CN117946660A - Freezing history indicator and application thereof - Google Patents
Freezing history indicator and application thereof Download PDFInfo
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- CN117946660A CN117946660A CN202410096215.1A CN202410096215A CN117946660A CN 117946660 A CN117946660 A CN 117946660A CN 202410096215 A CN202410096215 A CN 202410096215A CN 117946660 A CN117946660 A CN 117946660A
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- Prior art keywords
- freeze
- freezing
- history indicator
- guanidine
- viologen
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- 238000007710 freezing Methods 0.000 title claims abstract description 38
- 230000008014 freezing Effects 0.000 title claims abstract description 38
- ZRALSGWEFCBTJO-UHFFFAOYSA-N anhydrous guanidine Natural products NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 claims abstract description 28
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 claims abstract description 20
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 claims abstract description 20
- YCWSUKQGVSGXJO-NTUHNPAUSA-N nifuroxazide Chemical group C1=CC(O)=CC=C1C(=O)N\N=C\C1=CC=C([N+]([O-])=O)O1 YCWSUKQGVSGXJO-NTUHNPAUSA-N 0.000 claims abstract description 18
- -1 guanidine macrocycles Chemical class 0.000 claims abstract description 15
- 238000002360 preparation method Methods 0.000 claims abstract description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 30
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- 239000007788 liquid Substances 0.000 claims description 19
- 239000000243 solution Substances 0.000 claims description 11
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 10
- 239000000853 adhesive Substances 0.000 claims description 10
- 230000001070 adhesive effect Effects 0.000 claims description 10
- 238000002347 injection Methods 0.000 claims description 10
- 239000007924 injection Substances 0.000 claims description 10
- 238000012544 monitoring process Methods 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 8
- 238000004062 sedimentation Methods 0.000 claims description 8
- 238000003860 storage Methods 0.000 claims description 6
- HTRYWXJIGDXDLF-UHFFFAOYSA-L 1-(2,4-dinitrophenyl)-4-[1-(2,4-dinitrophenyl)pyridin-1-ium-4-yl]pyridin-1-ium;dichloride Chemical compound [Cl-].[Cl-].[O-][N+](=O)C1=CC([N+](=O)[O-])=CC=C1[N+]1=CC=C(C=2C=C[N+](=CC=2)C=2C(=CC(=CC=2)[N+]([O-])=O)[N+]([O-])=O)C=C1 HTRYWXJIGDXDLF-UHFFFAOYSA-L 0.000 claims description 5
- 229930040373 Paraformaldehyde Natural products 0.000 claims description 5
- 230000002378 acidificating effect Effects 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 229920002866 paraformaldehyde Polymers 0.000 claims description 5
- 239000000376 reactant Substances 0.000 claims description 5
- 238000001953 recrystallisation Methods 0.000 claims description 5
- 238000010992 reflux Methods 0.000 claims description 5
- 238000002390 rotary evaporation Methods 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 238000001291 vacuum drying Methods 0.000 claims description 5
- 238000004090 dissolution Methods 0.000 claims description 4
- VPVSTMAPERLKKM-UHFFFAOYSA-N glycoluril Chemical compound N1C(=O)NC2NC(=O)NC21 VPVSTMAPERLKKM-UHFFFAOYSA-N 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 238000007789 sealing Methods 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 20
- 230000008569 process Effects 0.000 abstract description 17
- 230000000694 effects Effects 0.000 abstract description 5
- 238000005516 engineering process Methods 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 4
- 238000005538 encapsulation Methods 0.000 abstract description 2
- 239000003086 colorant Substances 0.000 abstract 2
- 239000003814 drug Substances 0.000 description 5
- 229940079593 drug Drugs 0.000 description 5
- 235000013305 food Nutrition 0.000 description 5
- 230000007613 environmental effect Effects 0.000 description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- 229930182478 glucoside Natural products 0.000 description 2
- 150000008131 glucosides Chemical class 0.000 description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 2
- 125000002816 methylsulfanyl group Chemical group [H]C([H])([H])S[*] 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000004913 activation Effects 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 150000005347 biaryls Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000295 emission spectrum Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000010257 thawing Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
Landscapes
- Investigating Or Analysing Materials By The Use Of Chemical Reactions (AREA)
Abstract
The invention provides a freezing history indicator, which comprises diaryl viologen and guanidine macrocycles, wherein the diaryl viologen has the structure: R is an electron donating group such as methylthio, methoxy, azomethine and the like; the guanidine macrocyclic structure is as follows: The freezing history indicator has low cost, can independently indicate samples after encapsulation, generates fluorescent colors with obvious contrast before and after freezing, keeps unchanged after the fluorescent colors are restored to normal state from freezing, does not restore to normal state before freezing, has good display effect, and can clearly indicate whether a substance is subjected to the freezing process. The technology is based on the materials with low cost, small dosage and easy preparation of portable labels, and can be used for detecting the freezing history of the whole logistics process of the products.
Description
Technical Field
The invention relates to the field of monitoring and indicating, in particular to a freezing history indicator and application thereof, in particular to a composition, a device comprising the composition and a method for monitoring whether food, medicines and the like are frozen or not by using the freezing history indicator and the device.
Background
In daily life, because of the complexity of environmental factors, articles such as food, medicines and the like may undergo a supercooled freezing ice way and recover to a non-freezing state, ice crystals generated by the way damage cells or protein structures, so that phenomena such as accelerated spoilage of the food, inactivation of the medicines and the like are caused, and for observers, historical information of the way is missing, observers hardly judge whether the substances undergo a freezing process from appearance, and in the actual production and transportation process, although accurate temperature recording devices such as a digital thermometer and the like can be adopted to record whether batch articles undergo the freezing process, the batch articles are difficult to accurately reach single objects, the display effect is not clear enough, and the problem of judging the appearance is not solved. The current lack of a low cost, easy freeze indication technique, and the application of low cost, easy indicators to monitor this historical process, has become a need and challenge.
The freezing history indicator has low cost, can independently indicate samples after encapsulation, generates fluorescent color with obvious contrast when the indicator is frozen, keeps unchanged when the fluorescent color is restored to a normal state from freezing, does not restore to the normal state before freezing, has good display effect, and can clearly indicate whether a substance is subjected to a freezing process. The technology is based on the materials with low cost, small dosage and easy preparation of portable labels, and can be used for detecting the freezing history of the whole logistics process of the products.
Disclosure of Invention
The invention aims to solve the problem that the freezing history information may be lost in the transportation and preservation process of foods or medicines, and provides an indicator for simply monitoring the freezing history and an application thereof, so as to solve the problem in the background technology.
In order to achieve the above purpose, the present invention provides the following technical solutions:
a freeze history indicator comprising a diaryl viologen and a guanidine macrocycle:
the diaryl viologen structure is as follows:
R is an electron donating group;
The guanidine macrocyclic structure is as follows:
still further, the electron donating group is methylthio, methoxy or azomethine. Still further, n=8 in the guanidine macrocyclic structure.
Further, the molar ratio of the diaryl viologen to the guanidine macrocycle is 1:0.5-2.
Still further, the method also comprises a solvent, wherein the solvent is pure water.
Further, the preparation method of the diaryl viologen comprises the following steps: heating and refluxing 1,1 '-bis (2, 4-dinitrophenyl) -4,4' -bipyridinium dichloride and aniline with electron donating groups at para position in ethanol solution, cooling reactants to room temperature, removing ethanol by rotary evaporation under reduced pressure, adding a small amount of methanol into the obtained solid for dissolution, dripping a large amount of diethyl ether for sedimentation, repeating the sedimentation of the methanol solution and the diethyl ether for multiple times, and then carrying out vacuum drying to obtain the product.
Further, the glucoside urea and the paraformaldehyde are condensed under the acidic condition and subjected to multistage recrystallization to obtain the glucoside urea.
The invention further aims to provide a freezing history indicating device, wherein a slice with a groove is bonded with an interface of an article storage container by ultraviolet photosensitive adhesive, a liquid injection port is reserved at a bonding position in advance during bonding, a mixed liquid prepared by diaryl viologen and guanidine macrocycles at room temperature is injected under the condition of ensuring no bubble residue, and finally the liquid injection port is sealed by the adhesive to obtain the freezing history indicating device.
The flakes deform or melt when heated to 80 ℃.
The material of the article storage container includes glass, plastic, etc.
It is another object of the present invention to provide a use of a freeze history indicator for monitoring a freeze history.
Upon freeze activation, R is an electron donating group that facilitates the formation of a specific assembled structure between the biaryl viologen and the guanidine macrocycle, and after the temperature returns to room temperature, the thermal fluctuation is insufficient to be overcomeThe activated assembly structure returns to the state before being frozen and activated, so that the freezing history indication and record are realized.
The electron donating group containing the hetero atom has n-pi transition, and absorption and emission are red-shifted and fall in a visible light region, so that the electron donating group is convenient for naked eyes to observe.
Compared with the prior art, the technical scheme provided by the invention has the following technical effects:
The freezing history indicator has low cost, the packaged freezing history indicator can independently indicate the sample, the indicator generates fluorescent color with obvious contrast when the indicator is frozen, the fluorescent color is unchanged after the indicator is restored to a normal state from freezing, the indicator is not restored to the normal state before freezing, the display effect is good, and whether a substance is frozen or not can be clearly indicated. The technology is based on the materials with low cost, small dosage and easy preparation of portable labels, and can be used for detecting the freezing history of the whole logistics process of the products.
Drawings
In order to more clearly illustrate the embodiments of the application or the technical solutions in the prior art, the drawings that are required in the embodiments or the description of the prior art will be briefly described, it being obvious that the drawings in the following description are only some embodiments of the application, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 shows an indicator B formed by packaging an experimental group 1 and a control group 2 according to the present invention;
fig. 2 shows the indication states of the experimental group 1 and the control group 2 of the indication device B of the present invention at room temperature;
Fig. 3 shows the indication states of the indication device B of the present invention in the experimental group 1 (subjected to the freezing process, not thawed) and the control group 2 (subjected to the cooling process, not frozen);
fig. 4 shows the indication state of the indicator B of the present invention in the experimental group 1 (subjected to the freezing process, thawed) and the control group 2 (subjected to the cooling process, not frozen).
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
The diaryl viologen structure is as follows:
R is methylthio;
heating and refluxing 1,1 '-bis (2, 4-dinitrophenyl) -4,4' -bipyridinium dichloride and aniline with electron donating group methylthio at para position in ethanol solution for 6 hours, cooling reactant to room temperature, removing ethanol by reduced pressure rotary evaporation at 50 ℃, adding a small amount of methanol into the obtained solid for dissolution, dripping a large amount of diethyl ether for sedimentation, repeating the sedimentation of methanol solution-diethyl ether twice, and vacuum drying to obtain the product.
The guanidine macrocyclic structure is as follows:
n＝8。
Condensing the glycoluril and the paraformaldehyde under the acidic condition, and performing multistage recrystallization to obtain the product.
And (3) the indicating device A is formed by bonding a sheet with a groove and an interface of an article storage container by using an ultraviolet photosensitive adhesive, leaving a liquid injection port at the bonding position in advance, injecting a mixed liquid prepared by the diaryl viologen and the guanidine macrocycle according to the molar ratio of 1:0.5 into the mixed liquid under the condition of ensuring no bubble residue, and finally sealing the liquid injection port by using the adhesive to obtain the freezing history indicating device A.
Example 2
The diaryl viologen structure is as follows:
R is methoxy;
heating and refluxing 1,1 '-bis (2, 4-dinitrophenyl) -4,4' -bipyridinium dichloride and aniline with electron donating group methoxy at para position in ethanol solution for 6 hours, cooling reactant to room temperature, removing ethanol by reduced pressure rotary evaporation at 50 ℃, adding a small amount of methanol into the obtained solid to dissolve, dripping a large amount of diethyl ether to settle, repeating the above methanol solution-diethyl ether settlement for two times, and vacuum drying to obtain the product.
The guanidine macrocyclic structure is as follows:
n＝8。
Condensing the glycoluril and the paraformaldehyde under the acidic condition, and performing multistage recrystallization to obtain the product.
And the indicating device B is used for bonding the interface of the sheet with the groove and the article storage container by using an ultraviolet photosensitive adhesive, a liquid injection port is reserved at the bonding position in advance during bonding, the mixed liquid prepared by the diaryl viologen and the guanidine macrocycle according to the molar ratio of 1:1 is injected into the mixed liquid under the condition of ensuring no bubble residue, and finally the liquid injection port is sealed by using the adhesive, so that the freezing history indicating device B is obtained.
Example 3
The diaryl viologen structure is as follows:
r is azomethine;
Heating and refluxing 1,1 '-bis (2, 4-dinitrophenyl) -4,4' -bipyridinium dichloride and aniline with electron donating group nitrogen dimethyl at para position in ethanol solution for 6 hours, cooling reactant to room temperature, removing ethanol by reduced pressure rotary evaporation at 50 ℃, adding a small amount of methanol into the obtained solid for dissolution, dripping a large amount of diethyl ether for sedimentation, repeating the above methanol solution-diethyl ether sedimentation for three times, and vacuum drying to obtain the product.
The guanidine macrocyclic structure is as follows:
n＝8。
Condensing the glycoluril and the paraformaldehyde under the acidic condition, and performing multistage recrystallization to obtain the product.
And the indicating device C is used for bonding the interface of the sheet with the groove and the article storage container by using an ultraviolet photosensitive adhesive, a liquid injection port is reserved at the bonding position in advance during bonding, the mixed liquid prepared by the diaryl viologen and the guanidine macrocycle according to the molar ratio of 1:2 is injected into the mixed liquid under the condition of ensuring no bubble residue, and finally the liquid injection port is sealed by using the adhesive, so that the freezing history indicating device C is obtained.
Example 4
The experimental group 1 and the control group 2 are all pure water, and freeze history indicators are encapsulated on a bottle cap to form an indicating device 2, see figure 1; both experimental group 1 and control group 2 showed orange fluorescence in the initial non-iced state indicator, see fig. 2; the indicator after the freezing process (not thawed) of experimental group 1 showed green fluorescence, and the indicator was still orange after the cooling process (not frozen) of control group 2, see fig. 3; the indicator still showed green fluorescence after thawing of the experimental group 1, and the control group 2 showed orange fluorescence, see fig. 4, i.e. it was able to indicate that the sample underwent a freeze history.
The invention has important application value and wide application potential. The indicator can be applied to the application scene of an aqueous phase system with the monitoring requirement below 0 ℃ not only for monitoring the freezing histories of foods, medicines and the like. For example: in environments where temperature changes are sensitive, such as polar or mountain research stations, such indicators may be used to monitor environmental changes, providing a visual indication of temperature history.
The fluorescence or solution color of the indicator A, B, C in the initial unfrozen state, as well as apparent fluorescence or solution color changes and absorption emission spectrum changes after undergoing an environmental freeze and thaw process at 0 degrees and below.
When the indicator is heated to over 80 ℃, the frozen and activated product can be erased, so that reversible recycling is realized.
Thus, embodiments of the present invention have been described in detail with reference to the accompanying drawings. It should be noted that, in the drawings or the text of the specification, implementations not shown or described are all forms known to those of ordinary skill in the art, and not described in detail.
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 invention thereto, but to limit the invention thereto, and any modifications, equivalents, improvements and equivalents thereof may be made without departing from the spirit and principles of the invention.
Claims (10)
1. A freeze history indicator comprising a diaryl viologen and a guanidine macrocycle, the diaryl viologen having the structure:
R is an electron donating group;
The guanidine macrocyclic structure is as follows:
2. a freeze history indicator according to claim 1, wherein: the electron donor group is methylthio, methoxy or azomethine.
3. A freeze history indicator according to claim 1, wherein: n=8 in the guanidine macrocyclic structure.
4. A freeze history indicator according to claim 1, wherein: the molar ratio of the diaryl viologen to the guanidine macrocycle is 1:0.5-2.
5. A freeze history indicator according to claim 1, wherein: the water-soluble organic solvent also comprises a solvent, wherein the solvent is pure water.
6. A freeze history indicator according to claim 1, wherein: the preparation method of the diaryl viologen comprises the following steps: heating and refluxing 1,1 '-bis (2, 4-dinitrophenyl) -4,4' -bipyridinium dichloride and aniline with electron donating groups at para position in ethanol solution, cooling reactants to room temperature, removing ethanol by rotary evaporation under reduced pressure, adding a small amount of methanol into the obtained solid for dissolution, dripping a large amount of diethyl ether for sedimentation, repeating the sedimentation of the methanol solution and the diethyl ether for multiple times, and then carrying out vacuum drying to obtain the product.
7. A freeze history indicator according to claim 1, wherein: the preparation method of the guanidine macrocycle comprises the following steps: condensing the glycoluril and the paraformaldehyde under the acidic condition, and performing multistage recrystallization to obtain the product.
8. A freeze history indicating device characterized by: encapsulating the freeze history indicator of claim 1, the encapsulating step comprising: and (3) bonding the sheet with the groove with an interface of an article storage container by using an ultraviolet photosensitive adhesive, leaving a liquid injection port at the bonding position in advance during bonding, injecting a mixed liquid prepared from diaryl viologen and guanidine macrocycles at room temperature into the mixed liquid under the condition of ensuring no bubble residue, and finally sealing the liquid injection port by using the adhesive to obtain the freezing history indicating device.
9. Use of a freeze history indicator according to claim 1 or a freeze history indicator according to claim 8 in monitoring a freeze history.
10. The use according to claim 9 in monitoring freeze history, characterized in that: the freeze history indicator or freeze history indicator is capable of monitoring a history indicating whether or not freeze was experienced.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202410096215.1A CN117946660A (en) | 2024-01-24 | 2024-01-24 | Freezing history indicator and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202410096215.1A CN117946660A (en) | 2024-01-24 | 2024-01-24 | Freezing history indicator and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117946660A true CN117946660A (en) | 2024-04-30 |
Family
ID=90791817
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202410096215.1A Pending CN117946660A (en) | 2024-01-24 | 2024-01-24 | Freezing history indicator and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117946660A (en) |
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2024
- 2024-01-24 CN CN202410096215.1A patent/CN117946660A/en active Pending
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