can be made.

In a third aspect, an embodiment of the present invention provides a colorimetric sensing smart tag based on the colorimetric sensing reagent, as shown in fig. 6 to 9, including:

the first color matching device comprises a first closed reaction container for containing the liquid polymer 2 which is not aged and a first openable glass tubule; a first glass tubule for holding a first gold nanoparticle solution;

Optionally, the air-selective permeable membrane is a polyethylene film or a polytetrafluoroethylene waterproof and breathable membrane.

Further, the colorimetric sensing smart tag further comprises:

the color recognition graph is arranged outside the colorimetric container;

and the sealing indicator label is arranged outside the colorimetric container.

Referring to fig. 6-9, a colorimetric sensing smart tag for a colorimetric sensing reagent comprises: the color comparison device comprises a first color comparison device, a second color comparison device and a third color comparison device; optionally, the first closed reaction container and the second closed reaction container are both closed plastic shells 1, the first aging polymer solution and the second aging polymer solution are both aging polymer solutions 5, and the first glass tubule, the second glass tubule and the third glass tubule are all glass tubules 4; the first gold nanoparticle solution, the second gold nanoparticle solution and the third gold nanoparticle solution are all gold nanoparticle solution 3; the openable reaction vessel comprises an openable plastic shell 6 and a cover body; the cover body is detachably connected with the opening of the openable plastic shell 6, the opening of the openable plastic shell 6 is sealed with an air selective permeation film 12, and the outer side of the colorimetric container is provided with a color mark 7, a time indication label 8, a color combination, a corresponding time mark 9, a temperature indication label 10 and a sealing indication label 11. Optionally, the color combination and the corresponding time mark 9 are the color combination of two reactions of AB and the corresponding time. Optionally, the glass tubule is broken up during use, so that the gold nanoparticle solution is mixed with the liquid polymer or polymer solution for reaction. The structure similar to a fluorescent rod can be adopted, the first closed reaction container, the second closed reaction container and the openable reaction container are all made of elastic materials, glass tubules are arranged in the elastic materials, and the glass tubules seal gold nanoparticle solution. When the gold nanoparticle solution is used, the first closed reaction container, the second closed reaction container or the openable reaction container is bent to enable the closed reaction container, the second closed reaction container or the openable reaction container to squeeze the glass tubule, so that the glass tubule is broken, and the gold nanoparticle solution and the liquid polymer or the polymer solution are mixed for reaction.

The first colorimetric device, the second colorimetric device and the third colorimetric device utilize gold nanoparticle solution surface plasma nanomaterial to construct a transient assembly reaction system, so that ABC three reaction scenes are realized, and the functions of a time tag, a temperature tag and a sealing tag can be realized through the colorimetry of the three scenes.

Alternatively, the polymer used for the polymer solution and the liquid polymer is polyethylene glycol, further, the polyethylene glycol is polyethylene glycol 200. Two nanoparticle self-assembly processes, including static self-assembly and chemically driven transient assembly, can be achieved by adjusting the different aging levels of polyethylene glycol. The assembled and disassembled states of the nano particles show different colors, the chemical reaction is greatly influenced by temperature, humidity, polymer aging degree and oxygen, and the adjustment and control can be performed (shown by referring to figures 2-5), so that the design of various application conditions can be performed according to different requirements.

Static self-assembly only goes through the process from a dispersed state to an assembled state, namely, the color change is only from red to blue; chemically driven transient assembly includes two processes, self-assembly and self-disassembly, which occur programmatically without additional stimulus, i.e., undergo a process from a dispersed state to an assembled state and then from the assembled state to the dispersed state, the color change process including a red to blue change and a consequent blue to red change (see fig. 1); the reaction at the self-assembly stage of static self-assembly and transient assembly is synchronous, the influencing factors are the same, and the assembly principle is the same; the transient assembly oxygen content and the polyethylene glycol aging degree have a larger influence.

Static self-assembly, wherein the gold nano solution reacts with untreated colorless transparent liquid polyethylene glycol, and the color change process is red to purple, deep purple and then blue; b and C are transient assembly processes that react from gold nanoparticle solutions and aging-treated polymer solutions, and the color change process involves a change from red to blue and also a consequent change from blue to red.

Referring to fig. 9, the positions of the indicia A, B, C in the cuvette are used to house a first, second and third colorimeter, respectively; the A reaction system can change from red, purple, deep purple and blue in color in the time range t1, the change is unidirectional, and the time range is adjustable due to temperature dependence. The B reaction system can realize the color change from red, purple, deep purple and blue synchronous with A in the time range of t1 under the same condition as A, and the direction of the color change of B is reverse after the B is changed into blue, and the color change gradually changes from blue, deep purple, purple to red in the time range of t1 to t 2. Thus, due to the synchronicity of AB within t1 and the transient assembly characteristics of B without additional stimulus, the time-stamping function can be exercised according to the combined color change. Red by a, purple by b, dark purple by c, and blue by d. The color combination of AB is represented by a combination of letters, thereby corresponding to a period of time. The process is simple and convenient, for example aa indicates that the food or medicine is fresh and can be used, and the date of production is near; dd represents the time t1 from production, which belongs to the intermediate phase of the shelf life of the article, should be used rapidly; da indicates that the item is in a temporary state and is recommended to be unused. The indication function is singly used, is suitable for scenes needing to conveniently and rapidly read the approximate state of the effective period of the article, is used for treatment, and is particularly suitable for consumers to rapidly read effective information. However, when the time-stamp is used alone, the time-stamp can only show the function of the time stamp and has certain temperature dependence, so that deterioration of food or articles caused by temperature or aerobic conditions cannot be eliminated, and when the time-stamp is used alone, higher-precision judgment is required, and known food or medicine is required to be stored in a relatively stable temperature environment. For temperature-sensitive foods or medicines, not only time is needed to be known, but also whether temperature change exists in the process is needed to be judged, and then the temperature indication function is needed to be combined for judgment. If the read time is less than the calculated time based on the package production date, it is known that there is a process in which the temperature is higher than the storage condition within this time range. If the read time is greater than the calculated time based on the package production date, it is known that there is a process in which the temperature is below the storage condition within this time range. The color change process is detailed and definite in sections, so that a specific section of temperature change can be known through multiple observations, and the method is particularly suitable for rapid monitoring of food and medicine states by intermediate personnel in transportation and storage, and judging possible problem sections and problems, thereby improving and solving the problems. And foods or medicines sensitive to oxygen or sensitive to both temperature and oxygen, such as foods or medicines sensitive to temperature under sealed conditions, need to be monitored. The function of the seal indication may be used on the basis of the function of the temperature indication.

B and C are identical in reaction conditions and the sensitivity to temperature is identical, except that B is a closed condition, and C is not a completely closed state, and a film hole which can pass through gas but cannot pass through liquid is formed above the B and C, so that if the package is damaged, oxygen enters the C, the color change process of the C is accelerated, and the colors of the B and the C are different, so that judgment can be made.

Therefore, the embodiment of the invention can realize three reaction scenes with different conditions through the combination of ABC, thereby realizing the functions of time labels, temperature labels and sealing labels; specifically, the AB combination may have a time-stamping function by colorimetry; comparing the time length of AB calibration with the time length calculated according to the package or calibration time, the condition that whether the temperature is higher or lower than the known temperature exists in the time period can be known, and the approximate time interval can be known; in the sealed space, the presence or absence of oxygen contamination can be known by comparing BC, the condition of leakage is sealed.

Therefore, the embodiment of the invention has the advantages of multifunction, convenient and quick use, time and labor saving, sufficient information content, wide application range and wide application range, and can be realized by regulation and control.

The foregoing description of the embodiments has been provided for the purpose of illustrating the general principles of the invention, and is not meant to limit the scope of the invention, but to limit the invention to the particular embodiments, and any modifications, equivalents, improvements, etc. that fall within the spirit and principles of the invention are intended to be included within the scope of the invention.

Claims

1. A colorimetric sensing reagent comprising:

the aging time of the first aging treatment polymer solution is consistent with that of the second aging treatment polymer solution;

the first reagent, the second reagent and the third reagent adopt polyethylene glycol as a polymer;

the gold nanoparticles in the first gold nanoparticle solution, the second gold nanoparticle solution and the third gold nanoparticle solution are gold nanoparticles coated by bis (p-sulfonylphenyl) phenylphosphinated dipotassium dihydrate; the preparation method of the gold nanoparticle coated by the di-potassium bis (p-sulfonylphenyl) phenylphosphinate dihydrate comprises the following steps:

preparing gold nanoparticles by adopting a sodium citrate reduction method;

2. A colorimetric method for the colorimetric sensing reagent of claim 1, comprising:

colorimetry is carried out on the color combination of the first reagent and the color combination of the second reagent so as to realize a time tag function and a temperature tag function; comprising the following steps:

comparing whether the time length is greater than the standard time length of the article to be colorimetrically monitored to realize the temperature label function, if so, judging that the article to be colorimetrically monitored has the condition that the temperature in the time length is less than the temperature in the standard time length; if not, judging that the object to be colorimetrically monitored has the condition that the temperature in the time length is greater than the temperature in the standard time length;

colorimetry of the color combination of the second reagent and the color combination of the third reagent to achieve the sealing label function includes:

3. A colorimetric sensing smart tag based on the colorimetric sensing reagent of claim 1, comprising:

a third colorimetric device comprising an openable reaction vessel comprising a lid and a container body for holding a second aging-treated polymer solution and an openable third glass tubule; the opening of the container body is sealed by an air-selective permeable membrane; a third glass tubule for holding a third gold nanoparticle solution;

the color recognition graph is arranged outside the colorimetric container;

and the sealing indicator label is arranged outside the colorimetric container.

4. Use of the colorimetric sensing reagent of claim 1 for a smart label.