CN110903495A - Fluorescent hydrogel and multi-dimensional information storage system and method - Google Patents
Fluorescent hydrogel and multi-dimensional information storage system and method Download PDFInfo
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Abstract
The invention discloses a preparation method of a fluorescent hydrogel, which comprises the following steps: at least mixing and dissolving a fluorescent monomer, acrylamide, acrylic acid, an initiator and a cross-linking agent to form a pre-polymerization solution, and carrying out polymerization reaction on the pre-polymerization solution to obtain the fluorescent hydrogel. The invention also discloses a multi-dimensional information storage system, which comprises: the fluorescent hydrogel; and the printing agent is used for forming a printing and dyeing pattern on the fluorescent hydrogel. Compared with the prior art, the target fluorescent hydrogel material can be obtained through simple free radical copolymerization, meanwhile, any character information or three-dimensional (gesture) information can be loaded into the fluorescent hydrogel material through a simple ion printing and dyeing technology, the information is encrypted while being recorded, and the hidden information can be presented only under specific ultraviolet light or after water-induced driving is realized. And the loaded information can be erased through acid or other chelating agent treatment, so that the reusability of the material is realized.
Description
Technical Field
The invention relates to the fields of polymer hydrogel and information storage materials, in particular to fluorescent hydrogel and a preparation method thereof, application of the fluorescent hydrogel in multi-level and multi-dimensional information storage, and a multi-dimensional information storage system and method.
Background
In this era of artificial intelligence, the storage of information and its encryption and decryption techniques have become more and more important in the face of the endless phenomena of counterfeiting, privacy disclosure, and other problems. The encryption and decryption of the character information can be traced to the writing with rice water at the earliest time, the hidden information is displayed by iodine through the color reaction, and then the information is displayed by slightly baking on fire after the writing with vinegar or lemon juice. In the 21 st century, new information encryption technologies, including security codes, holographic anti-counterfeiting, fluorescent identification and the like, have been developed successively. However, the above techniques developed at present have some key problems, such as short service life, poor safety, non-reusability, poor flexibility of the substrate material, poor designability, etc.
The hydrogel material with stimulus response can change shape or color under external stimulus (pH, ionic strength, temperature, light, etc.), and particularly, after special molecular design, the hydrogel material can only generate corresponding response to specific stimulus. Therefore, the stimuli-responsive hydrogel material is a good information storage material, and the stored information can be hidden due to the special property of the hydrogel material, so that decryption can be realized under specific conditions.
There is no patent report on the use of hydrogel or soft material for information storage and encryption.
Disclosure of Invention
The invention mainly aims to provide a fluorescent hydrogel and a preparation method thereof, so as to overcome the defects in the prior art.
Another object of the present invention is to provide a multi-dimensional information storage system and method.
In order to achieve the purpose, the invention adopts the following technical scheme:
the embodiment of the invention provides a preparation method of a fluorescent hydrogel, which comprises the following steps: at least mixing and dissolving a fluorescent monomer, acrylamide, acrylic acid, an initiator and a cross-linking agent to form a pre-polymerization solution, and carrying out polymerization reaction on the pre-polymerization solution to obtain the fluorescent hydrogel.
An embodiment of the present invention further provides a multidimensional information storage system, including:
the aforementioned fluorescent hydrogels are,
and the printing agent is used for forming a printing and dyeing pattern on the fluorescent hydrogel.
The embodiment of the invention also provides a multi-dimensional information storage method, which comprises the steps of providing the fluorescent hydrogel and forming a printing and dyeing pattern on the fluorescent hydrogel by using a printing and dyeing agent.
Compared with the prior art, the invention has the beneficial effects that:
1) the fluorescent hydrogel provided by the embodiment of the invention is provided with the fluorescent monomer, can emit fluorescence under ultraviolet light, can realize information storage by controlling the local environment difference on the surface of the gel, and can realize multi-dimensional information storage by changing the internal crosslinking state of the gel. The multidimensional information storage fluorescent hydrogel can realize multilevel and multidimensional information storage and encryption-decryption processes thereof by gradually introducing external stimuli, and the stored information can be erased simply by acid or other chelating agent treatment, so that the material has good reusability.
2) The method comprises the steps of firstly obtaining fluorescent hydrogel through free radical polymerization, then selectively attaching the printing and dyeing substrate material containing corresponding ions to the hydrogel, and realizing two-dimensional, three-dimensional and multi-level information storage and corresponding encryption-decryption processes through the design of time, content and attachment areas. The preparation method is simple, and the target fluorescent hydrogel material can be obtained through simple free radical copolymerization.
3) Through a simple ion printing and dyeing technology, any character information or three-dimensional (gesture) information can be loaded into the fluorescent hydrogel material, the information is encrypted while being recorded, and the hidden information can be presented only under specific ultraviolet light or after water-induced driving is realized.
Drawings
FIG. 1 shows the use of ionic dye-printed controlled fluorescent hydrogels for multi-level, multi-dimensional information storage and decryption in an exemplary embodiment of the present invention.
Fig. 2a and 2b illustrate the storage and decryption process of two-dimensional plane information according to an exemplary embodiment of the present invention.
Fig. 3a, 3b, 3c, and 3d illustrate the storage and decryption process of three-dimensional stereo information according to an exemplary embodiment of the present invention.
Fig. 4 illustrates multiple, multi-level decryption of information in accordance with an exemplary embodiment of the present invention.
Fig. 5a and 5b illustrate an information erasure procedure in an exemplary embodiment of the invention.
Detailed Description
Aiming at the defects of the prior art, the inventor of the invention provides the technical scheme of the invention through long-term research and massive practice. The technical solution, its implementation and principles, etc. will be further explained as follows. It is to be understood, however, that within the scope of the present invention, each of the above-described features of the present invention and each of the features described in detail below (examples) may be combined with each other to form new or preferred embodiments. Not to be reiterated herein, but to the extent of space.
In one aspect of the present invention, a method for preparing a fluorescent hydrogel includes:
at least mixing and dissolving a fluorescent monomer, acrylamide, acrylic acid, an initiator and a cross-linking agent to form a pre-polymerization solution, and carrying out polymerization reaction on the pre-polymerization solution to obtain the fluorescent hydrogel.
In some embodiments, the fluorescent monomer comprises a derivative of pyrene and/or perylene;
in some embodiments, the initiator comprises a free radical initiator.
Further, the free radical initiator comprises any one or the combination of more than two of potassium persulfate, ammonium persulfate and 2-hydroxy-4' - (2-hydroxyethoxy) -2-methyl propiophenone;
in some embodiments, the crosslinking agent comprises a monomer comprising a plurality of double bonds.
Further, the crosslinking agent includes N, N' -methylenebisacrylamide and/or ethylene glycol diacrylate.
In some embodiments, the amount of fluorescent monomer per 5mL of the pre-polymerization solution is 10-30mg, the amount of acrylamide is 1-3g, the amount of acrylic acid is 0.1-0.5mL, the amount of initiator is 50-100mg, and the amount of cross-linking agent is 10-50 mg.
In some embodiments, the polymerization reaction is at a temperature of 4 to 80 ℃ for a time of 2 to 48 hours.
In some embodiments, the method of making comprises: and adding the pre-polymerization solution into a mold for polymerization reaction to obtain the fluorescent hydrogel.
The die is a self-made die and comprises an upper flat plate, a lower flat plate and a middle hollow plate, wherein the upper flat plate and the lower flat plate comprise glass and/or metal plates, the length and the width of the upper flat plate and the lower flat plate are 1mm x 1mm-10mm x 10mm, the middle hollow plate is silicon rubber, and the specification thickness of the middle hollow plate is 0.5mm-3 mm.
The embodiment of the invention also provides the fluorescent hydrogel prepared by the method.
As another aspect of the present invention, a multidimensional information storage system includes:
the aforementioned fluorescent hydrogels are,
and the printing agent is used for forming a printing and dyeing pattern on the fluorescent hydrogel.
In some embodiments, the system further comprises a substrate to support the dye.
In some preferred embodiments, the material of the substrate includes any one or a combination of two or more of filter paper, weighing paper, printing paper and a stamp.
In some embodiments, the source of the dye comprises a solution containing iron ions or an alkaline solution.
In some embodiments, the system further comprises an ultraviolet light source to provide 365nm ultraviolet light to illuminate the fluorescent hydrogel with the printed pattern.
In some embodiments, the system further comprises deionized water to soak the fluorescent hydrogel with the printed pattern.
In some embodiments, the system further comprises an erasing agent to erase the printed pattern formed on the fluorescent hydrogel.
In some preferred embodiments, the scrubbing agent comprises an acid or a chelating agent.
Further, the acid is selected to provide H+The Lewis acid of (1).
Further, the acid includes hydrochloric acid or sulfuric acid.
Further, the erasing agent is an acid solution with the concentration of 0.01-10M.
Further, the chelating agent is selected from chelating agents capable of replacing iron ions.
Further, the chelating agent comprises EDTA.
Further, the erasing agent is EDTA solution with the concentration of 0.1-20M.
The embodiment of the invention also provides a multi-dimensional information storage method, which comprises the following steps: providing the fluorescent hydrogel, and forming a printed pattern on the fluorescent hydrogel by using a printing agent.
In some embodiments, the multi-dimensional information storage method comprises: and contacting the substrate carrying the printing agent with the fluorescent hydrogel, so as to form a printing and dyeing pattern on the fluorescent hydrogel.
In some preferred embodiments, the multidimensional information storage method includes: the same or different substrates carrying the printing agent are contacted with different areas of the fluorescent hydrogel simultaneously or sequentially respectively, so that a plurality of printing patterns are formed on the fluorescent hydrogel.
In some preferred embodiments, the multidimensional information storage method includes: the fluorescent hydrogel with the printed pattern was irradiated with ultraviolet rays having a wavelength of 365nm, thereby displaying corresponding two-dimensional information.
In some embodiments, the fluorescent hydrogel with the printed pattern is soaked in deionized water, such that the fluorescent hydrogel is driven and deformed, thereby displaying the corresponding three-dimensional information.
In some preferred embodiments, the method for preparing the substrate carrying the printing agent comprises: immersing the matrix in the solution containing iron ions or alkaline solution, taking out and drying.
Further, the solution includes a solution containing iron ions or an alkaline solution.
Furthermore, the concentration of the iron ion-containing solution or the alkaline solution is 1-150mM, the dipping time is 0.5-10h, and the drying temperature is 30-100 ℃.
In some preferred embodiments, the material of the substrate includes any one or a combination of two or more of filter paper, weighing paper, printing paper and a stamp.
In some preferred embodiments, the method for preparing the substrate carrying the printing agent further comprises: the substrate is cut into the desired two-dimensional pattern.
Wherein the substrate can be cut into a desired two-dimensional pattern using scissors, a nicking tool, a laser cutter, or the like. For example, wherein a laser cutter is used with a power of 2-80W.
In some preferred embodiments, the substrate carrying the dye is contacted with the fluorescent hydrogel for 0.5-10min to form a printed pattern on the fluorescent hydrogel.
And the hydrogel after primary printing and dyeing realizes patterned display of two-dimensional information under ultraviolet light.
Or contacting the substrate carrying the printing agent with the fluorescent hydrogel for 1-20min, thereby forming a printed pattern on the fluorescent hydrogel.
The hydrogel after the secondary printing and dyeing displays three-dimensional information in water.
In some embodiments, further comprising: the printed pattern on the fluorescent hydrogel is erased with an erase agent.
In some preferred embodiments, the scrubbing agent comprises an acid or a chelating agent.
Further, the acid is selected to provide H+The Lewis acid of (1).
Further, the acid includes hydrochloric acid or sulfuric acid.
Further, the erasing agent is an acid solution with the concentration of 0.01-10M.
Further, the chelating agent is selected from chelating agents capable of replacing iron ions.
Further, the chelating agent comprises EDTA.
Further, the erasing agent is EDTA solution with the concentration of 0.1-20M.
The ionic printing and dyeing controlled fluorescent hydrogel is used for multi-stage and multi-dimensional information storage and decryption processes, and is shown in figure 1.
The storage and decryption process of the two-dimensional plane information is shown in fig. 2a and fig. 2 b.
Wherein, FIG. 2a contains the letters "UCAS", the Chinese characters "Chinese academy" and the decryption of the two-dimensional plane information of various flower-shaped patterns;
fig. 2b includes two-dimensional code 1 and two-dimensional code 2 and the information decryption of the corresponding scanning result. The two-dimensional code hydrogel with the printed patterns is formed by contacting a substrate carrying a printing agent with original hydrogel, and then is scanned under ultraviolet light to realize patterned display of two-dimensional information and obtain decryption information.
The storage and decryption process of the three-dimensional stereo information is shown in fig. 3a, 3b, 3c and 3 d.
Wherein, fig. 3a is a decryption mechanism diagram of three-dimensional information, the hydrogel after the secondary printing and dyeing can display the three-dimensional information in water, and since iron ions are diffused on the gel thickness layer in the printing and dyeing process and give an anisotropic structure to the hydrogel, the hydrogel can be driven due to unbalanced swelling in water; and displaying three-dimensional information when the driving balance is realized.
FIG. 3b is an anisotropic Structure (SEM) of the hydrogel obtained during ionic printing;
FIG. 3c shows different bending angles of the straight hydrogel due to different concentrations of the printing and dyeing ions, and the bending angle increases with the increase of the concentration of the printing and dyeing ions;
FIG. 3d shows that the deformation degree of the three-dimensional complex pattern caused by different concentrations of the printing and dyeing ions is different, and the deformation degree of the printed hydrogel is increased along with the increase of the concentration of the printing and dyeing ions.
The multi-level and multi-level information decryption process is as shown in fig. 4, when the hydrogel is placed under ultraviolet irradiation, the first heavy two-dimensional information is displayed, and when the hydrogel is placed in water, the second heavy three-dimensional information is displayed, so that multi-level and multi-level information decryption is realized.
The erasing of information and the re-use of material are described in fig. 5a, 5 b.
Wherein, FIG. 5a is a mechanism diagram of information erasing, and the printed pattern on the fluorescent hydrogel is erased by the erasing agent.
FIG. 5b shows a process of repeatedly printing and erasing the hydrogel, which can be repeatedly printed and erased.
The technical solutions of the present invention will be described in further detail below with reference to several preferred embodiments and accompanying drawings, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention. The conditions used in the following examples may be further adjusted as necessary, and the conditions used in the conventional experiments are not generally indicated.
Example 1
The embodiment provides a fluorescent hydrogel and a preparation method thereof, which can be used for multi-dimensional information storage, the preparation method adopts free radical polymerization to prepare the fluorescent hydrogel, then filter paper containing iron ions is selectively attached to the hydrogel, and two-dimensional, three-dimensional and multi-level information storage and corresponding encryption-decryption processes are realized through the design of time, iron ion content and attachment areas, and the specific steps are as follows:
(1) firstly, preparing a pyrene monomer with double bonds in a condensation mode; 10mg of PyMA and 10mg of N, N' -dimethylbisacrylamide, 1g of acrylamide and 0.5mL of acrylic acid were subsequently dissolved in deionized water; finally, adding 50mg of initiator Ammonium Persulfate (APS), quickly and uniformly oscillating, and pouring into a grinding tool; the reaction temperature is 4 ℃, the reaction time is 48 hours, and the hydrogel is obtained and cut into the required shape for standby.
(2) Soaking filter paper in 150mM ferric chloride solution for 0.5h, taking out, drying in an oven at 30 ℃, and cutting into required shapes (bar, circle, two-dimensional code, Chinese character and letter) by using a laser cutting machine (with power of 5W); soaking the flower-shaped seal in 150mM ferric chloride solution for 0.5h, taking out, and drying in an oven at 30 deg.C for use.
(3) And (3) contacting the Chinese characters, the two-dimensional codes, the letter filter paper sheets and the flower-shaped seals soaked with 150mM ferric chloride in the step (2) with the bar-shaped, the flower-shaped and the square hydrogel respectively, taking away the printing and dyeing substrate after 0.5min, and realizing decryption of two-dimensional plane information under an ultraviolet lamp with the wavelength of 365 nm.
(4) And (3) respectively contacting the strip-shaped, flower-shaped and circular filter paper sheets in the step (2) with strip-shaped, flower-shaped and circular hydrogel, controlling the contact time to be 1min, taking away the printing and dyeing substrate, and putting the hydrogel into deionized water to obtain three-dimensional shapes with different deformation degrees.
(5) Attaching the letter filter paper obtained in the step 2 to the palm part (surface is wiped with water) of the hand-shaped hydrogel obtained in the step 1 for 0.5 min; printing and dyeing the positions of the thumb, the index finger, the middle finger and the ring finger printed with the P-letter hand-shaped hydrogel for 1min by using strip-shaped filter paper; printing and dyeing the middle finger, ring finger and little finger of the hand-shaped hydrogel printed with the R letter for 1min by using strip-shaped filter paper; printing with strip filter paper at index finger, middle finger, and ring finger of the C-letter printed hand hydrogel for 1 min. Wherein each letter may also be formed by substrate printing.
(6) And (3) placing the three chiral hydrogels obtained in the step (5) under an ultraviolet lamp with the wavelength of 365nm, wherein the iron ions can cause the quenching of pyrene fluorescence, and the first two-dimensional plane character information can display ' PRC ' (abbreviation of the people's republic of China).
(7) Putting the three hand-shaped hydrogels obtained in the step 5 into deionized water, and driving the hydrogels in water due to unbalanced swelling because iron ions are diffused on the gel thickness layer surface and an anisotropic structure is given to the hydrogels in the printing and dyeing process; when the driving balance is required, gestures representing letters 'I', 'L' and 'Y' in American sign language are displayed, and the gesture means 'I LOVE YOU'. Therefore, if the hydrogel is placed under an ultraviolet lamp of 365nm at the same time, the double two-dimensional and three-dimensional information can be interpreted as 'I love you, China'.
(8) Due to the fact that under the acidic condition, H+The binding capacity with carboxylate ions is stronger than that of Fe3+Therefore, the hydrogel carrying the information in step 5 can be erased in 0.01M HCl solution.
Example 2
(1) By means of polymer grafting, a fluorescent monomer perylene tetracarboxylic acid PTCA is grafted in natural macromolecular gelatin; then, 30mg of PTCA, 50mg of ethylene glycol diacrylate, 2g of acrylamide and 0.3mL of acrylic acid are dissolved in deionized water and are uniformly mixed with the solution; finally, adding 75mg of initiator Ammonium Persulfate (APS), quickly oscillating uniformly, and pouring into a grinding tool; the reaction temperature is 42 ℃, the reaction time is 25 hours, the obtained hydrogel is soaked in deionized water, and the hydrogel is cut into the required shape for standby.
(2) Soaking filter paper in 75mM sodium hydroxide solution for 5h, taking out, drying in an oven at 60 ℃, and cutting into required shapes (bar, circle, two-dimensional code, Chinese character and letter) by using a laser cutting machine (with power of 10W); soaking the flower-shaped seal in 75mM sodium hydroxide solution for 5h, taking out, and drying in an oven at 60 deg.C for use.
(3) And (3) contacting the Chinese characters, the two-dimensional codes, the letter filter paper sheets and the flower-shaped seals soaked in the 75mM sodium hydroxide in the step (2) with the bar-shaped, the flower-shaped and the square hydrogel respectively, taking away the printing and dyeing substrate after 5min, and realizing decryption of two-dimensional plane information under an ultraviolet lamp with the wavelength of 365 nm.
(4) And (3) respectively contacting the strip-shaped, flower-shaped and circular filter paper sheets in the step (2) with strip-shaped, flower-shaped and circular hydrogel, controlling the contact time to be 10min, taking away the printing and dyeing substrate, and putting the hydrogel into deionized water to obtain three-dimensional shapes with different deformation degrees.
(5) Attaching the letter filter paper obtained in the step 2 to the palm part (surface is wiped with water) of the hand-shaped hydrogel obtained in the step 1 for 5 min; printing and dyeing the positions of the thumb, the index finger, the middle finger and the ring finger printed with the P-letter hand-shaped hydrogel for 10min by using strip-shaped filter paper; printing and dyeing the middle finger, ring finger and little finger of the hand-shaped hydrogel printed with the R letter for 10min by using strip-shaped filter paper; printing with strip filter paper for 10min at index finger, middle finger, and ring finger of the C-letter printed hand hydrogel. Wherein each letter may also be formed by substrate printing.
(6) And (3) placing the three chiral hydrogels obtained in the step (5) under an ultraviolet lamp with the wavelength of 365nm, wherein the iron ions can cause the quenching of pyrene fluorescence, and the first two-dimensional plane character information can display ' PRC ' (abbreviation of the people's republic of China).
(7) Putting the three hand-shaped hydrogels obtained in the step 5 into deionized water, and driving the hydrogels in water due to unbalanced swelling because iron ions are diffused on the gel thickness layer surface and an anisotropic structure is given to the hydrogels in the printing and dyeing process; when the driving balance is required, gestures representing letters 'I', 'L' and 'Y' in American sign language are displayed, and the gesture means 'I LOVE YOU'. Therefore, if the hydrogel is placed under an ultraviolet lamp of 365nm at the same time, the double two-dimensional and three-dimensional information can be interpreted as 'I love you, China'.
(8) Due to the fact that under the acidic condition, H+The binding capacity with carboxylate ions is stronger than that of Fe3+So the hydrogel carrying the information of step 5 can be erased in 10M HCl solution.
Example 3
(1) Firstly, preparing a pyrene monomer with double bonds in a condensation mode; subsequently 20mg of PyMA and 30mg of N, N' -dimethylbisacrylamide, 3g of acrylamide and 0.1mL of acrylic acid were dissolved in deionized water; finally, 100mg of initiator Ammonium Persulfate (APS) is added, and the mixture is poured into a grinding tool after being rapidly and uniformly oscillated; the reaction temperature is 80 ℃, the reaction time is 2 hours, and the obtained hydrogel is cut into the required shape for standby.
(2) Soaking filter paper in 1mM ferric chloride solution for 10h, taking out, drying in an oven at 100 ℃, and cutting into required shapes (bar, circle, two-dimensional code, Chinese character and letter) by using a laser cutting machine (with power of 80W); the flower-shaped seal is soaked in 1mM ferric chloride solution for 10h, taken out and put in an oven at 100 ℃ for drying for later use.
(3) And (3) contacting the Chinese characters, the two-dimensional codes, the letter filter paper sheets and the flower-shaped seals soaked with 1mM ferric chloride in the step (2) with the bar-shaped, flower-shaped and square hydrogel respectively, taking away the printing and dyeing substrate after 10min, and realizing decryption of two-dimensional plane information under an ultraviolet lamp with the wavelength of 365 nm.
(4) And (3) respectively contacting the strip-shaped, flower-shaped and circular filter paper sheets in the step (2) with strip-shaped, flower-shaped and circular hydrogel, controlling the contact time to be 20min, taking away the printing and dyeing substrate, and putting the hydrogel into deionized water to obtain three-dimensional shapes with different deformation degrees.
(5) Attaching the letter filter paper obtained in the step 2 to the palm part (surface is wiped with water) of the hand-shaped hydrogel obtained in the step 1 for 10 min; printing and dyeing the positions of the thumb, the index finger, the middle finger and the ring finger printed with the P-letter hand-shaped hydrogel for 20min by using strip-shaped filter paper; printing and dyeing the middle finger, ring finger and little finger of the hand-shaped hydrogel printed with the R letter for 20min by using strip-shaped filter paper; printing with strip filter paper at index finger, middle finger, and ring finger of the C-letter printed hand type hydrogel for 20 min. Wherein each letter may also be formed by substrate printing.
(6) And (3) placing the three chiral hydrogels obtained in the step (5) under an ultraviolet lamp with the wavelength of 365nm, wherein the iron ions can cause the quenching of pyrene fluorescence, and the first two-dimensional plane character information can display ' PRC ' (abbreviation of the people's republic of China).
(7) Putting the three hand-shaped hydrogels obtained in the step 5 into deionized water, and driving the hydrogels in water due to unbalanced swelling because iron ions are diffused on the gel thickness layer surface and an anisotropic structure is given to the hydrogels in the printing and dyeing process; when the driving balance is required, gestures representing letters 'I', 'L' and 'Y' in American sign language are displayed, and the gesture means 'I LOVE YOU'. Therefore, if the hydrogel is placed under an ultraviolet lamp of 365nm at the same time, the double two-dimensional and three-dimensional information can be interpreted as 'I love you, China'.
(8) Because the binding capacity of EDTA and carboxylate ions is stronger than that of Fe under the acidic condition3+So step 5 the information carrying hydrogel can be erased in a 20M EDTA solution.
Example 4
(1) Firstly, preparing a pyrene monomer with double bonds in a condensation mode; subsequently 20mg of PyMA and 50mg of N, N' -dimethylbisacrylamide, 3g of acrylamide and 0.1mL of acrylic acid were dissolved in deionized water; finally, 100mg of initiator Ammonium Persulfate (APS) is added, and the mixture is poured into a grinding tool after being rapidly and uniformly oscillated; the reaction temperature is 80 ℃, the reaction time is 2 hours, and the obtained hydrogel is cut into the required shape for standby.
(2) Soaking filter paper in 1mM ferric chloride solution for 10h, taking out, drying in an oven at 100 ℃, and cutting into required shapes (bar, circle, two-dimensional code, Chinese character and letter) by using a laser cutting machine (with power of 80W); the flower-shaped seal is soaked in 1mM ferric chloride solution for 10h, taken out and put in an oven at 100 ℃ for drying for later use.
(3) And (3) contacting the Chinese characters, the two-dimensional codes, the letter filter paper sheets and the flower-shaped seals soaked with 1mM ferric chloride in the step (2) with the bar-shaped, flower-shaped and square hydrogel respectively, taking away the printing and dyeing substrate after 10min, and realizing decryption of two-dimensional plane information under an ultraviolet lamp with the wavelength of 365 nm.
(4) And (3) respectively contacting the strip-shaped, flower-shaped and circular filter paper sheets in the step (2) with strip-shaped, flower-shaped and circular hydrogel, controlling the contact time to be 20min, taking away the printing and dyeing substrate, and putting the hydrogel into deionized water to obtain three-dimensional shapes with different deformation degrees.
(5) Attaching the letter filter paper obtained in the step 2 to the palm part (surface is wiped with water) of the hand-shaped hydrogel obtained in the step 1 for 10 min; printing and dyeing the positions of the thumb, the index finger, the middle finger and the ring finger printed with the P-letter hand-shaped hydrogel for 20min by using strip-shaped filter paper; printing and dyeing the middle finger, ring finger and little finger of the hand-shaped hydrogel printed with the R letter for 20min by using strip-shaped filter paper; printing with strip filter paper at index finger, middle finger, and ring finger of the C-letter printed hand type hydrogel for 20 min. Wherein each letter may also be formed by substrate printing.
(6) And (3) placing the three chiral hydrogels obtained in the step (5) under an ultraviolet lamp with the wavelength of 365nm, wherein the iron ions can cause the quenching of pyrene fluorescence, and the first two-dimensional plane character information can display ' PRC ' (abbreviation of the people's republic of China).
(7) Putting the three hand-shaped hydrogels obtained in the step 5 into deionized water, and driving the hydrogels in water due to unbalanced swelling because iron ions are diffused on the gel thickness layer surface and an anisotropic structure is given to the hydrogels in the printing and dyeing process; when the driving balance is required, gestures representing letters 'I', 'L' and 'Y' in American sign language are displayed, and the gesture means 'I LOVE YOU'. Therefore, if the hydrogel is placed under an ultraviolet lamp of 365nm at the same time, the double two-dimensional and three-dimensional information can be interpreted as 'I love you, China'.
(8) Because the binding capacity of EDTA and carboxylate ions is stronger than that of Fe under the acidic condition3+Therefore, the hydrogel carrying information in step 5 can be erased in 0.1M EDTA solution.
In summary, according to the above technical solution of the present invention, the method for preparing the fluorescent hydrogel of the present invention can obtain the target fluorescent hydrogel material through simple radical copolymerization, and at the same time, through a simple ion printing and dyeing technology, arbitrary text information or three-dimensional (gesture) information can be loaded into the fluorescent hydrogel material, and the information is encrypted while being recorded, so that the hidden information can be presented only under specific ultraviolet light or after water-induced driving is realized. And the loaded information can be erased through acid or other chelating agent treatment, so that the reusability of the material is realized.
In addition, the inventors also conducted experiments with other materials and conditions listed in the present specification, and the like, in the manner of examples 1 to 3, and also produced a fluorescent hydrogel that can be used for multi-level, multi-dimensional information storage.
It should be noted that, in the present document, in a general case, an element defined by the phrase "includes.
It should be understood that the above-mentioned examples are only for illustrating the technical idea and features of the present invention, and the purpose of the present invention is to enable those skilled in the art to understand the content of the present invention and to implement the present invention, and not to limit the protection scope of the present invention. All equivalent changes and modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.
Claims (10)
1. A method of making a fluorescent hydrogel, comprising: at least mixing and dissolving a fluorescent monomer, acrylamide, acrylic acid, an initiator and a cross-linking agent to form a pre-polymerization solution, and carrying out polymerization reaction on the pre-polymerization solution to obtain the fluorescent hydrogel.
2. The method of claim 1, wherein: the fluorescent monomer comprises pyrene and/or perylene derivatives;
and/or, the initiator comprises a free radical initiator; preferably, the free radical initiator comprises any one or the combination of more than two of potassium persulfate, ammonium persulfate and 2-hydroxy-4' - (2-hydroxyethoxy) -2-methyl propiophenone;
and/or, the cross-linking agent comprises a monomer comprising a plurality of double bonds; preferably, the cross-linking agent comprises N, N' -methylenebisacrylamide and/or ethylene glycol diacrylate;
and/or, the content of the fluorescent monomer in each 5mL of the pre-polymerization solution is 10-30mg, the content of acrylamide is 1-3g, the content of acrylic acid is 0.1-0.5mL, the content of the initiator is 50-100mg, and the content of the cross-linking agent is 10-50 mg;
and/or the temperature of the polymerization reaction is 4-80 ℃ and the time is 2-48 h;
and/or the preparation method comprises the following steps: and adding the pre-polymerization solution into a mold for polymerization reaction to obtain the fluorescent hydrogel.
3. A fluorescent hydrogel prepared by the method of any one of claims 1-2.
4. A multi-dimensional information storage system, comprising:
the fluorescent hydrogel of claim 3,
and the printing agent is used for forming a printing and dyeing pattern on the fluorescent hydrogel.
5. The system of claim 4, wherein: the system further comprises a substrate to support the dye; preferably, the material of the substrate comprises any one or a combination of more than two of filter paper, weighing paper, printing paper and a stamp; and/or the source of the printing agent comprises a solution containing iron ions or an alkaline solution; and/or the system further comprises an ultraviolet light source, wherein the ultraviolet light source is used for providing ultraviolet light with the wavelength of 365nm to irradiate the fluorescent hydrogel with the printed patterns; and/or the system also comprises deionized water used for soaking the fluorescent hydrogel with the printed patterns; and/or, the system further comprises an erasing agent for erasing the printed pattern formed on the fluorescent hydrogel; preferably, the scrubbing agent comprises an acid or a chelating agent; preferably, the acid is selected to provide H+The Lewis acid of (1); preferably, the acid comprises a saltAn acid or sulfuric acid; preferably, the erasing agent is an acid solution with the concentration of 0.01-10M; preferably, the chelating agent is selected from chelating agents capable of replacing iron ions; preferably, the chelating agent comprises EDTA; preferably, the erasing agent is EDTA solution with the concentration of 0.1-20M.
6. A multi-dimensional information storage method is characterized by comprising the following steps: providing the fluorescent hydrogel of claim 3 and forming a printed pattern on the fluorescent hydrogel with a dye.
7. The multidimensional information storage method of claim 6, wherein the multidimensional information storage method comprises: contacting the substrate carrying the printing agent with the fluorescent hydrogel, thereby forming a printed pattern on the fluorescent hydrogel;
preferably, the multidimensional information storage method includes: simultaneously or sequentially contacting the same or different substrates carrying the printing dye with different areas of the fluorescent hydrogel respectively so as to form a plurality of printing and dyeing patterns on the fluorescent hydrogel;
preferably, the multidimensional information storage method includes: irradiating the fluorescent hydrogel with the printed patterns by using ultraviolet rays with the wavelength of 365nm so as to display corresponding two-dimensional information; and/or soaking the fluorescent hydrogel with the printed patterns in deionized water, so that the fluorescent hydrogel is driven and deformed, and corresponding three-dimensional information is displayed.
8. The multidimensional information storage method of claim 7, wherein the preparation method of the substrate carrying the printing agent comprises: soaking the matrix in iron ion-containing solution or alkaline solution, taking out, and drying; preferably, the solution comprises a solution containing iron ions or an alkaline solution; preferably, the concentration of the iron ion-containing solution or the alkaline solution is 1-150mM, the dipping time is 0.5-10h, and the drying temperature is 30-100 ℃; and/or the substrate material comprises any one or the combination of more than two of filter paper, weighing paper, printing paper and a seal;
and/or the preparation method of the substrate carrying the printing agent further comprises the following steps: the substrate is cut into the desired two-dimensional pattern.
9. The multidimensional information storage method of claim 7, wherein: contacting the substrate carrying the printing and dyeing agent with the fluorescent hydrogel for 0.5-10min, thereby forming a printed and dyed pattern on the fluorescent hydrogel; or contacting the substrate carrying the printing agent with the fluorescent hydrogel for 1-20min, thereby forming a printed pattern on the fluorescent hydrogel.
10. The multidimensional information storage method of claim 6, further comprising: erasing the printed and printed patterns on the fluorescent hydrogel by using an erasing agent; preferably, the scrubbing agent comprises an acid or a chelating agent; preferably, the acid is selected to provide H+The Lewis acid of (1); preferably, the acid comprises hydrochloric acid or sulfuric acid; preferably, the erasing agent is an acid solution with the concentration of 0.01-10M; preferably, the chelating agent is selected from chelating agents capable of replacing iron ions; preferably, the chelating agent comprises EDTA; preferably, the erasing agent is EDTA solution with the concentration of 0.1-20M.
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| CN114907842A (en) * | 2022-05-17 | 2022-08-16 | 中国科学院宁波材料技术与工程研究所 | Fluorescent carbon quantum dot gel, preparation method thereof and information circulating storage method |
| CN114907842B (en) * | 2022-05-17 | 2023-12-22 | 中国科学院宁波材料技术与工程研究所 | Fluorescent carbon quantum dot gel, preparation method thereof and information circulating storage method |
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