CN115746167B - Room-temperature phosphorescent material, and preparation method and application thereof - Google Patents
Room-temperature phosphorescent material, and preparation method and application thereof Download PDFInfo
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Abstract
The application provides a room-temperature phosphorescent material, a preparation method and application thereof, and relates to the field of materials, so as to solve the technical problems of unfriendly environment, short phosphorescent life and poor processability of the room-temperature phosphorescent material. The preparation method comprises the following steps: adding an activating agent into an organic acid solution, wherein the organic acid is one of 4,4 '-tricarboxylic acid triphenylamine, 1-naphthoic acid, biphenyl-4-carboxylic acid, 1, 8-naphthalene dicarboxylic anhydride and 1-pyrene butyric acid, and the activating agent is N- (3-dimethylaminopropyl) -N' -ethylcarbodiimide hydrochloride/N-hydroxysuccinimide; completely reacting the organic acid solution with chitosan aqueous solution after carboxyl activation, wherein the molar ratio of chitosan to organic acid is (8:1) - (3:100); removing the activator to obtain the chitosan derivative.
Description
Technical Field
The disclosure relates to the field of materials, in particular to a room-temperature phosphorescent material, and a preparation method and application thereof.
Background
Organic luminescent materials are used in a variety of fields such as illumination display, optoelectronic devices, information storage, optical anti-counterfeiting, biological imaging, chemical sensing, and the like. Compared with fluorescence emission, phosphorescence emission wavelength is longer, stokes shift is larger, and luminescence life is longer.
In the prior art, the room temperature phosphorescent materials are mostly organic small molecules, and long-life room temperature phosphorescence is mainly realized through strategies such as crystal engineering, hydrogen bonding, self-assembly, heavy atom effect, host-guest doping and the like. However, the organic micromolecular material has harsh conditions in the preparation process, the introduced heavy atoms have great harm to human bodies, and the material has poor processability and poor flexibility.
Disclosure of Invention
The application aims to provide a room-temperature phosphorescent material, and a preparation method and application thereof, so as to solve the technical problems of unfriendly environment, short phosphorescent life and poor processability of the room-temperature phosphorescent material.
In order to achieve the above object, the present application provides the following technical solutions:
the embodiment of the application provides a preparation method of a room-temperature phosphorescent material, which comprises the following steps:
adding an activating agent into an organic acid solution, wherein the organic acid is one of 4,4 '-triphenylamine tricarboxylic acid, 1-naphthoic acid, biphenyl-4-carboxylic acid, 1, 8-naphthalene dicarboxylic anhydride and 1-pyrene butyric acid, and the activating agent is N- (3-dimethylaminopropyl) -N' -ethylcarbodiimide hydrochloride/N-hydroxysuccinimide;
completely reacting the organic acid solution with chitosan aqueous solution after carboxyl activation, wherein the molar ratio of the chitosan to the organic acid is (8:1) - (3:100);
removing the activator to obtain the chitosan derivative.
According to at least one embodiment of the present disclosure, the molar ratio of N- (3-dimethylaminopropyl) -N' -ethylcarbodiimide hydrochloride to N-hydroxysuccinimide in the activator is (20:1) - (1:1).
According to at least one embodiment of the present disclosure, the step of completely reacting the organic acid solution after the activation of the carboxyl group with the chitosan aqueous solution is performed under the protection of an inert gas.
According to at least one embodiment of the present disclosure, the preparation method further includes dissolving the chitosan derivative in an aqueous acetic acid solution, and adding cyclodextrin to obtain a chitosan derivative-cyclodextrin, wherein a molar ratio of the cyclodextrin to the organic acid contained in the chitosan derivative is (1:5) - (20:1).
According to at least one embodiment of the present disclosure, the cyclodextrin is one or more of α -cyclodextrin, β -cyclodextrin, γ -cyclodextrin.
According to at least one embodiment of the present disclosure, the aqueous acetic acid solution has a concentration of no greater than 50%.
Compared with the prior art, the preparation method of the room-temperature phosphorescent material disclosed by the application has the advantage that the aromatic compound rich in carbonyl is modified on the chitosan chain through a simple amidation reaction between the organic acid and the chitosan. The unique semi-rigid structure of the chitosan chain and a large number of hydrogen bonds among chitosan molecules provide a rigid microenvironment, limit the non-radiative transition of triplet excitons, isolate oxygen in the air and limit the phosphorescence to be quenched by the oxygen, so that a series of chitosan derivatives with multicolor long-life room-temperature phosphorescence emission can be obtained. Specifically, a series of molecules containing carboxylic acid or anhydride groups, including triphenylamine 4,4 '-tricarboxylic acid (abbreviated as NTBA), 1-naphthoic acid (abbreviated as 1-NA), biphenyl-4-carboxylic acid (abbreviated as BPA), 1, 8-naphthalic anhydride (1, 8-NA), 1-pyrenebutyric acid (abbreviated as 1-PyBA), were activated by N- (3-dimethylaminopropyl) -N' -ethylcarbodiimide hydrochloride (abbreviated as EDC) and N-hydroxysuccinimide (abbreviated as NHS), and after activation by an amidation reaction between carboxylate and amino groups, successfully grafted the organic phosphorescent molecule onto the chitosan chain. Thus, a chitosan derivative having color afterglow of blue, cyan, green, yellow and red after the ultraviolet lamp irradiation is stopped was prepared.
Meanwhile, the chitosan derivative prepared by the preparation method provided by the embodiment of the application also shows phosphorescence response under the stimulation of water/heat, the heating/steam fumigation process is repeated for five times, and the phosphorescence signal basically disappears even if the film is fumigated by steam each time, but the phosphorescence signal can be recovered and basically stable and unchanged only after being heated for 5mm at 80 ℃, and the chitosan derivative has the characteristic of reversibility in circulation.
Furthermore, the method for preparing the chitosan derivative is simple and environment-friendly, and the prepared chitosan derivative has good processability, such as excellent film forming performance.
The application also aims to provide application of the chitosan derivative prepared by the preparation method in anti-counterfeiting ink.
The application also provides a room-temperature phosphorescent material, wherein the chitosan derivative prepared by the preparation method is dissolved in acetic acid aqueous solution, and the chitosan derivative film is obtained after drying, and the phosphorescence of the chitosan derivative film has stimulus response to water/heat and is reversible in circulation, or the chitosan derivative-cyclodextrin film is obtained after drying the chitosan derivative-cyclodextrin prepared by the preparation method.
The application also provides application of the room temperature phosphorescent material in preparing a product with room temperature phosphorescent performance.
Compared with the prior art, the room temperature phosphorescent material and the application thereof have the same advantages as the preparation method of the room temperature phosphorescent material, and are not repeated.
Drawings
The accompanying drawings, which are included to provide a further understanding of the disclosure and are incorporated in and constitute a part of this specification, illustrate exemplary embodiments of the disclosure and together with the description serve to explain the principles of the disclosure.
Fig. 1 is a schematic flow diagram of room temperature phosphorescent material preparation according to an embodiment of the present disclosure.
FIG. 2 is a schematic illustration of the stimulus-responsiveness of a room temperature phosphorescent material, wherein (a) is CS-1-A hydrothermal cycling phosphorescent intensity, (b) is stimulus-responsiveness to heat, and (c) is stimulus-responsiveness to water, according to an embodiment of the present disclosure.
FIG. 3 is a graph of before and after cyclodextrin fortification of BPA in various ratios, wherein (a) the phosphorescent intensity of the various ratios, (b) the phosphorescent lifetime of the various ratios, (c) the XRD pattern of the various ratios, (d) the TEM pattern without cyclodextrin fortification, (e) the TEM pattern with cyclodextrin to BPA ratio of 2:1, and (f) the TEM pattern with cyclodextrin to BPA ratio of 8:1, according to an embodiment of the present disclosure.
FIG. 4 is a graph of phosphorescence lifetime testing before and after CS-NTBA cyclodextrin fortification according to an example.
FIG. 5 is a graph of phosphorescence lifetime measurements before and after CS-BPA cyclodextrin fortification according to an example.
FIG. 6 is a graph of phosphorescence lifetime test before and after enhancement of CS-1-NA cyclodextrin according to an example.
FIG. 7 is a graph of phosphorescence lifetime test before and after enhancement of CS-1,8-NA cyclodextrin according to an example.
FIG. 8 is a graph of phosphorescence lifetime testing before and after CS-PyBA cyclodextrin fortification according to an embodiment.
FIG. 9 is a graph of phosphorescence lifetime test before and after CS-Pyr cyclodextrin fortification according to an embodiment.
Detailed Description
The present disclosure is described in further detail below with reference to the drawings and the embodiments. It is to be understood that the specific embodiments described herein are merely illustrative of the relevant content and not limiting of the present disclosure. It should be further noted that, for convenience of description, only a portion relevant to the present disclosure is shown in the drawings.
In addition, embodiments of the present disclosure and features of the embodiments may be combined with each other without conflict. The present disclosure will be described in detail below with reference to the accompanying drawings in conjunction with embodiments. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
The organic acid provided by the application comprises 4,4' -triphenylamine tricarboxylic acid (NTBA), biphenyl-4-carboxylic acid (BPA), 1-naphthoic acid (1-NA) and 1-pyrene butyric acid (1-PyBA) which are purchased from Shanghai Biget medical science and technology Co., ltd; 1, 8-naphthalene dicarboxylic anhydride (1, 8-NA), alpha-cyclodextrin (abbreviated as alpha-CD), beta-cyclodextrin, gamma-cyclodextrin were purchased from Shanghai microphone Lin Shenghua Co., ltd; short chain chitosan (abbreviated CS) was purchased from Jin Hu crustacean limited; n- (3-dimethylaminopropyl) -N' -ethylcarbodiimide hydrochloride (abbreviated EDC) was purchased from Beijing carbofuran technologies Co. N-hydroxysuccinimide (abbreviated NHS) is available from Shanghai Michelson chemical technologies Co.
Illustratively, the activator uses two EDC and NHS to activate a molecule containing a carboxylic acid or anhydride group, and the amidation reaction between carboxylate and amino groups at room temperature conditions successfully grafts the organic phosphorescent molecule onto the chitosan chain. IR analysis of the polymer indicated that the target compound was successfully prepared. 1548cm -1 The absorption at this point can be attributed to the c=o extension of the ester group, whereas 1647cm -1 And 1548cm -1 The absorption at this point is attributed to the expansion and contraction of c=o in CONH and COO-respectively, thus proving successful grafting of the luminophore. At the same time at 1255cm -1 The characteristic bands associated with C-N extension were observed, further confirming successful preparation of the target compound. Under the irradiation of a 310nm ultraviolet lamp, all the processed films emitted bright blue or cyan light. Spectroscopic measurements showed their maximum emission values from 351nm to 498nm, which is consistent with the observed emission color. And immediately after stopping the irradiation of the ultraviolet lamp, it can be seen that the solid film exhibits color afterglow of blue (CS-NTBA), cyan (CS-BPA), green (CS-1-NA), yellow (CS-1, 8-NA) and red (CS-1-PyBA), respectively.
Illustratively, the molar ratio of chitosan to organic acid is (8:1) - (3:100), alternatively (8:1) - (3:50), further alternatively (5:1) - (3:50), further alternatively (3:1) - (3:40).
Illustratively, the molar ratio of EDC to NHS is (20:1) - (1:1), alternatively (15:1) - (1:1), further alternatively (10:1) - (1:1), and further alternatively (5:1) - (1:1).
The preparation methods of chitosan derivatives are various, and exemplary preparation methods according to embodiments of the present application include, as shown in fig. 1:
step S10: adding an activating agent into an organic acid solution, wherein the organic acid is one of 4,4 '-tricarboxylic acid triphenylamine, 1-naphthoic acid, biphenyl-4-carboxylic acid, 1, 8-naphthalene dicarboxylic anhydride and 1-pyrene butyric acid, and the activating agent is N- (3-dimethylaminopropyl) -N' -ethylcarbodiimide hydrochloride/N-hydroxysuccinimide;
step S20: completely reacting the organic acid solution with chitosan aqueous solution after carboxyl activation, wherein the molar ratio of chitosan to the organic acid is (8:1) - (3:100);
step S30: and removing the activator to obtain the chitosan derivative, namely the room-temperature phosphorescent material.
Specifically, in the operation steps, the preparation method of the room-temperature phosphorescent material comprises the following steps:
step S100: purifying chitosan: dissolving chitosan in pure water, magnetically stirring overnight at room temperature to dissolve completely, transferring the completely dissolved solution into a centrifuge tube, centrifuging, collecting supernatant, repeatedly centrifuging at high speed for 3 times, collecting the centrifuged solution in a beaker, slowly adding absolute ethyl alcohol under the condition of continuous stirring to observe that chitosan is slowly separated out, standing the solution in room temperature environment to completely separate out chitosan, performing suction filtration, washing with absolute ethyl alcohol, and finally drying the solid after suction filtration for 48h under 30 DEG vacuum.
Step S200: synthesis of chitosan derivatives:
step S210: dissolving chitosan in pure water, stirring until the chitosan is fully dissolved, and dissolving organic acid in DMF;
step S220: EDC and NHS are dissolved in pure water and added to DMF solution of the organic acid to activate the carboxyl groups of the organic acid;
step S230: and under the protection of nitrogen, slowly dropwise adding the DMF solution of the activated organic acid into the chitosan water solution, and completing the reaction.
Step S300: EDC and NHS were removed: and (3) putting the solution after the reaction in the step (S230) into a dialysis bag, dialyzing in pure water, changing water every 4 hours to remove EDC and NHS, and freeze-drying after the dialysis is finished to obtain the chitosan organic acid derivative.
Step S400: cyclodextrin fortification: dissolving chitosan organic acid derivative in acetic acid water solution, adding cyclodextrin, ultrasonic treating, pouring into mold, and oven drying to form film.
In the step S210, chitosan is dissolved in water, and stirred for 1 to 24 hours at the temperature of between 0 and 90 ℃ to obtain a chitosan aqueous solution;
in the above step S230, the reaction time is illustratively 6 to 96 hours.
In step S400, in order to break through the second order of phosphorescence lifetime of the chitosan derivative, the embodiment of the application constructs a supermolecule assembly system by using the chitosan derivative and cyclodextrin through a simple self-assembly strategy, so that the room temperature phosphorescence material with the lifetime reaching the second order is very conveniently prepared. A portion of the cyclodextrin-formed hydrophobic cavity can effectively contain phosphorescent small molecules in the aqueous phase to form an intermolecular supramolecular system. The intermolecular hydrogen bond interaction provided by another part of cyclodextrin molecules can be used as a driving force to form a chitosan/cyclodextrin composite association structure. Under the action of two supermolecules, the fixed phosphor group inhibits the non-radiative relaxation of the supermolecules, and isolates the phosphor group from external quenching substances, so that the molecules can realize room-temperature phosphorescence emission with longer service life.
In an alternative embodiment, the chitosan organic acid derivative obtained in the step S300 is dissolved in 0% -50% acetic acid aqueous solution, and then is dripped into a die, and dried for 1-48 hours at 30-100 ℃ to obtain the chitosan derivative film. The film stimulus responsiveness, phosphorescence color, phosphorescence lifetime, and the like were tested.
In another alternative embodiment, the chitosan derivative-cyclodextrin film obtained after step S400 is subjected to a phosphorescent lifetime test.
Illustratively, the cyclodextrin in step S400 is one or more of α -cyclodextrin, β -cyclodextrin, and γ -cyclodextrin, the molar ratio of cyclodextrin to organic acid contained in the chitosan derivative is (1:5) - (20:1), illustratively (1:1) - (20:1), further alternatively (3:1) - (20:1), alternatively (5:1) - (17:1), and alternatively (7:1) - (12:1).
Illustratively, the aqueous acetic acid solution has a concentration of no greater than 50%, alternatively 0.1% to 25%, and still alternatively 0.15% to 10%, and 0.5% to 5%.
Specifically, the purification of chitosan includes: weighing 7g of chitosan, dissolving the chitosan in 200ml of pure water, magnetically stirring the solution at room temperature overnight to enable the chitosan to be completely dissolved, transferring the completely dissolved solution into a centrifuge tube, centrifuging the solution at 10000rmp for 10 minutes, collecting supernatant, repeatedly centrifuging the solution at high speed for 3 times, collecting the centrifuged solution in a beaker, slowly adding absolute ethyl alcohol under the condition of continuous stirring, observing that the chitosan is slowly separated out, standing the solution in the room temperature environment for 12 hours, enabling the chitosan to be completely separated out, carrying out suction filtration, washing the solution with the absolute ethyl alcohol for 9 times, and finally carrying out vacuum drying on the solid after suction filtration at 30 ℃ for 48 hours.
Examples of several room temperature phosphorescent materials are given below, and representative room temperature phosphorescent materials were selected for material performance analysis.
Example 1
The preparation method of the room-temperature phosphorescent material provided by the embodiment specifically comprises the following steps:
s1, dissolving 0.5g of chitosan (0.045 mmol) in 50ml of pure water, and stirring for 2 hours until the chitosan is fully dissolved;
s2, 0.026g of 1-naphthoic acid (1-NA, 0.15 mmol) is dissolved in 50ml DMF;
s3, 0.291g (1.5 mmol) of EDC and 0.174g (1.5 mmol) of NHS were dissolved in 1ml of pure water, respectively, and added to the 1-naphthoic acid solution;
s4, slowly dripping the activated 1-naphthoic acid solution into the chitosan water solution under the protection of nitrogen, and reacting for 24 hours at 30 ℃;
s5, after the reaction is finished, the reaction solution is filled into a dialysis bag with the speed of 3000Da and dialyzed for 3d in pure water, water is changed every 4 hours, EDC and NHS are removed, and freeze drying is finished after the dialysis to obtain chitosan-1-naphthoic acid product (abbreviated as CS-1-NA);
s6, dissolving CS-1-NA (1-NA content 1 mu mol) in 4ml of 1% acetic acid aqueous solution, adding 2 mu mol of alpha-cyclodextrin, carrying out ultrasonic treatment for 1h, pouring into a mould, and drying at 40 ℃ for 18h to form the film.
Example 2
The preparation method of the room-temperature phosphorescent material provided by the embodiment specifically comprises the following steps:
s1, dissolving 0.5g of chitosan (0.045 mmol) in 50ml of pure water, and stirring for 2 hours until the chitosan is fully dissolved;
s2, 0.057g of triphenylamine 4,4' -tricarboxylic acid (NTBA, 0.15 mmol) was dissolved in 50ml DMF;
s3, 0.291g (1.5 mmol) of EDC and 0.174g (1.5 mmol) of NHS were dissolved in 1ml of pure water and added to the NTBA solution, respectively;
s4, slowly dropwise adding the activated NTBA solution into the chitosan water solution under the protection of nitrogen, and reacting for 24 hours at 30 ℃;
s5, after the reaction is finished, the reaction solution is filled into a dialysis bag with the speed of 3000Da and dialyzed for 3d in pure water, water is changed every 4 hours, EDC and NHS are removed, and freeze drying is finished after the dialysis to obtain chitosan-4, 4' -triphenylamine tricarboxylic acid (abbreviated as CS-NTBA);
s6, dissolving CS-NTBA (NTBA content 1 mu mol) in 4ml of 1% acetic acid aqueous solution, adding 4 mu mol of alpha-cyclodextrin, performing ultrasonic treatment for 1h, pouring into a mould, and drying at 40 ℃ for 18h to form the film.
Example 3
The preparation method of the room-temperature phosphorescent material provided by the embodiment specifically comprises the following steps:
s1, dissolving 0.5g of chitosan (0.045 mmol) in 50ml of pure water, and stirring for 2 hours until the chitosan is fully dissolved;
s2, 0.030g of biphenyl-4-carboxylic acid (BPA, 0.15 mmol) was dissolved in 50ml DMF;
s3, 0.291g (1.5 mmol) of EDC and 0.174g (1.5 mmol) of NHS were dissolved in 1ml of pure water and added to the BPA solution, respectively;
s4, slowly dropwise adding the activated BPA solution into the chitosan water solution under the protection of nitrogen, and reacting for 24 hours at 30 ℃;
s5, after the reaction is finished, the reaction solution is filled into a dialysis bag with the speed of 3000Da and dialyzed for 3d in pure water, water is changed every 4 hours, EDC and NHS are removed, and freeze drying is finished after the dialysis to obtain chitosan-BPA product (abbreviated as CS-BPA);
s6, dissolving CS-BPA (BPA content 1 mu mol) in 4ml of 1% acetic acid aqueous solution, adding 8 mu mol of alpha-cyclodextrin, performing ultrasonic treatment for 1h, pouring into a mould, and drying at 40 ℃ for 18h to form the film.
Example 4
The preparation method of the room-temperature phosphorescent material provided by the embodiment specifically comprises the following steps:
s1, dissolving 0.5g of chitosan (0.045 mmol) in 50ml of pure water, and stirring for 2 hours until the chitosan is fully dissolved;
s2, 0.030g of 1, 8-naphthalene dicarboxylic anhydride (1, 8-NA,0.15 mmol) is dissolved in 50ml DMF;
s3, 0.291g (1.5 mmol) of EDC and 0.174g (1.5 mmol) of NHS were dissolved in 1ml of pure water, respectively, and added to the 1-naphthoic acid solution;
s4, slowly dripping the activated 1,8-NA solution into the chitosan water solution under the protection of nitrogen, and reacting for 24 hours at 30 ℃;
s5, after the reaction is finished, the reaction solution is filled into a dialysis bag with the speed of 3000Da and dialyzed for 3d in pure water, water is changed every 4 hours, EDC and NHS are removed, and freeze drying is finished after the dialysis to obtain chitosan-1, 8-NA (abbreviated as CS-1, 8-NA);
s6, dissolving CS-1,8-NA (1, 8-NA content 1 mu mol) in 4ml of 1% acetic acid aqueous solution, adding 5 mu mol of alpha-cyclodextrin, carrying out ultrasonic treatment for 1h, pouring into a mould, and drying at 40 ℃ for 18h to form the film.
Example 5
The preparation method of the room-temperature phosphorescent material provided by the embodiment specifically comprises the following steps:
s1, dissolving 0.5g of chitosan (0.045 mmol) in 50ml of pure water, and stirring for 2 hours until the chitosan is fully dissolved;
s2, 0.043g of 1-pyrenebutyric acid (1-PyBA, 0.15 mmol) was dissolved in 50ml DMF;
s3, dissolving 0.291g (1.5 mmol) of EDC and 0.174g (1.5 mmol) of NHS in 1ml of pure water respectively, and adding the mixture into the 1-PyBA solution;
s4, slowly dripping the activated 1-PyBA solution into the chitosan water solution under the protection of nitrogen, and reacting for 24 hours at 30 ℃;
s5, after the reaction is finished, the reaction solution is filled into a dialysis bag with the speed of 3000Da and dialyzed for 3d in pure water, water is changed every 4 hours, EDC and NHS are removed, and freeze drying is finished after the dialysis to obtain chitosan-1-PyBA (abbreviated as CS-PyBA);
s6, dissolving CS-PyBA (1-PyBA content 1 mu mol) in 4ml of 1% acetic acid aqueous solution, adding 1 mu mol of gamma-cyclodextrin, performing ultrasonic treatment for 1h, pouring into a mould, and drying at 40 ℃ for 18h to form the membrane.
Example 6
This embodiment differs from embodiment 3 only in that: the alpha-cyclodextrin in step S6 is not used for fortification.
Example 7
This embodiment differs from embodiment 3 only in that: the amount of α -cyclodextrin used in step S6 was 1. Mu. Mol.
Example 8
This embodiment differs from embodiment 3 only in that: the amount of α -cyclodextrin used in step S6 was 2. Mu. Mol.
Example 9
This embodiment differs from embodiment 3 only in that: the amount of α -cyclodextrin used in step S6 was 4. Mu. Mol.
Example 10
This embodiment differs from embodiment 3 only in that: the amount of α -cyclodextrin used in step S6 was 12. Mu. Mol.
Example 11
This embodiment differs from embodiment 1 only in that: and S6, dissolving the CS-1-NA obtained in the step S5 in 1% acetic acid aqueous solution, and dripping into a polytetrafluoroethylene mould to prepare the film.
Example 12
This embodiment differs from embodiment 2 only in that: and (6) without the step (S6), dissolving the CS-NTBA obtained in the step (S5) in 1% acetic acid aqueous solution, and dripping into a polytetrafluoroethylene mould to prepare the film.
Example 13
This embodiment differs from embodiment 3 only in that: and S6, dissolving the CS-BPA obtained in the step S5 in 1% acetic acid aqueous solution, and dripping into a polytetrafluoroethylene mould to prepare a film.
Example 14
This embodiment differs from embodiment 4 only in that: and (6) without the step (S6), dissolving the CS-1,8-NA obtained in the step (S5) in a 1% acetic acid aqueous solution, and dripping the solution into a polytetrafluoroethylene mould to prepare the film.
Example 15
This embodiment differs from embodiment 5 only in that: and (6) without the step (S6), dissolving the CS-PyBA obtained in the step (S5) in 1% acetic acid aqueous solution, and dripping into a polytetrafluoroethylene mould to prepare the film.
Example 16
This embodiment differs from embodiment 5 only in that: without step S6, 1-pyrene butyric acid is replaced by 1-pyrene formic acid (abbreviated as 1-Pyr), CS-Pyr obtained in step S5 is dissolved in 1% acetic acid aqueous solution, and the solution is dripped into a polytetrafluoroethylene mould to prepare a film.
Example 17
This embodiment differs from embodiment 5 only in that: 1-pyrene butyric acid was replaced with 1-pyrene formic acid.
In example 3 and examples 6-10, referring to FIGS. 3a and 3b, the phosphorescent lifetime at room temperature gradually increases as the amount of α -CD added increases, and the phosphorescent emission (abbreviated as RTP) emission and lifetime are strongest when the α -CD addition ratio is 8 times the BPA content. And when the alpha-CD addition ratio is 12 times of the BPA content, the emission and the service life are reduced compared with 8 times. The CS main chain is a cyclic macromolecule, the diameter of the cross section of the molecular chain is about 0.85nm, the diameter of the inner ring of the alpha-CD is about 0.47nm, and the CD can not sleeve the CS main chain therein. As seen from the transmission chart, spherical CS-BPA hydrophobic associates with a diameter of about 50-100nm are dispersed in a film with an alpha-CD addition of 0 (FIG. 3 d), while when the alpha-CD addition is 2 times (FIG. 3 e), the size of part of the associates is consistent with that of 0, but spherical associates with a diameter of about 200nm and irregularly shaped ellipsoidal associates with a large size still appear. This is because, in addition to forming inclusion complexes with BPA on CS-BPA, α -CD can act as a crosslinker to link more CS-BPA associates together, forming a complex association of CS-BPA-CD-CS-BPA, where the otherwise dense CS-BPA associates become loose, and the size of the association becomes larger, and α -CD can readily interact with CS-BPA molecules to allow a portion of α -CD to adhere to the CS-BPA-CD-CS-BPA surface, such that the spherical association is changed to an irregularly shaped ellipsoidal association. The crystal peaks of the channel-mounted crystalline domains formed by α -CD/CS-BPA are approximately 13℃and 20 ℃. From the XRD curve (FIG. 3 c), the addition of α -CD was 8-fold, showing distinct characteristic peaks at 13℃and 20℃indicating that α -CD forms a pipeline-like crystalline domain in CS-BPA. The formation of the crystalline domains greatly limits non-radiative relaxation, enhances room temperature phosphorescent emission, and greatly increases room temperature phosphorescent lifetime.
The film obtained in example 11, CS-1-NA, is dried at 80℃as shown in FIG. 2. The delayed emission spectrum of CS-1-NA in the dry state was measured and showed a maximum phosphorescence emission peak at 524 nm. The film was fumigated with water vapor, and the phosphorescence emission peak of CS-1-NA was gradually decreased as the time of the fumigated film was gradually increased (FIG. 2 c). After the steam fumigates for 30 seconds, the phosphorescence emission peak of the film is obviously and greatly reduced, and then gradually reduced until the phosphorescence emission peak almost completely disappears after the steam fumigates the film for 4 minutes. This demonstrates that the presence of water has an effect on the room temperature phosphorescent properties of the film. To further verify the effect of water on film room temperature phosphorescence, the film was fumigated in water vapor for 4min with little to no phosphorescence emission signal detected at 524 nm. The heating time was fixed at 5min, the temperature of the heated film was varied, and as the heating temperature was increased, a gradual increase in the phosphorescence emission peak at 524nm was detected for the film, and when heated to 70 ℃, the phosphorescence emission at room temperature was substantially recovered for the CS-1-NA film, and there was substantially no change in the phosphorescence emission at room temperature for the film continued to be heated at 80 ℃ (FIG. 2 b). At this time, the moisture in the CS-1-NA film is considered to be substantially removed, and the phosphorescence emission intensity of the CS-1-NA film from which the moisture was removed is restored to the phosphorescence emission intensity in the dry state. To determine if the RTP response of the CS-1-NA film was cyclic reversible under water/heat stimulation, the phosphorescent signal at 524nm of the CS-1-NA film in the 80℃dry state was measured, and the phosphorescent signal at 524nm after 4min of the steam fumigated film was repeated five times, and it was found that the phosphorescent signal was recovered and substantially stable after 5min of heating at 80℃each time even though the film was fumigated with steam (FIG. 2 a).
In addition to the CS-1-NA film, the CS-NTBA, CS-BPA, CS-1,8-NA and CS-PyBA films obtained in examples 12-15 also exhibited RTP responsiveness under water/heat stimulation, and also had the characteristic of being reversible in circulation. Thus, the room temperature phosphorescent change of the film can also be used as a means of monitoring the ambient humidity.
The phosphorescent lifetime before and after the enhancement of each substituted acid cyclodextrin is given below.
TABLE 1 phosphorescent lifetime before and after cyclodextrin fortification
| Substituted acid name | Chitosan derivative lifetime (ms) | Cyclodextrin enhanced lifetime (ms) |
| NTBA | 46 | 70 |
| BPA | 500 | 1443 |
| 1-NA | 825 | 934 |
| 1,8-NA | 257 | 331 |
| 1-PyBA | 232 | 285 |
| 1-Pyr | 180 | 186 |
Referring to FIGS. 4-9, and Table 1 shows a comparison of phosphorescent lifetimes before and after enhancement of the cyclodextrins of examples 1-5 and 11-17 of the present application, it can be seen that the cyclodextrins enhance the phosphorescent lifetimes of the respective films, especially for CS-BPA, the lifetime after cyclodextrin enhancement is increased to approximately 3 times before enhancement, reaching lifetimes exceeding seconds, and the lifetime after cyclodextrin enhancement of CS-1-NA is also increased to 934ms approaching seconds. The life of the cyclodextrin before and after strengthening of other embodiments is greatly improved except that the life of the phosphorescence before and after strengthening of the CS-1-Pyr cyclodextrin is less improved.
In the description of the present specification, reference to the terms "one embodiment/manner," "some embodiments/manner," "example," "a particular example," "some examples," etc., means that a particular feature, structure, material, or characteristic described in connection with the embodiment/manner or example is included in at least one embodiment/manner or example of the application. In this specification, the schematic representations of the above terms are not necessarily for the same embodiment/manner or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments/modes or examples. Furthermore, the various embodiments/modes or examples described in this specification and the features of the various embodiments/modes or examples can be combined and combined by persons skilled in the art without contradiction.
It will be appreciated by those skilled in the art that the above-described embodiments are merely for clarity of illustration of the disclosure, and are not intended to limit the scope of the disclosure. Other variations or modifications will be apparent to persons skilled in the art from the foregoing disclosure, and such variations or modifications are intended to be within the scope of the present disclosure.
Claims (6)
1. A method for preparing a room temperature phosphorescent material, comprising:
adding an activating agent into an organic acid solution, wherein the organic acid is one of triphenylamine 4,4' -tricarboxylic acid, 1-naphthoic acid, biphenyl-4-carboxylic acid, 1, 8-naphthalene dicarboxylic anhydride and 1-pyrene butyric acid, and the activating agent is N- (3-dimethylaminopropyl) -N ' -ethylcarbodiimide hydrochloride/N-hydroxysuccinimide, wherein the molar ratio of N- (3-dimethylaminopropyl) -N ' -ethylcarbodiimide hydrochloride to N-hydroxysuccinimide is (20:1) - (1:1);
completely reacting the organic acid solution with chitosan aqueous solution after carboxyl activation, wherein the molar ratio of the chitosan to the organic acid is (8:1) - (3:100);
removing the activating agent to obtain chitosan derivative;
dissolving the chitosan derivative in an acetic acid aqueous solution, and adding cyclodextrin to obtain a chitosan derivative-cyclodextrin, wherein the molar ratio of the cyclodextrin to the organic acid contained in the chitosan derivative is (1:5) - (20:1);
the cyclodextrin is alpha-cyclodextrin.
2. The method according to claim 1, wherein the step of completely reacting the activated carboxylic acid solution with the chitosan aqueous solution is performed under the protection of an inert gas.
3. The method according to claim 1, wherein the concentration of the aqueous acetic acid solution is not more than 50%.
4. Use of the chitosan derivative produced by the production process of any one of claims 1 to 3 in water with a stimulus-responsive product.
5. A room temperature phosphorescent material characterized in that a chitosan derivative prepared by the preparation method of any one of claims 1 to 3 is dissolved in an aqueous acetic acid solution, and dried to obtain a chitosan derivative film, and phosphorescence of the chitosan derivative film has stimulus responsiveness to water and is reversible in circulation, or a chitosan derivative-cyclodextrin film is obtained after drying the chitosan derivative-cyclodextrin prepared by the preparation method of any one of claims 1 to 3.
6. Use of the room temperature phosphorescent material of claim 5 in the preparation of a product having room temperature phosphorescent properties.
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