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CN-117946660-B - Freezing history indicator and application thereof

CN117946660BCN 117946660 BCN117946660 BCN 117946660BCN-117946660-B

Abstract

The invention provides a freezing history indicator, which comprises diaryl viologen and guanidine macrocycles, wherein the diaryl viologen has the structure: The R is electron donating groups such as methylthio, methoxy, azomethine and the like, and 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.

Inventors

  • WU GUANGLU
  • QU HAOYUAN

Assignees

  • 吉林大学

Dates

Publication Date
20260512
Application Date
20240124

Claims (6)

  1. 1. A freezing history indicator is characterized by comprising the steps of packaging a freezing history indicator, wherein the freezing history indicator comprises diaryl viologen and guanidine macrocycle, the packaging steps comprise the steps of bonding a slice with a groove and an interface of an article storage container by 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 at room temperature into the mixed liquid under the condition of ensuring no bubble residue, finally sealing the liquid injection port by the adhesive to obtain the freezing history indicator, The diaryl viologen structure is as follows: , wherein R is an electron donating group; the guanidine macrocyclic structure is as follows: ,n=8; the electron donating group in the diaryl viologen structure is methylthio, methoxy or azomethine, and the molar ratio of the diaryl viologen to the guanidine macrocycle is 1:0.5-2.
  2. 2. The freezing history indicating apparatus as claimed in claim 1, wherein the freezing history indicator further comprises a solvent, and the solvent is pure water.
  3. 3. The freezing history indicating apparatus according to claim 1, wherein the diaryl viologen is prepared by heating and refluxing 1,1 '-bis (2, 4-dinitrophenyl) -4,4' -bipyridinium dichloride and aniline having an electron donating group at the para position in an ethanol solution, cooling the reactant to room temperature, removing ethanol by rotary evaporation under reduced pressure, dissolving the obtained solid with methanol, dropping in diethyl ether, settling, repeating the above methanol dissolution-diethyl ether settling, and vacuum drying to obtain the product.
  4. 4. The freezing history indicating apparatus according to claim 1, wherein the guanidine macrocycle is prepared by condensing and recrystallizing a guanylurea and a paraformaldehyde under an acidic condition.
  5. 5. Use of a freeze history indicator according to claim 1 in monitoring a freeze history.
  6. 6. The use of claim 5, wherein said freeze history indicator is capable of monitoring a history indicating whether or not a freeze has been experienced.

Description

Freezing history indicator and application thereof 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. And the preparation method of the diaryl viologen comprises the steps of heating and refluxing 1,1 '-bis (2, 4-dinitrophenyl) -4,4' -bipyridinium dichloride and aniline with an electron donating group at the 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 fluct