Organic room-temperature phosphorescent material, preparation method and application thereof

Abstract

This application relates to an organic room-temperature phosphorescent material, its preparation method, and its applications. The organic room-temperature phosphorescent material comprises a polymer matrix composed of polyvinyl alcohol and biomolecules, and aromatic luminescent guest materials containing N, S, O, and B dispersed within the polymer matrix, thereby constituting a composite organic room-temperature phosphorescent material. This invention introduces aromatic luminescent guest materials containing the characteristic elements N, S, O, and B into a polymer matrix composed of polyvinyl alcohol and biomolecules, and constructs an organic room-temperature phosphorescent material with a host-guest structure and high efficiency and long lifetime characteristics through the interaction between the host and guest components. The preparation method of this material is simple, and its room-temperature phosphorescence is tunable, making it widely applicable in fields such as smart displays, data encryption, and disease detection.

Description

Technical Field

[0001] This invention relates to the field of polymer-based organic room-temperature phosphorescent materials, and particularly to a polymer-based organic room-temperature phosphorescent material with a polymer matrix consisting of polyvinyl alcohol and biomacromolecules having a multiple hydrogen bond network, as well as its preparation method and application. Background Technology

[0002] Polymer-based organic room-temperature phosphorescent materials have seen rapid development in research in recent years as a novel type of luminescent material. Their excellent properties, such as long luminescent lifetime and tunable emission color, enable their application in many fields, including information encryption, data storage, and ultraviolet detection. Furthermore, long-lifetime phosphorescent materials can utilize time-resolved techniques to eliminate the influence of biological background fluorescence, making them suitable for bioimaging and bioinformatics monitoring. In optical encryption, information is encrypted by writing it down and then re-exposing it using ultraviolet excitation. Long-lifetime phosphorescent materials are a type of long-afterglow luminescent material: they can still be observed with the naked eye for several seconds or even days after photoexcitation.

[0003] With the development in recent years, organic phosphorescence has made great progress from metal complexes to today's pure organic room temperature phosphorescence. The strategies for realizing long-lifetime pure organic room temperature phosphorescent materials are mainly as follows: (1) promoting the efficiency of intersystem crossing, so that more singlet excitons become triplet states; (2) suppressing nonradiative transitions of luminescent materials to reduce energy loss. Currently, common methods for realizing long-lifetime pure organic room temperature phosphorescent materials include H aggregation, crystal engineering, self-assembly, host-guest doping, and polymers. However, these materials with crystalline or powder states are difficult to process, have complex processing methods, and are prone to phase separation. These preparation problems greatly limit the development and application of room temperature phosphorescent materials. Therefore, constructing inexpensive and mass-producible room temperature phosphorescent materials is of great significance for promoting the application of phosphorescent materials and improving their economic value. It has profound significance in the development of long-lifetime phosphorescent material systems that are flexible, can be prepared on a large scale, and can be spliced, and has greatly promoted the commercialization of phosphorescent materials. If thin film materials with the above capabilities can be prepared by simple methods, this will solve the current bottleneck problem of large-scale preparation and use of long-lifetime phosphorescent materials.

[0004] Existing technology discloses a room-temperature phosphorescent material based on polyacrylonitrile doping, its preparation method, and its application. The preparation method includes: dispersing polyacrylonitrile in an organic solvent to obtain a polyacrylonitrile solution; adding a methoxylated aromatic compound to the polyacrylonitrile solution and stirring to obtain a blend solution; and annealing the blend solution to obtain the room-temperature phosphorescent material based on polyacrylonitrile doping. After ultraviolet excitation, the phosphorescent material emits visible green phosphorescence and delayed fluorescence with a decay lifetime of up to 100 ms. The methoxylated aromatic compound, which donates electrons, is selected as the guest material. The host material and the guest material bind through donor-acceptor (DA) interactions to form a room-temperature phosphorescent material, and this method can solve the problems of poor stability and difficulty in color control of currently reported doped materials. However, one of the polymer matrix constraints in this system is weak, the use of organic solvents to dissolve the polymer is environmentally harmful, making it unsuitable for application in biomonitoring. Furthermore, its color tuning controllability is poor, and the introduction of multiple luminescent groups requires high material ratios once the material is formed. However, color control in this system requires multiple chromophores and a large number of doped components, necessitating multiple components to achieve tunable color. Summary of the Invention

[0005] Therefore, this application discloses a highly efficient room-temperature phosphorescent material that is flexible, can be fabricated over a large area, and can be spliced ​​together.

[0006] To address the shortcomings of existing technologies, one of the objectives of this invention is to provide an organic room-temperature phosphorescent material, particularly a flexible organic room-temperature phosphorescent thin film material with a double hydrogen bond network. This organic room-temperature phosphorescent material not only possesses properties such as high flexibility, large-area fabrication capability, and repairability.

[0007] To achieve this objective, the present invention adopts the following technical solution: This application provides an organic room-temperature phosphorescent material, which includes a polymer matrix and an aromatic luminescent material. The polymer matrix serves as the main material of the entire organic room-temperature phosphorescent material system, and the aromatic luminescent material is the guest material of the organic room-temperature phosphorescent material system. The polymer matrix includes polyvinyl alcohol and at least one biomolecule with a non-aromatic structure, and the aromatic luminescent material includes one or more aromatic luminescent materials containing N, S, O, and B. The general formula I of the biomolecule with a non-aromatic structure is as follows:

[0008]

[0009] Where m, n, o, p, q, and r are One or more of them;

[0010] X is one or more of the following: C atom, O atom, etc.; n is a natural number from 1 to 20000.

[0011] This application also provides a method for preparing the aforementioned organic room-temperature phosphorescent material, the method comprising the following steps:

[0012] Step 1: Add polyvinyl alcohol and at least one biomolecule with a non-aromatic structure to the solution, dissolve them under heating conditions, and cool to obtain a mixed solution of polyvinyl alcohol and a biomolecule with a non-aromatic structure;

[0013] Step 2: Add the aromatic luminescent material containing N, S, O, and B to the mixed solution obtained in Step 1, and stir under heating conditions to disperse it evenly, thus obtaining a mixed solution;

[0014] Step 3: Pour the mixed solution obtained in Step 2 onto the mold and dry it to obtain the organic room temperature phosphorescent film.

[0015] This application provides the application of the described organic room temperature phosphorescent material in the fields of smart display, data encryption, and disease detection.

[0016] Beneficial effects

[0017] This invention transforms the polymer matrix of the common single hydrogen bond network into a polymer matrix of multiple hydrogen bond network by using polyvinyl alcohol and one or more biomacromolecules in multiple blends. The multiple hydrogen bonds achieve stronger confinement, and the inherent properties of biomacromolecules expand the functional possibilities of the system, enabling multiple stimulus responses.

[0018] This invention discloses an organic room-temperature phosphorescent material and its preparation method. This organic room-temperature phosphorescent material achieves room-temperature phosphorescence emission by mixing an aromatic luminescent guest material with polyvinyl alcohol and one or more biomacromolecules, and by limiting the non-radiative transition of the aromatic luminescent guest material through hydrogen bonding interactions between the polymer matrix and the aromatic luminescent material. In this organic room-temperature phosphorescent material system, the photophysical properties of the aromatic luminescent guest material can be controlled by introducing multiple polymer matrices and utilizing the specific properties of different polymers, thereby achieving specific stimulus response modes such as ion response and temperature response. The luminescent properties of this adjustable room-temperature phosphorescent material can be used in fields such as information encryption, multi-color patterning, visual detection, secure printing, and stimulus response. Attached Figure Description

[0019] Figure 1 This is the emission spectrum of the organic room-temperature phosphorescent material obtained in Example 1 of the present invention;

[0020] Figure 2 This is a graph showing the phosphorescence intensity-time variation of the emission peak at 420 nm and 485 nm obtained in Example 1 of the present invention;

[0021] Figure 3 This is the time-resolved spectrum in Embodiment 1 of the present invention;

[0022] Figure 4 This is the 1H NMR spectrum of 10H-phenthiazine 5,5-dioxide in Example 1 of this invention;

[0023] Figure 5 This is the infrared spectrum of the organic room-temperature phosphorescent material system in Example 2 of the present invention;

[0024] Figure 6 This is the emission spectrum of the organic room temperature phosphorescent material system in Example 2 of the present invention. Detailed Implementation

[0025] The present invention will be further illustrated below with reference to specific embodiments. It should be understood that these embodiments are only used to illustrate the present invention and not to limit the scope of the present invention. After reading the present invention, any modifications of the present invention in various equivalent forms by those skilled in the art will fall within the scope defined by the appended claims.

[0026] One embodiment of this application provides an organic room-temperature phosphorescent material, which includes a polymer matrix and an aromatic luminescent material. The polymer matrix serves as the host material of the entire organic room-temperature phosphorescent material system, and the aromatic luminescent material serves as the guest material of the organic room-temperature phosphorescent material system. The polymer matrix includes polyvinyl alcohol and at least one biomolecule with a non-aromatic structure. The aromatic luminescent material includes one or more aromatic luminescent materials containing N, S, O, and B. The general formula I of the biomolecule with a non-aromatic structure is as follows:

[0027]

[0028] Where m, n, o, p, q, and r are One or more of them;

[0029] X is one or more of the following: C atom, O atom, etc.; N is a natural number from 1 to 20000.

[0030] In one embodiment, the biomacromolecule with a non-aromatic structure is:

[0031]

[0032] In one embodiment, the material is an aromatic luminescent material containing N, S, O, and B, with the following general structural formula II:

[0033]

[0034] Where Ar is one or a combination of the following structures:

[0035]

[0036] Where X is a heteroatom of N, S, O or B.

[0037] In one embodiment, the aromatic luminescent guest material containing N, S, O, and B comprises one or more of the following compounds:

[0038]

[0039]

[0040]

[0041] Where n is an integer between 0 and 20.

[0042] One embodiment of this application provides a method for preparing the aforementioned organic room-temperature phosphorescent material, characterized in that the preparation method includes the following steps:

[0043] Step 1: Add polyvinyl alcohol and at least one biomolecule with a non-aromatic structure to the solution, dissolve them under heating conditions, and cool to obtain a mixed solution of polyvinyl alcohol and a biomolecule with a non-aromatic structure;

[0044] Step 2: Add the aromatic luminescent material containing N, S, O, and B to the mixed solution obtained in Step 1, and stir under heating conditions to disperse it evenly, thus obtaining a mixed solution;

[0045] Step 3: Pour the mixed solution obtained in Step 2 onto the mold and dry it to obtain the organic room temperature phosphorescent film.

[0046] In one embodiment, the polyvinyl alcohol has a molecular weight of 1000 or higher and accounts for 1%-90% of the mass fraction; the biomolecule with a non-aromatic structure accounts for 1%-90% of the mass fraction; and the mass of the solution is 2-5 times the mass of the solute.

[0047] In one embodiment, the aromatic luminescent guest material containing N, S, O, and B accounts for 5%-0.001% of the mass of the polymer matrix host material.

[0048] In one embodiment, the solution for dissolving the polymer matrix and the aromatic luminescent guest material containing N, S, O, and B in steps 1 and 2 can be one or more of the following solutions:

[0049] (1) A mixed solution of deionized water and dimethyl sulfoxide (of which deionized water accounts for 5%-95%)

[0050] (2) A mixed solution of deionized water and ethanol (of which the proportion of deionized water is 5%-95%)

[0051] (3) A mixed solution of deionized water and methanol (of which deionized water accounts for 5%-95%)

[0052] (4) Pure deionized water.

[0053] One embodiment of this application provides the application of the described organic room temperature phosphorescent material in the fields of smart display, data encryption, and disease detection.

[0054] Example 1

[0055] This embodiment provides a method for preparing an organic room-temperature phosphorescent material, the specific method of which is as follows:

[0056] Step 1: Weigh 0.5 g of polyvinyl alcohol, add 5 ml of deionized water and stir until homogeneous. Then add 0.15 g of carrageenan and stir at 90 degrees Celsius for 5 hours to dissolve, obtaining a mixed solution of polyvinyl alcohol and carrageenan. While heating and stirring, add 0.015 g of 10H-phenothiazine 5,5-dioxide and 0.065 g of potassium hydroxide to the above solution and stir for another 5 hours until homogeneous.

[0057] Step 2: Apply the mixed solution described in Step 1 evenly into a 20*20 cm mold and dry it in an oven at 80 degrees Celsius for one day.

[0058] Step 3: Peel off the film obtained in Step 2 to obtain a large-area flexible organic room temperature phosphorescent film.

[0059] The structure of the prepared compound is as follows:

[0060]

[0061] Using 355 nm ultraviolet light as the excitation source, the following was obtained at room temperature: Figure 1 The emission spectrum from Figure 1 It can be determined that the main peaks of phosphorescence emission and fluorescence emission of the thin film are 420 nm and 485 nm, respectively. Figure 2 The figure shows the phosphorescence intensity-time variation curve, where the phosphorescence lifetime is 112.09 ms and 165.87 ms respectively. Figure 3 It is a time-resolved spectrum. Figure 4 The hydrogen NMR spectrum of [the sample is missing].

[0062] Example 2

[0063] This embodiment provides a method for preparing an organic room-temperature phosphorescent material, the specific method of which is as follows:

[0064] Step 1: Weigh 0.5 g of polyvinyl alcohol, add 5 ml of deionized water and stir until homogeneous. Then add 0.15 g of carrageenan and stir at 90 degrees Celsius for 5 hours to dissolve, obtaining a mixed solution of polyvinyl alcohol and carrageenan. While heating and stirring, add 0.015 g of 10H-phenothiazine-5,5-dioxide to the above solution and stir for another 5 hours until homogeneous.

[0065] Step 2: Apply the mixed solution described in Step 1 evenly into a 20*20 cm mold and dry it in an oven at 80 degrees Celsius for one day.

[0066] Step 3: Peel off the film obtained in Step 2 to obtain a large-area flexible organic room temperature phosphorescent film.

[0067] The structure of the prepared compound is as follows:

[0068]

[0069] in Figure 5 The infrared spectrum of the interaction between 10H-phenothiazine-5,5-dioxide and the polymer matrix, obtained by passing through the infrared peak at 3500 cm⁻¹. -1 The redshift indicates that it forms intermolecular hydrogen bonds with the polymer matrix. Figure 6 The steady-state and delayed spectra are those of 10H-phenothiazine-5,5-dioxide reacting with the polymer matrix without the addition of potassium ions.

[0070] In Examples 1 and 2, the addition or absence of potassium ions resulted in a change in the emission spectrum of the same aromatic luminescent material, 10H-phenothiazine 5,5-dioxide, which makes it promising for applications in fields such as information encryption and secure printing.

[0071] Example 3

[0072] This embodiment provides a method for preparing an organic room-temperature phosphorescent material, the specific method of which is as follows:

[0073] Step 1: Weigh 0.5 g of polyvinyl alcohol, add 5 ml of deionized water and stir until homogeneous. Then add 0.15 g of carrageenan and stir and dissolve at 90 degrees Celsius for 5 hours to obtain a mixed solution of polyvinyl alcohol and carrageenan. While heating and stirring, add 0.015 g of 10H-phenothiazine 5,5-dioxide to the above solution and stir for another 5 hours until homogeneous.

[0074] Step 2: Evenly apply the mixed solution described in Step 1 into a 20*20 mold with a partition in the middle. Add potassium hydroxide solution to one side, and then remove the partition after solidification. Continue drying in an oven at 80 degrees Celsius for one day.

[0075] Step 3: Peel off the film obtained in Step 2 to obtain a large-area flexible organic room temperature phosphorescent film.

[0076] The structure of the prepared compound is as follows:

[0077]

[0078] In Example 3, a single luminescent group can emit two colors of organic room temperature phosphorescence on a single thin film by introducing potassium ions. This will be beneficial for the application of organic room temperature phosphorescent materials in the field of information encryption.

[0079] Example 4

[0080] This embodiment provides a method for preparing an organic room-temperature phosphorescent material with water-adjustable ON-OFF capability. The specific method is as follows:

[0081] Step 1: Weigh 0.5 g of polyvinyl alcohol, add 5 ml of deionized water and stir until homogeneous. Then add 0.15 g of cellulose and stir and dissolve at 90 degrees Celsius for 5 hours to obtain a mixed solution of polyvinyl alcohol and cellulose. While heating and stirring, add 0.015 g of triphenylamine phenylboronic acid to the above solution and stir for another 5 hours until homogeneous.

[0082] Step 2: Apply the mixed solution described in Step 1 evenly into a 20*20 cm mold, add ammonia to the solution and stir well to remove air bubbles. After solidification, remove the partition and continue drying in an oven at 80 degrees Celsius for one day.

[0083] Step 3: Peel off the film obtained in Step 2 to obtain a large-area flexible organic room temperature phosphorescent film.

[0084] Step 4: Apply a layer of deionized water solution to the film obtained in step 3 with a brush. The dry side exhibits long afterglow, while the wet side does not.

[0085] The structure of the prepared compound is as follows:

[0086]

[0087] In Implementation Example 4, the ON-OFF adjustment of long afterglow emission can be achieved by introducing or not introducing moisture, making the system easier to apply in fields such as information encryption and secure printing.

[0088] Example 5

[0089] This embodiment provides a method for preparing splicable organic room temperature phosphorescent materials. By splicing the materials, the ON-OFF ion response of different regions of the same thin film can be adjusted, thereby achieving information encryption.

[0090] Step 1: Weigh 0.5 g of polyvinyl alcohol and add 5 ml of deionized water, stirring until homogeneous. Then add 0.15 g of chitosan and stir at 90°C for 5 hours to dissolve, obtaining a mixed solution of polyvinyl alcohol and carrageenan. While heating and stirring, add 0.00065 g of 10H-phenothiazine-7-boric acid 5,5-dioxide to the above solution and stir for another 5 hours until homogeneous. (This process is repeated twice in the original text.)

[0091] Step 2: Apply the two mixed solutions described in Step 1 evenly into a 20*20 mold and dry them in an oven at 80 degrees Celsius for one day.

[0092] Step 3: Peel off the two films obtained in Step 2 to obtain a large-area flexible organic room temperature phosphorescent film.

[0093] The structure of the prepared compound is as follows:

[0094]

[0095] Step 4: Add water between the two films to form a single film, and dry it at 40 degrees Celsius for 5 hours.

[0096] The introduction of potassium hydroxide resulted in a color change response only on the side containing carrageenan.

[0097] Example 6

[0098] This embodiment provides a method for preparing a polymer-based organic room-temperature phosphorescent material, the specific steps of which are as follows:

[0099] Step 1: Weigh 0.5 g of polyvinyl alcohol, add 5 ml of deionized water and stir until homogeneous. Then add 0.15 g of carrageenan and stir at 90 degrees Celsius for 5 hours to dissolve, obtaining a mixed solution of polyvinyl alcohol and carrageenan. While heating and stirring, add 0.015 g of 1,8-naphthalenedicarboxylic anhydride dimethyl sulfoxide solution to the above solution and stir for another 5 hours until homogeneous.

[0100] Step 2: Apply the mixed solution described in Step 1 evenly into a 20*20 cm mold and dry it in an oven at 80 degrees Celsius for one day.

[0101] Step 3: Peel off the film obtained in Step 2 to obtain a large-area flexible organic room temperature phosphorescent film.

[0102] Step 4: Apply a layer of deionized water solution to the film obtained in step 3 with a brush. The dry side exhibits long afterglow, while the wet side does not.

[0103] The structure of the prepared compound is as follows:

[0104]

[0105]

[0106] In Implementation Example 6, the ON-OFF adjustment of long afterglow emission can be achieved by introducing or not introducing moisture, making the system easier to apply in fields such as information encryption and secure printing.

[0107] Example 7

[0108] This embodiment provides an acid-base responsive polymer-based organic room-temperature phosphorescent material, and the specific steps are as follows:

[0109] Step 1: Weigh 0.5 g of polyvinyl alcohol, add 5 ml of deionized water and stir well. Then add 0.15 g of cellulose and 0.15 g of carrageenan and stir at 90 degrees Celsius for 5 hours to dissolve, obtaining a mixed solution of polyvinyl alcohol and cellulose. While heating and stirring, add 0.015 g of triphenylamine phenylboronic acid to the above solution and stir for another 5 hours until well mixed.

[0110] Step 2: Apply the mixture described in Step 1 evenly into a 20*20 cm mold, stir well to remove air bubbles, then remove the partition after solidification and continue drying in an oven at 80 degrees Celsius for one day.

[0111] Step 3: Peel off the film obtained in Step 2 to obtain a large-area flexible phosphorescent film.

[0112] Step 4: Apply a layer of saturated sodium hydroxide aqueous solution to one side of the film obtained in Step 3 using a brush, and then dry it to obtain a film with one side exhibiting blue fluorescence and the other side exhibiting green room-temperature phosphorescence. This method will be applied in fields such as information display and information encryption.

[0113] Its specific structure is as follows:

[0114]

[0115] In Example 7, the ON-OFF adjustment of organic room temperature phosphorescence can be achieved by adjusting the pH level, while simultaneously achieving green organic room temperature phosphorescence.

[0116] Example 8

[0117] This embodiment provides a method for preparing a polymer-based organic room-temperature phosphorescent material, the specific steps of which are as follows:

[0118] Step 1: Weigh 0.5 g of polyvinyl alcohol, add 5 ml of deionized water and stir until homogeneous. Then add 0.15 g of carrageenan and stir at 90 degrees Celsius for 5 hours to dissolve, obtaining a mixed solution of polyvinyl alcohol and carrageenan. While heating and stirring, add 0.015 g of a dimethyl sulfoxide solution of 9,9-dimethyl-10-propionyl chloride acridine to the above solution and stir for another 5 hours until homogeneous.

[0119] Step 2: Apply the mixed solution described in Step 1 evenly into a 20*20 cm mold and dry it in an oven at 80 degrees Celsius for one day.

[0120] Step 3: Peel off the film obtained in Step 2 to obtain a large-area flexible organic room temperature phosphorescent film.

[0121] Step 4: Apply a layer of deionized water solution to the film obtained in step 3 with a brush. The dry side exhibits long afterglow, while the wet side does not.

[0122] Its specific structure is as follows:

[0123]

[0124] In Implementation Example 8, the ON-OFF adjustment of long afterglow emission can be achieved by introducing or not introducing moisture, making the system easier to apply in fields such as information encryption and secure printing.

[0125] Example 9

[0126] This embodiment provides a method for preparing a polymer-based organic room-temperature phosphorescent material, the specific steps of which are as follows:

[0127] Step 1: Weigh 0.5 g of polyvinyl alcohol, add 5 ml of deionized water and stir until homogeneous. Then add 0.15 g of carrageenan and stir at 90 degrees Celsius for 5 hours to dissolve, obtaining a mixed solution of polyvinyl alcohol and carrageenan. While heating and stirring, add 0.015 g of a dimethyl sulfoxide solution of 1,4,5,8-naphthalenetetracarboxylic diimide to the above solution and stir for another 5 hours until homogeneous.

[0128] Step 2: Apply the mixed solution described in Step 1 evenly into a 20*20 cm mold and dry it in an oven at 80 degrees Celsius for one day.

[0129] Step 3: Peel off the film obtained in Step 2 to obtain a large-area flexible organic room temperature phosphorescent film.

[0130] Step 4: Apply a layer of deionized water solution to the film obtained in step 3 with a brush. The dry side exhibits long afterglow, while the wet side does not.

[0131] Its specific structure is as follows:

[0132]

[0133] In Implementation Example 9, the ON-OFF adjustment of long afterglow emission can be achieved by introducing or not introducing moisture, making the system easier to apply in fields such as information encryption and secure printing.

[0134] Example 10

[0135] This embodiment provides a method for preparing a polymer-based organic room-temperature phosphorescent material, the specific steps of which are as follows:

[0136] Step 1: Weigh 0.5 g of polyvinyl alcohol, add 5 ml of deionized water and stir until homogeneous. Then add 0.15 g of sodium alginate and 0.15 g of carboxymethyl chitosan and stir at 90 degrees Celsius for 5 hours to dissolve, obtaining a mixed solution of polyvinyl alcohol and carrageenan. While heating and stirring, add 0.015 g of 9,9-dimethylacridine dimethyl sulfoxide solution to the above solution and stir for another 5 hours until homogeneous.

[0137] Step 2: Apply the mixed solution described in Step 1 evenly into a 20*20 cm mold and dry it in an oven at 80 degrees Celsius for one day.

[0138] Step 3: Peel off the film obtained in Step 2 to obtain a large-area flexible organic room temperature phosphorescent film.

[0139] Step 4: Apply a layer of deionized water solution to the film obtained in step 3 with a brush. The dry side exhibits long afterglow, while the wet side does not.

[0140] Its specific structure is as follows:

[0141]

[0142] In Implementation Example 10, the on / off adjustment of long afterglow emission can be achieved by introducing or not introducing moisture, making the system easier to apply in fields such as information encryption and secure printing.

[0143] Example 11

[0144] This embodiment provides a method for preparing polymer-based organic room temperature phosphorescence, the specific steps of which are as follows:

[0145] Step 1: Weigh 0.5 g of polyvinyl alcohol, add 5 ml of deionized water and stir well. Then add 0.15 g of sodium alginate and 0.15 g of carboxymethyl chitosan. Stir and dissolve at 90 degrees Celsius for 5 hours to obtain a mixed solution of polyvinyl alcohol and carrageenan. While heating and stirring, pour 0.08 g of pyrene dimethyl sulfoxide solution into the above solution and stir for another 5 hours until well mixed.

[0146] Step 2: Apply the mixed solution described in Step 1 evenly into a 20*20 cm mold and dry it in an oven at 80 degrees Celsius for one day.

[0147] Step 3: Peel off the film obtained in Step 2 to obtain a large-area flexible organic room temperature phosphorescent film.

[0148] Step 4: Apply a layer of deionized water solution to the film obtained in step 3 with a brush. The dry side exhibits long afterglow, while the wet side does not.

[0149] Its specific structure is as follows:

[0150]

[0151] In Implementation Example 11, the on / off regulation of long afterglow emission can be achieved by introducing or not introducing moisture.

[0152] Example 12

[0153] This embodiment provides a method for preparing polymer-based organic room temperature phosphorescence, the specific steps of which are as follows:

[0154] Step 1: Weigh 0.5 g of polyvinyl alcohol, add 5 ml of deionized water and stir until homogeneous. Then add 0.15 g of cellulose and stir and dissolve at 90 degrees Celsius for 5 hours to obtain a polyvinyl alcohol mixture. While heating and stirring, add 0.08 g of 1-boron pyrene dimethyl sulfoxide solution to the above solution and stir for another 5 hours until homogeneous.

[0155] Step 2: Apply the mixed solution described in Step 1 evenly into a 20*20 cm mold and dry it in an oven at 80 degrees Celsius for one day.

[0156] Step 3: Peel off the film obtained in Step 2 to obtain a large-area flexible organic room temperature phosphorescent film.

[0157] Step 4: Apply a layer of deionized water solution to the film obtained in step 3 with a brush. The dry side exhibits long afterglow, while the wet side does not.

[0158] Its specific structure is as follows:

[0159]

[0160]

[0161] In Implementation Example 12, the on / off regulation of long afterglow emission can be achieved by introducing or not introducing moisture.

[0162] Example 13

[0163] This embodiment provides a method for preparing an organic room-temperature phosphorescent material, the specific method of which is as follows:

[0164] Step 1: Weigh 0.5 g of polyvinyl alcohol, add 5 ml of deionized water and stir until homogeneous. Then add 0.15 g of carrageenan and stir and dissolve at 90 degrees Celsius for 5 hours to obtain a mixed solution of polyvinyl alcohol and carrageenan. While heating and stirring, add 0.015 g of 1-boron pyrene dimethyl sulfoxide solution to the above solution and stir for another 5 hours until homogeneous.

[0165] Step 2: Evenly apply the mixed solution described in Step 1 into a 20*20 mold with a partition in the middle. Add potassium hydroxide solution to one side, and then remove the partition after solidification. Continue drying in an oven at 80 degrees Celsius for one day.

[0166] Step 3: Peel off the film obtained in Step 2 to obtain a large-area flexible organic room temperature phosphorescent film.

[0167] Its specific structure is as follows:

[0168]

[0169] In Implementation Example 13, the on / off regulation of long afterglow emission can be achieved by introducing or not introducing moisture.

[0170] Example 14

[0171] This embodiment provides a method for preparing an organic room-temperature phosphorescent material and its application in the detection of serum potassium. The specific method is as follows:

[0172] Step 1: Weigh 0.5 g of polyvinyl alcohol, add 5 ml of deionized water and stir until homogeneous. Then add 0.15 g of carrageenan and stir at 90 degrees Celsius for 5 hours to dissolve, obtaining a mixed solution of polyvinyl alcohol and carrageenan. While heating and stirring, add 0.015 g of 10H-phenothiazine 5,5-dioxide and 0.065 g of potassium hydroxide to the above solution and stir for another 5 hours until homogeneous.

[0173] Step 2: Apply the mixed solution described in Step 1 evenly into a 20*20 cm mold and dry it in an oven at 80 degrees Celsius for one day.

[0174] Step 3: Peel off the film obtained in Step 2 to obtain a large-area flexible organic room temperature phosphorescent film.

[0175] The structure of the prepared compound is as follows:

[0176]

[0177] A serum solution with a potassium ion concentration of 6 mmol (mimicking the serum of patients with hypokalemia) was prepared and dropped onto a phosphorescent film. When the film was irradiated with a 365°C handheld UV lamp, the dropped area showed green phosphorescence, while the undropped area showed blue phosphorescence. This material shows good promise for convenient detection of hypokalemia.

[0178] The above are merely preferred embodiments of the present invention. It should be noted that, for those skilled in the art, numerous improvements and modifications can be made without departing from the principles of the present invention, and these improvements and modifications should also be considered within the scope of protection of the present invention.

Claims

1. An organic room-temperature phosphorescent material, characterized in that, The organic room-temperature phosphorescent material comprises a polymer matrix and an aromatic light-emitting material, the polymer matrix serves as a host material of the entire organic room-temperature phosphorescent material system, and the aromatic light-emitting material is a guest material of the organic room-temperature phosphorescent material system, wherein the polymer matrix comprises polyvinyl alcohol, carrageenan and / or at least one biological macromolecule with a non-aromatic structure, and the aromatic light-emitting material comprises one or more aromatic light-emitting materials containing N, S, O and B; wherein the biological macromolecule with a non-aromatic structure has the following structure: The aromatic light-emitting guest material containing N, S, O and B comprises a combination of one or more of the following compounds: .

2. A method of producing the organic room-temperature phosphorescent material according to claim 1, characterized by, The preparation method comprises the following steps: Step 1: polyvinyl alcohol, carrageenan and / or at least one biological macromolecule with non-aromatic structure are added into a solvent, dissolved under heating condition, and cooled to obtain a mixed solution of polyvinyl alcohol and biological macromolecule with non-aromatic structure; Step 2: aromatic luminescent material containing N, S, O and B is added into the mixed solution obtained in step 1, stirred under heating condition to make it uniformly dispersed, and a mixed solution is obtained; Step 3: the mixed solution obtained in step 2 is poured into a mold, and dried to obtain an organic room-temperature phosphorescent film.

3. The method of claim 2, wherein, The molecular weight of the polyvinyl alcohol is above 1000, and the mass fraction in the polymer matrix is 1%-90%; the mass fraction of the biological macromolecule with non-aromatic structure in the polymer matrix is 1%-90%; and the mass of the solvent is 2-5 times of the mass of the solute.

4. The preparation method according to claim 2, characterized in that, The mass ratio of the aromatic luminescent guest material containing N, S, O and B to the polymer matrix host material is 5%-0.001%.

5. The preparation method according to claim 2, characterized in that, The solvents for dissolving the polymer matrix and the aromatic luminescent guest material containing N, S, O and B in steps 1 and 2 are one or more of the following solvents: (1) a mixed solution of deionized water and dimethyl sulfoxide, wherein the mass fraction of deionized water is 5%-95%; (2) a mixed solution of deionized water and ethanol, wherein the mass fraction of deionized water is 5%-95%; (3) a mixed solution of deionized water and methanol, wherein the mass fraction of deionized water is 5%-95%; (4) pure deionized water.

6. Application of the organic room-temperature phosphorescent material in claim 1 in the fields of intelligent display, data encryption and disease detection.

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