Preparation and application method of room-temperature phosphorescent material based on cucurbit [8] uril and 6-bromoisoquinoline derivative

Abstract

The invention discloses a preparation method and an application method of a room-temperature phosphorescent material based on a cucurbit [8] uril and 6-bromoisoquinoline derivative. According to the room-temperature phosphorescent material, cucurbit [8] urils and 6-bromoisoquinoline derivatives are combined through host-guest interaction to form a supramolecular compound, and then the supramolecular compound is doped into polyvinyl alcohol (PVA) to prepare a light-emitting film or a light-emitting viscous liquid. The luminescent material can be applied to the field of encryption and counterfeiting prevention, and the specific operation steps are as follows: 1) preparing a supramolecular compound Q [8]-2BI-BOH; (2) doping the supramolecular compound into polyvinyl alcohol (PVA) to prepare a light-emitting film or light-emitting mucus; 3) different dyes are introduced as energy acceptors, the afterglow color is adjusted according to energy transfer between the acceptors, and the multi-color afterglow luminescent material is applied to the field of anti-counterfeiting encryption based on the characteristic of multi-color afterglow luminescence and has the advantages of being easy to prepare, simple in color matching, easy to operate and obvious in visual effect.

Description

Technical Field

[0001] The invention relates to preparation and application of a room temperature phosphorescent material based on an eight-membered cucurbit ring and a 6-bromoisoquinoline derivative, and belongs to the technical field of analytical chemistry. Background Art

[0002] With the rapid development of society, the speed and amount of information generated are increasing. How to effectively store and manage this information has become a major challenge. There are counterfeiting problems in many fields, such as tickets, banknotes, certificates, etc. Information security has become a global challenge! Then a variety of anti-counterfeiting encryption technologies emerged, but these technologies have problems such as cumbersome production process, high technical difficulty, and high manufacturing cost. Luminescent materials play an important role in the field of encryption and anti-counterfeiting due to their advantages such as easy operation, high concealment and easy design.

[0003] Therefore, the development of a simple and advanced optical security technology with complex properties is very necessary to combat counterfeiting and is of great significance for strengthening the encryption and anti-counterfeiting of information. Summary of the invention

[0004] The purpose of the present invention is to provide a preparation method and application of a room temperature phosphorescent material based on an eight-membered cucurbitacin and a 6-bromoisoquinoline derivative, so as to enhance the security of information.

[0005] The technical solution of the present invention is a method for preparing a room temperature phosphorescent material based on an eight-membered cucurbitacin and a 6-bromoisoquinoline derivative. The room temperature phosphorescent material is prepared from an eight-membered cucurbitacin aqueous solution and a 6-bromoquinoline derivative aqueous solution.

[0006] The aforementioned method for preparing a room temperature phosphorescent material based on an eight-membered cucurbit ring and a 6-bromoisoquinoline derivative specifically comprises the following steps: (1) 6-bromoisoquinoline and phenylboronic acid were used as raw materials, acetonitrile solution was added until they were dissolved, and the reaction was refluxed at 80°C for 8 hours. After cooling, methanol was used as an eluent, and separation and purification were performed using a thin layer chromatography column to obtain an eluent, which was then subjected to reduced pressure distillation to obtain a white solid. The white solid was then washed with dichloromethane for 2 to 3 times, and finally vacuum dried to obtain a 6-bromoquinoline derivative, 6-bromoisoquinoline: phenylboronic acid: acetonitrile solution = 400 mg: 413 mg: 30 mL; (2) Weigh the eight-membered cucurbitacin and 6-bromoquinoline derivative in a molar ratio of 1:2 to prepare a solution with a concentration of 1.0×10 -2 mol / L Q[8]-2BI-BOH assembly solution; (3) Weigh an appropriate amount of polyvinyl alcohol and heat under reflux at 90 °C to obtain a PVA solution with a concentration of 20 g / L; (4) Press V PVA : VQ[8]-2BI-BOH =100:1, add PVA solution, Q[8]-2BI-BOH assembly solution, or different dyes, heat and stir until the viscosity of the solution is appropriate, and then the desired different room temperature phosphorescent materials can be obtained.

[0007] In the aforementioned method for preparing room temperature phosphorescent materials based on eight-membered cucurbit rings and 6-bromoisoquinoline derivatives, in said (4), when different dyes are added, different room temperature phosphorescent materials are prepared according to the following method: (4) Weigh the dyes rhodamine B and butyl rhodamine B and prepare them to a concentration of 1.0×10 -2 mol / L solution, press V PVA : V Q[8]-2BI-BOH =100:1, N 染料 : N Q[8]-2BI-BOH =1:20, add PVA solution, Q[8]-2BI-BOH assembly solution and different dyes, heat and stir, and when the viscosity of the solution is appropriate, different room temperature phosphorescent materials can be obtained.

[0008] The invention discloses an application method of a room temperature phosphorescent material based on an eight-membered cucurbit ring and a 6-bromoisoquinoline derivative, and the room temperature phosphorescent material is applied to encryption and anti-counterfeiting.

[0009] In the aforementioned application method of the room temperature phosphorescent material based on the eight-membered cucurbit ring and the 6-bromoisoquinoline derivative, the room temperature phosphorescent material is drawn into the desired shape on the filter paper; or painted into the desired numbers or letters, and then the material is irradiated with 365 nm ultraviolet light, and then the light source is turned off. The pattern, numbers, and letters will change according to the different afterglow colors of the material, thereby achieving the effect of encryption and anti-counterfeiting.

[0010] In the aforementioned application method of the room temperature phosphorescent material based on the eight-membered cucurbit ring and the 6-bromoisoquinoline derivative, the encryption methods are as follows: (1) The three prepared viscous liquids Q[8]-BI-BOH-PVA-BRhB, Q[8]-BI-BOH-PVA and Q[8]-BI-BOH-PVA-RhB are used to draw the desired pattern, number or letter on the filter paper, and the filter paper is dried at 80°C. The pattern, number or letter drawn by the Q[8]-BI-BOH-PVA viscous liquid is basically invisible under a fluorescent light. The filter paper is irradiated with a 365 nm ultraviolet light for a period of time, and the ultraviolet light is turned off. After 1.5 seconds, only the pattern, number or letter drawn by the Q[8]-BI-BOH-PVA viscous liquid can be seen, and the afterglow shows the information that cannot be seen under the fluorescent light, thereby achieving the effect of information encryption; (2) Use Q[8]-BI-BOH-PVA viscous liquid to paint the first pattern, letters or numbers, place it in an oven at 80 °C for 1 h, then use the corresponding Q[8]-BI-BOH-PVA viscous liquid to paint the above shape into the second pattern, letters or numbers, continue to dry for 0.5 h, and under the irradiation of 365 nm ultraviolet light, the information of the second pattern, letters or numbers is displayed in blue. After irradiation for a period of time, turn off the UV light, and the afterglow displays the information of the first pattern, letters or numbers; (3) First, use Q[8]-BI-BOH-PVA-BRhB viscous liquid to paint the first pattern, letters or numbers, place it in an oven at 80°C for 1 hour, and then use the corresponding Q[8]-BI-BOH-PVA-BRhB viscous liquid to paint the above numbers into the second pattern, letters or numbers. Continue to dry for 0.5 hours. Under the irradiation of 365 nm ultraviolet light, the second pink pattern, letters or numbers will be displayed. After irradiation for a period of time, turn off the UV light, and the afterglow will display the information of the first pattern, letters or numbers.

[0011] Beneficial effects of the present invention: Compared with the prior art, the material used for encryption and anti-counterfeiting prepared by the present invention using the above technical solution is a new supramolecular luminescent material based on an eight-membered cucurbit ring and a 6-bromoquinoline derivative (BI-BOH), and different dyes can be added as energy acceptors to adjust the afterglow color according to the energy transfer between the donor and the acceptor, showing afterglow of different colors, achieving an anti-counterfeiting encryption effect. The present invention has the characteristics of simple preparation, simple coloring, simple operation and obvious visual effect. BRIEF DESCRIPTION OF THE DRAWINGS

[0012] Attached Figure 1 This is a synthetic route for 6-bromoisoquinoline derivatives (BI-BOH).

[0013] Attached Figure 2 6-bromoisoquinoline derivative (BI-BOH) 1 H NMR (25°C, 400 MHz, DMSO-d6).

[0014] Attached Figure 3 The fluorescence spectra and UV absorption spectra of the eight-membered cucurbit ring and 6-bromoisoquinoline derivatives; where: (a) the fluorescence spectrum of BI-BOH, the content of Q[8] increases from 0 to 1.0 equivalents with an interval of 0.2; (b) the Job diagram of BI-BOH and Q[8] drawn based on the fluorescence spectrum; (c) the UV absorption spectrum of BI-BOH as the Q[8] content increases from 0, 0.2 ... to 1.2 equivalents; (d) the Job diagram of BI-BOH and Q[8] drawn based on the UV absorption spectrum.

[0015] Attached Figure 4 Phosphorescence emission spectra of the film. (a), (b), and (c) are the cross-plots of the ultraviolet absorption spectra of fluorescent dyes Eosin Y, Butyl Rhodamine B, and Rhodamine B with the phosphorescence emission spectra of Q[8]-BI-BOH film, respectively; (d) is the phosphorescence emission spectra of each dye film.

[0016] Attached Figure 5 The phosphorescence change images of each luminescent film after being dried at 30 ℃, 50 ℃, and 80 ℃ for 1 h, irradiated with ultraviolet light (365 nm) for a period of time, and then turned off the UV light. (a), (b), (c), and (d) are Q[8]-BI-BOH-PVA-BRhB, Q[8]-BI-BOH-PVA-RhB, Q[8]-BI-BOH-PVA-ESY, and Q[8]-BI-BOH-PVA films, respectively.

[0017] Attached Figure 6 The phosphorescence emission spectra of each luminescent film were measured when placed in water vapor fumigation at 30 ℃, 50 ℃, and 80 ℃.

[0018] Attached Figure 7 The infrared spectra of each film after fumigation with water and heating.

[0019] Attached Figure 8 Schematic diagram of the application of luminous viscous liquid materials in encryption and anti-counterfeiting. DETAILED DESCRIPTION

[0020] The present invention is further described below in conjunction with the accompanying drawings and embodiments, but they are not intended to limit the present invention.

[0021] The present invention provides a preparation method and application method of a room temperature phosphorescent material based on an eight-membered cucurbit ring and a 6-bromoisoquinoline derivative. A film or a viscous liquid prepared by adding polyvinyl alcohol (PVA) and using the eight-membered cucurbit ring and a 6-bromoisoquinoline derivative (abbreviated as BI-BOH) is used as a luminescent material, and different dyes such as eosin Y (ESY), rhodamine B (RhB) and butyl rhodamine B (BRhB) are introduced as energy acceptors. The afterglow color is adjusted according to the energy transfer between the donor and the acceptor. Based on the multi-color afterglow luminescence characteristics, the room temperature phosphorescent material is applied to the field of anti-counterfeiting encryption.

[0022] Embodiment 1 of the present invention: A method for preparing a room temperature phosphorescent material based on an eight-membered cucurbitacin and a 6-bromoisoquinoline derivative, wherein the room temperature phosphorescent material is prepared from an aqueous solution of an eight-membered cucurbitacin (Q[8]) and an aqueous solution of a 6-bromoquinoline derivative (BI-BOH).

[0023] The specific steps include: (1) If Figure 1 As shown, 6-bromoisoquinoline (400 mg, 1.922 mmol) and phenylboronic acid (413 mg, 1.922 mmol) are used as raw materials, 30 mL of acetonitrile solution is added until they are dissolved, and the reaction is refluxed at 80°C for 8 h. After cooling, methanol is used as an eluent and separated and purified by a thin layer chromatography column to obtain an eluent, which is then distilled under reduced pressure to obtain a white solid. The white solid is then washed 2 to 3 times with 25 mL of dichloromethane each time, and finally dried in vacuo to obtain a 6-bromoquinoline derivative.

[0024] (2) Weigh the eight-membered cucurbitacin (66 mg, 0.05 mmol) and 6-bromoquinoline derivative (42 mg, 0.10 mmol), add secondary water at pH = 7 to dissolve, and prepare a solution with a concentration of 1.0×10 -2 mol / L Q[8]-2BI-BOH assembly solution. Figure 3 It can be clearly inferred from the spectrum that the reaction ratio of Q[8] to BI-BOH is 1:2.

[0025] (3) Weigh an appropriate amount of polyvinyl alcohol (PVA), add secondary water with a pH of 7, and heat under reflux at 90°C to obtain a PVA solution with a concentration of 20 g / L; (4) Press V PVA : V Q[8]-2BI-BOH =100:1, add PVA solution, Q[8]-2BI-BOH assembly solution, or add different dyes, heat and stir, and when the viscosity of the solution is appropriate, the desired different room temperature phosphorescent materials can be obtained. When no dye is added, the prepared material is Q[8]-BI-BOH-PVA room temperature phosphorescent material.

[0026] When different dyes are added, different room temperature phosphorescent materials are prepared according to the following method: Weigh the dyes eosin Y (ESY), rhodamine B (RhB), and butyl rhodamine B (BRhB) to prepare a concentration of 1.0×10 -2 mol / L solution, press V PVA : V Q[8]-2BI-BOH =100:1, N 染料 : N Q[8]-2BI-BOH =1:20, add PVA solution, Q[8]-2BI-BOH assembly solution and different dyes, heat and stir, and when the viscosity of the solution is appropriate, Q[8]-BI-BOH-PVA-ESY room temperature phosphorescent material, Q[8]-BI-BOH-PVA-RhB room temperature phosphorescent material and Q[8]-BI-BOH-PVA-BRhB room temperature phosphorescent material can be obtained.

[0027] After the above room temperature phosphorescent material is dried, a thin film sample can be obtained, which is convenient for testing the phosphorescence spectrum. Figure 4 It can be seen that the ultraviolet absorption spectra of the fluorescent dyes ESY, BRhB and RhB have obvious spectral overlap with the phosphorescence emission spectrum of the Q[8]-BI-BOH-PVA film, which meets the premise of energy transfer from the triplet state to the singlet state. From Figure 4 (d), it can be seen that the wavelengths of the phosphorescence emission peaks of the Q[8]-BI-BOH-PVA, Q[8]-BI-BOH-PVA-BRhB, Q[8]-BI-BOH-PVA-RhB, and Q[8]-BI-BOH-PVA-ESY films are 515 nm, 579 nm, 580 nm, and 548 nm, respectively.

[0028] The specific preparation process is as follows: 200 μL of Q[8]-2BI-BOH assembly solution was added to four beakers containing 20 mL of PVA solution, and then 10 μL of rhodamine B (1x10 -2 mol•L -1 ), 1 mL of butyl rhodamine B (1x10 -5 mol•L -1 ) and 10 μL of ESY (1x10 -2 mol·L -1 ), heat and stir the solution, and when the solution has an appropriate viscosity, pour the solution into a culture dish or molds of different shapes, and dry at 80°C to obtain Q[8]-BI-BOH-PVA, Q[8]-BI-BOH-PVA-BRhB, Q[8]-BI-BOH-PVA-RhB, and Q[8]-BI-BOH-PVA-ESY film samples.

[0029] Embodiment 2 of the present invention: An application method of a room temperature phosphorescent material based on an eight-membered cucurbitacin and a 6-bromoisoquinoline derivative, wherein the room temperature phosphorescent material is applied to encryption and anti-counterfeiting.

[0030] Specifically, there are several encryption anti-counterfeiting methods: (1) First, three viscous liquids, Q[8]-BI-BOH-PVA-BRhB, Q[8]-BI-BOH-PVA, and Q[8]-BI-BOH-PVA-RhB, were prepared according to the method for preparing a thin film in Example 1. The three viscous liquids were used to draw the shape of a cherry on filter paper, which was then dried at 80°C. Under a fluorescent lamp, the cherry drawn with the Q[8]-BI-BOH-PVA aqueous solution was basically invisible. After irradiation with an ultraviolet lamp (365 nm) for a period of time, only the cherry drawn with the Q[8]-BI-BOH-PVA aqueous solution was visible 1.5 seconds after the UV lamp was turned off. The afterglow showed information that was invisible under the fluorescent lamp, thereby achieving the effect of information encryption.

[0031] (2) Use Q[8]-BI-BOH-PVA aqueous solution to paint the shape of "SOS" in Morse code, place it in an oven at 80 °C for 1 h, then use the corresponding Q[8]-BI-BOH-PVA aqueous solution to paint the above shape into the shape of "OOO" in Morse code, continue to dry for 0.5 h, and under the irradiation of ultraviolet light (365 nm), the information corresponding to "OOO" in Morse code is displayed in blue. After irradiation for a period of time, turn off the UV light, and the information displayed by the afterglow is "SOS".

[0032] (3) The digital code was prepared according to the above method. First, the number "206" was painted with Q[8]-BI-BOH-PVA-BRhB aqueous solution, which was placed in an oven at 80 °C for 1 h. Then, the number "888" was repainted with the corresponding Q[8]-BI-BOH-PVA-BRhB aqueous solution and continued to be dried for 0.5 h. Under the irradiation of ultraviolet light (365 nm), the pink "888" was displayed. After a period of irradiation, the UV light was turned off and the information displayed by the afterglow was "206".

[0033] The above encryption anti-counterfeiting method is combined with Figure 5 , which can prove the influence of temperature on the afterglow duration; Figure 6 It is proved that temperature has a certain influence on the phosphorescence emission of the film. As the temperature increases, the phosphorescence intensity of the film gradually increases. Figure 7 The effect of temperature on phosphorescence properties was further demonstrated by testing the difference in infrared of the film at different temperatures.

[0034] Among the three encryption anti-counterfeiting methods mentioned above, (1) three different viscous liquids with different afterglow colors are used for multi-color anti-counterfeiting, and (2) and (3) two viscous liquids are dried at different times and have different afterglow durations, thereby achieving multiple anti-counterfeiting encryption.

[0035] The reason why Q[8]-BI-BOH-PVA-ESY viscous liquid was not used in the above-mentioned encryption anti-counterfeiting method is that the effect of Q[8]-BI-BOH-PVA-ESY viscous liquid is not as obvious as the other three viscous liquids (Q[8]-BI-BOH-PVA, Q[8]-BI-BOH-PVA-BRhB, Q[8]-BI-BOH-PVA-RhB), so it was discarded.

[0036] The above description is only a preferred specific implementation manner of the present invention, but the protection scope of the present invention is not limited thereto. Any technician familiar with the technical field can make equivalent replacements or changes according to the technical solutions and inventive concepts of the present invention within the technical scope disclosed by the present invention, which should be covered by the protection scope of the present invention.

Claims

1. A method for preparing a room temperature phosphorescent material based on an eight-membered cucurbit ring and a 6-bromoisoquinoline derivative, characterized in that: The room temperature phosphorescent material is prepared from an eight-membered cucurbitacin aqueous solution and a 6-bromoquinoline derivative aqueous solution.

2. The method for preparing a room temperature phosphorescent material based on an eight-membered cucurbit ring and a 6-bromoisoquinoline derivative according to claim 1, characterized in that: The specific steps include: (1) 6-bromoisoquinoline and phenylboronic acid were used as raw materials, acetonitrile solution was added until they were dissolved, and the reaction was refluxed at 80°C for 8 h. After cooling, methanol was used as an eluent, and separation and purification were performed using a thin layer chromatography column to obtain an eluent, which was then subjected to reduced pressure distillation to obtain a white solid. The white solid was then washed with dichloromethane for 2 to 3 times, and finally vacuum dried to obtain a 6-bromoquinoline derivative, 6-bromoisoquinoline: phenylboronic acid: acetonitrile solution = 400 mg: 413 mg: 30 mL; (2) Weigh the eight-membered cucurbitacin and 6-bromoquinoline derivative in a molar ratio of 1:2 to prepare a solution with a concentration of 1.0×10 -2 mol / L Q[8]-2BI-BOH assembly solution; (3) Weigh an appropriate amount of polyvinyl alcohol and heat under reflux at 90 °C to obtain a PVA solution with a concentration of 20 g / L; (4) Press V PVA : V Q[8]-2BI-BOH =100:1, add PVA solution, Q[8]-2BI-BOH assembly solution, or different dyes, heat and stir until the viscosity of the solution is appropriate, and then the desired different room temperature phosphorescent materials can be obtained.

3. The method for preparing a room temperature phosphorescent material based on an eight-membered cucurbit ring and a 6-bromoisoquinoline derivative according to claim 2, characterized in that: In (4), when different dyes are added, different room temperature phosphorescent materials are prepared according to the following method: (4) Weigh the dyes rhodamine B and butyl rhodamine B and prepare them to a concentration of 1.0×10 -2 mol / L solution, press V PVA : V Q[8]-2BI-BOH =100:1, N 染料 : N Q[8]-2BI-BOH =1:20, add PVA solution, Q[8]-2BI-BOH assembly solution and different dyes, heat and stir, and when the viscosity of the solution is appropriate, different room temperature phosphorescent materials can be obtained.

4. The application method of the room temperature phosphorescent material based on the eight-membered cucurbitacin and 6-bromoisoquinoline derivative according to any one of claims 1 to 3, characterized in that: The room temperature phosphorescent material is used for encryption and anti-counterfeiting.

5. The application method of the room temperature phosphorescent material based on the eight-membered cucurbit ring and the 6-bromoisoquinoline derivative according to claim 4, characterized in that: Draw the desired shape on filter paper with room temperature phosphorescent material; or paint the desired numbers or letters, then irradiate the material with 365 nm ultraviolet light, and then turn off the light source. The pattern, numbers, and letters will change according to the different afterglow colors of the material, achieving an encryption and anti-counterfeiting effect.

6. The application method of the room temperature phosphorescent material based on the eight-membered cucurbit ring and the 6-bromoisoquinoline derivative according to claim 5, characterized in that: The encryption methods are as follows: (1) The three prepared viscous liquids Q[8]-BI-BOH-PVA-BRhB, Q[8]-BI-BOH-PVA and Q[8]-BI-BOH-PVA-RhB are used to draw the desired pattern, number or letter on the filter paper, and the filter paper is dried at 80°C. The pattern, number or letter drawn by the Q[8]-BI-BOH-PVA viscous liquid is basically invisible under a fluorescent light. The filter paper is irradiated with a 365 nm ultraviolet light for a period of time, and the ultraviolet light is turned off. After 1.5 seconds, only the pattern, number or letter drawn by the Q[8]-BI-BOH-PVA viscous liquid can be seen, and the afterglow shows the information that cannot be seen under the fluorescent light, thereby achieving the effect of information encryption; (2) Use Q[8]-BI-BOH-PVA viscous liquid to paint the first pattern, letters or numbers, place it in an oven at 80 °C for 1 h, then use the corresponding Q[8]-BI-BOH-PVA viscous liquid to paint the above shape into the second pattern, letters or numbers, continue to dry for 0.5 h, and under the irradiation of 365 nm ultraviolet light, the information of the second pattern, letters or numbers is displayed in blue. After irradiation for a period of time, turn off the UV light, and the afterglow displays the information of the first pattern, letters or numbers; (3) First, use Q[8]-BI-BOH-PVA-BRhB viscous liquid to paint the first pattern, letters or numbers, place it in an oven at 80 °C for 1 hour, and then use the corresponding Q[8]-BI-BOH-PVA-BRhB viscous liquid to paint the above numbers into the second pattern, letters or numbers. Continue to dry for 0.5 hours. Under the irradiation of 365 nm ultraviolet light, the second pink pattern, letters or numbers will be displayed. After irradiation for a period of time, turn off the UV light, and the afterglow will display the information of the first pattern, letters or numbers.

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