CN114957220B - Fluorescent molecule, multicolor system, and preparation method and application thereof - Google Patents
Fluorescent molecule, multicolor system, and preparation method and application thereof Download PDFInfo
- Publication number
- CN114957220B CN114957220B CN202210507670.7A CN202210507670A CN114957220B CN 114957220 B CN114957220 B CN 114957220B CN 202210507670 A CN202210507670 A CN 202210507670A CN 114957220 B CN114957220 B CN 114957220B
- Authority
- CN
- China
- Prior art keywords
- solution
- cucurbituril
- multicolor
- reaction
- assembly
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
- C07D401/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing three or more hetero rings
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
- G01N21/643—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes" non-biological material
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6447—Fluorescence; Phosphorescence by visual observation
-
- G—PHYSICS
- G06—COMPUTING; CALCULATING OR COUNTING
- G06Q—INFORMATION AND COMMUNICATION TECHNOLOGY [ICT] SPECIALLY ADAPTED FOR ADMINISTRATIVE, COMMERCIAL, FINANCIAL, MANAGERIAL OR SUPERVISORY PURPOSES; SYSTEMS OR METHODS SPECIALLY ADAPTED FOR ADMINISTRATIVE, COMMERCIAL, FINANCIAL, MANAGERIAL OR SUPERVISORY PURPOSES, NOT OTHERWISE PROVIDED FOR
- G06Q30/00—Commerce
- G06Q30/018—Certifying business or products
- G06Q30/0185—Product, service or business identity fraud
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02B—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
- Y02B20/00—Energy efficient lighting technologies, e.g. halogen lamps or gas discharge lamps
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Immunology (AREA)
- Business, Economics & Management (AREA)
- General Physics & Mathematics (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Pathology (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- Development Economics (AREA)
- Molecular Biology (AREA)
- Optics & Photonics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Entrepreneurship & Innovation (AREA)
- Accounting & Taxation (AREA)
- Materials Engineering (AREA)
- Economics (AREA)
- Strategic Management (AREA)
- Marketing (AREA)
- Finance (AREA)
- General Business, Economics & Management (AREA)
- Theoretical Computer Science (AREA)
- Investigating Or Analysing Materials By The Use Of Chemical Reactions (AREA)
Abstract
The invention discloses a fluorescent molecule, a multicolor system, a preparation method and application thereof, wherein the fluorescent molecule has the following structure:
Description
Technical Field
The invention relates to a fluorescent molecule, a preparation method thereof, a multicolor system containing the fluorescent molecule and application of the multicolor system in anti-counterfeiting, and belongs to the technical field of organic luminescent materials.
Background
The anti-counterfeiting technology is an important means for information protection in social production activities in human society, and has important significance for solving social problems such as technology plagiarism. At present, along with social development and scientific progress, the anti-counterfeiting period of some traditional anti-counterfeiting technologies is going to the end. On the one hand, the method promotes the upgrading and the updating of the traditional anti-counterfeiting technology, and on the other hand, the generation and the development of various novel and efficient anti-counterfeiting means are promoted. The application of a multicolor luminous system with responsiveness in developing anti-counterfeiting technology is one of the hot research directions of anti-counterfeiting technology.
To solve this problem, various responsive luminescent technologies, or smart luminescent materials, have been developed. Currently, pH, steam, electric field, temperature, mechanical force, solvent, etc. are used as control methods for controlling luminescence changes of a luminescent material. One of them is a light-emitting system with excitation light modulation, the light-emitting behavior of which can be modulated by changing the excitation wavelength. Meanwhile, the luminous system is simple to prepare, the regulation and control means are simple and efficient, complex equipment is not needed, and the application cost of the anti-counterfeiting technology can be effectively reduced.
However, most excitation light modulation luminescent systems have the disadvantage of a single luminescent color change. Therefore, the excitation light modulation and control luminescent system is used as a guest molecule to interact with a main guest body and perform hierarchical self-assembly with a macrocyclic molecule such as cucurbituril and the like, not only can the luminescence be regulated by changing the excitation wavelength, but also the proportion among the main guest body molecules can be changed to perform luminescence regulation, so that the luminescent color change of the multicolor luminescent system is greatly enriched. Therefore, the research of the self-assembled luminous system with multi-stimulus response has important significance for the development of novel anti-counterfeiting technology.
Disclosure of Invention
The invention aims to: in order to solve the problems of the prior art, a first object of the present invention is to provide a fluorescent molecule, a second object of the present invention is to provide a method for preparing the fluorescent molecule, a third object of the present invention is to provide a multicolor system comprising the fluorescent molecule, a fourth object of the present invention is to provide a method for preparing the multicolor system comprising the fluorescent molecule, and a fifth object of the present invention is to provide an application of the multicolor system comprising the fluorescent molecule in anti-counterfeit technology.
The technical scheme is as follows: the fluorescent molecule is formed by coupling a carbazolyl structural unit and an alkylpyridinium salt structural unit, and has the following structure:
wherein n is an integer of 0 to 12.
Preferably, n is 1, 3 or 7.
The preparation method of the fluorescent molecule comprises the following steps:
(1) Adding 2, 7-dibromocarbazole, 4-pyridine boric acid and potassium carbonate into a mixed solution of DMF and water from which dissolved oxygen is removed, adding tetrakis (triphenylphosphine) palladium, heating for reaction, collecting an organic layer after the reaction is finished, and purifying the organic layer to obtain a product 2, 7-bis (4-pyridyl) carbazole;
(2) Adding 2, 7-bis (4-pyridyl) carbazole and halogenated hydrocarbon into DMF, and reacting under the protection of nitrogen; and after the reaction is finished, acetone is added into the reaction liquid and is filtered, and the filter cake is washed with acetone, dichloromethane and n-hexane for multiple times in sequence to obtain fluorescent molecules.
Preferably, in the step (1), the molar ratio of the 2, 7-dibromocarbazole, 4-pyridine boric acid and potassium carbonate is 1:1.2 to 1.5:2 to 3.
Preferably, in the step (1), the temperature of the heating reaction is 70-120 ℃, and the time of the heating reaction is 12-18 hours.
Preferably, in step (2), the halogenated hydrocarbons are bromoethane, 1-bromobutane and 1-bromooctane.
Preferably, in step (2), the 2, 7-bis (4-pyridyl) carbazole and the halogenated hydrocarbon are present in a molar ratio of 1: 20-30 parts.
Preferably, in the step (2), the reaction temperature is 80-110 ℃ and the reaction time is 12-48 hours.
The invention also comprises a multicolor luminous system which comprises the fluorescent molecule and cucurbituril.
Preferably, the cucurbituril is cucurbituril [7] or cucurbituril [8 ].
The preparation method of the multicolor luminous system comprises the following steps: the fluorescent molecules are prepared into aqueous solution by water to obtain solution I, cucurbituril is added into part of the solution I to prepare cucurbituril-luminescent molecule solution, and solution II is obtained to obtain the multicolor luminescent system.
Preferably, the solution I and the solution II are mixed according to different proportions to obtain mixed solutions with different proportions, and then a plurality of multicolor luminous systems are obtained. When the proportion of the solution I and the solution II is different, the color of the obtained multicolor luminous system is different due to the different proportion of fluorescent molecules and cucurbiturils.
Preferably, when cucurbituril [7] uril is used, the ratio of the solution I to the solution II in the multicolor lighting system is 1:0.2-3.0.
Preferably, when cucurbituril [8] urils are used, the ratio of the solution I to the solution II in the multicolor lighting system is 1:0.1-1.5.
Preferably, the pH of the water is from 0 to 7.
More preferably, the pH of the water is 5.
The multi-stimulus-responsive multicolor luminous system designed by the invention is a hierarchical self-assembly body formed by excitation light regulation and control fluorescent molecules and interaction of the excitation light regulation and control fluorescent molecules and cucurbituril molecules. The luminescence behavior of the multicolor luminescence system can be regulated by changing the wavelength of the excitation light and regulating the proportion of host-guest molecules. Meanwhile, the multiple-light-emitting system has rich fluorescence colors and obvious effect, and is hopeful to become a novel material in the field of anti-counterfeiting technology.
The invention also comprises the application of the multicolor luminous system in anti-counterfeiting technology. The responsivity of partial components in the multicolor luminous system to the excitation light can be used for developing a multilayer encryption technology.
The anti-counterfeiting mechanism of the invention: the anti-counterfeiting purpose is realized by different patterns displayed under different excitation lights in the multicolor luminous system. The multicolor luminous system consists of background color luminous molecules, light-operated luminous molecules and luminous level self-assemblies. The background color luminescent molecules are used as the background, and the luminescent color of the background color luminescent molecules is not changed along with the change of the wavelength of the exciting light. The light-operated luminescent molecules and the luminescent layer self-assemblies are used for designing specific patterns and displaying the patterns at a fixed excitation wavelength. When the excitation wavelength is changed to a specific wavelength, the meaning of the expression of the specific pattern changes from the first background color to the second background color. Double-layer anti-counterfeiting is realized by the principle.
The beneficial effects are that: compared with the prior art, the invention has the following remarkable advantages:
the fluorescent molecule is formed by coupling a carbazolyl structural unit and an alkylpyridinium structural unit, has the wavelength responsiveness of excitation light, and has different luminescent colors under different excitation lights. Based on the fluorescent molecules, the invention provides a novel multicolor luminous system which consists of a class of excitation light modulation fluorescent molecules and a hierarchical self-assembly body formed by the class of excitation light modulation fluorescent molecules and cucurbituril molecules. The multicolor luminous system has the advantages of simple synthetic route, low cost and easy acquisition of synthetic raw materials, simple assembly preparation process and the like. Meanwhile, the system has dual stimulus responsiveness and obvious luminous effect, and can be used for developing information encryption technology.
Drawings
FIG. 1 is a graph showing fluorescence spectra of CPDE, CPDB and CPDO at excitation light of 330nm and 400 nm;
FIG. 2 is a photograph of the fluorescent colors of CPDE, CPDB and CPDO under different excitation light;
FIG. 3 is a graph of fluorescence spectra of CPDB under different excitation lights;
FIG. 4 is a graph of fluorescence spectra of CPDB and cucurbituril [8] urils in different molar ratios at excitation light of 330nm,365nm and 400 nm;
FIG. 5 is a photograph of the fluorescent color of CPDB and different molar ratios of cucurbiturils [8] urils under different excitation lights;
FIG. 6 is a graph of fluorescence spectra of CPDB and cucurbit [7] urils 330nm,365nm and 400nm in different molar ratios;
FIG. 7 is a photograph of a fluorescent color of CPDB and different molar ratios of cucurbit [7] urils under different excitation lights;
FIG. 8 is a CIE chart of CPDB and fluorescent colors of cucurbit [8] urils and cucurbit [7] urils at different molar ratios under different excitation;
fig. 9 is a diagram showing the effect of the multicolor illuminant system applied to anti-counterfeiting.
Detailed Description
The technical scheme of the invention is further described below with reference to the accompanying drawings.
Example 1 preparation of fluorescent molecules
(1) 3g of 2, 7-dibromocarbazole, 4-pyridineboronic acid and potassium carbonate are reacted in a molar ratio of 1:1.5:3, putting the mixture into a mixed solution of DMF and water which is pretreated by blowing nitrogen to remove dissolved oxygen, and taking tetra (triphenylphosphine) palladium as a catalyst, wherein the reaction temperature is 95 ℃ and the reaction time is 12 hours; after the completion of the reaction, the organic layer was collected and purified by column chromatography to give 1.5g of 2, 7-bis (4-pyridyl) carbazole as a product.
2, 7-bis (4-pyridyl) carbazole as product 1 H-NMR analysis gave the following results: 1 H-NMR(DMSO-d 6 ，600MHz)：δ11.77(s，1H)，8.78(d，J＝5.4Hz，4H)，8.38(d，J＝8.1Hz，2H)，8.07(d，J＝5.5Hz，4H)，8.03(s，2H)，7.73(d，J＝7.8Hz，2H)。
(2) 0.2g of 2, 7-bis (4-pyridyl) carbazole and bromoethane in a molar ratio of 1:20 is put into DMF, the nitrogen protection is adopted, the reaction temperature is 95 ℃, and the reaction time is 48 hours; after the reaction is finished, a large amount of acetone is added into the reaction liquid and filtered, and the filter cake is washed with acetone, dichloromethane and n-hexane for multiple times to obtain 0.2g of final product 4,4' -carbazole-2, 7-diylbis (1-ethylpyridine-1-bromo salt) (CPDE for short).
Nuclear magnetic resonance hydrogen spectrum of 4,4' -carbazole-2, 7-diylbis (1-ethylpyridine-1-bromo salt) 1 H-NMR) analysis, the results were as follows: 1 H-NMR(DMSO-d 6 ，600MHz)：δ：12.06(s，1H)，9.15-9.13(d，J＝6.9Hz，4H)，8.64-8.63(d，J＝7.0Hz，4H)，8.53-8.51(d，J＝8.3Hz，2H)，8.25(s，2H)，7.96-7.93(dd，2H)，4.67-4.63(t，J＝7.2Hz，4H)，1.61-1.58(t，J＝7.3Hz 6H)。
nuclear magnetic resonance carbon spectrum of 4,4' -carbazole-2, 7-diylbis (1-ethylpyridine-1-bromo salt) product 13 C-NMR) analysis, the results were as follows: 13 C-NMR(DMSO-d 6 )δ：155.81，144.90，141.84，132.45，125.20，122.90，119.65，111.85，55.83，16.82。
the product 4,4' -carbazole-2, 7-diylbis (1-ethylpyridine-1-bromo salt) was analyzed by high resolution mass spectrometry as follows: ESI-MS m/z: c (C) 26 H 25 N 3 Br 2 ，[M-2Br] 2+ ：189.60185。
Example 2 preparation of fluorescent molecules
(1) The procedure is as in example 1, except that the selected bromohydrocarbon is changed to 1-bromobutane to give 0.25g of 4,4' -carbazole-2, 7-diylbis (1-butylpyridine-1-bromide) (abbreviated as CPDB) as the final product.
The product 4,4' -carbazole-2, 7-diylbis (1-butylpyridine-1-bromide) was subjected to 1 H-NMR analysis gave the following results: 1 H-NMR(DMSO-d 6 )δ：12.06(s，1H)，9.13-9.12(d，J＝6.6Hz，4H)，8.64-8.63(d，J＝6.8Hz，4H)，8.53-8.51(d，J＝8.3Hz，2H)，8.24(s，2H)，7.95-7.94(dd，J＝1.7Hz，2H)，4.63-4.60(t，J＝7.4Hz，4H)，1.98-1.93(m，J＝7.5Hz，4H)，1.39-1.32(m，J＝7.5Hz，4H)，0.97-0.94(t，J＝7.4Hz，6H)。
the product 4,4' -carbazole-2, 7-diylbis (1-butylpyridine-1-bromide) was subjected to 13 C-NMR analysis gave the following results: 13 C-NMR(DMSO-d 6 )δ：155.80，145.08，141.83，132.38，125.18，124.96，122.89，119.66，60.01，33.13，19.29，13.85。
the product 4,4' -carbazole-2, 7-diylbis (1-butylpyridine-1-bromide) was analyzed by high resolution mass spectrometry as follows: ESI-MS m/z: c (C) 30 H 33 N 3 Br 2 ，[M-2Br] 2+ ：217.63306。
Example 3 preparation of fluorescent molecules
(1) The procedure is as in example 1, except that the selected bromohydrocarbon is changed to 1-bromooctane to give 0.25g of 4,4' -carbazole-2, 7-diylbis (1-octylpyridine-1-bromide) (abbreviated as CPDO) as a final product.
The product 4,4' -carbazole-2, 7-diylbis (1-octylpyridine-1-bromide) was subjected to 1 H-NMR analysis gave the following results: 1 H-NMR(DMSO-d 6 )δ:12.07(s，1H)，9.14-9.13(d，J＝5.2Hz，4H)，8.64-8.63(d，J＝7.0Hz，4H)8.52-8.51(d，J＝8.3Hz，2H)，8.25(s，2H)，7.96-7.94(dd，J＝8.3，1.7Hz，2H)，4.62-4.60(t，J＝7.5Hz，4H)，1.99-1.94(m，4H)，1.34-1.26(m，20H)，0.87-0.85(t，6H)。
for the product 4,4' -carbazole-2, 7-diylbis (1-octylpyridine-1-bromo salt) was used 13 C-NMR analysis gave the following results: 13 C-NMR(DMSO-d 6 )δ：155.81，145.07，141.84，132.42，125.18，124.98，122.91，119.67，111.87，60.24，31.63，31.18，28.95，28.88，25.95，22.53，14.42。
the product 4,4' -carbazole-2, 7-diylbis (1-octylpyridine-1-bromide) was analyzed by high resolution mass spectrometry as follows: ESI-MS m/z: c (C) 38 H 49 N 3 bBr 2 ：[M-2Br] 2+ ：273.69504。
Example 4 fluorescence testing of CPDE, CPDB and CPDO
Fluorescence tests were performed on CPDE, CPDB and CPDO with excitation light at 330nm and 400nm by fluorescence spectroscopy, and the results are shown in FIGS. 1-3.
FIG. 1 is a graph showing fluorescence spectra of CPDE, CPDB and CPDO at excitation light of 330nm and 400nm. Wherein, (a) is 330nm and (b) is 400nm. From FIG. 1, it can be seen that CPDE and CPDB have different fluorescence spectra under excitation of 330nm and 400nm, and maximum emission peak wavelengths are about 440nm (330 nm excitation) and 540nm (400 nm excitation), respectively; and under excitation of CPDO excitation light of 330nm and 400nm, the fluorescence spectrum is not obviously different, and the maximum emission peak wavelength is 540nm. Description: CPDE and CPDB have excitation light modulation phenomenon, can be regarded as the light response component, CPDO does not have excitation light modulation phenomenon, can regard as the background, is used for information camouflage.
Fig. 2 is a photograph of the fluorescent colors of CPDE, CPDB and CPDO under different excitation light. As can be seen from fig. 2, CPDE and CPDB exhibit blue fluorescence under 330nm excitation light irradiation, white fluorescence under 365nm excitation light irradiation, and yellow-green fluorescence under 400nm excitation light irradiation; CPDO exhibits a yellowish green fluorescence under both 330nm and 400nm excitation light illumination.
Fig. 3 is a graph of fluorescence spectra of CPDB under different excitation light. As can be seen from fig. 3, the maximum emission wavelength of the fluorescent molecule CPDB is changed from 540nm to 440nm as the excitation wavelength is changed from 400nm to 330 nm.
Example 5 preparation of multicolor light-emitting System
(1) 1.79mg of fluorescent molecule 4,4' -carbazol-2, 7-diylbis- (1-butylpyridine-1-bromide) (CPDB) prepared in example 2 was dissolved in 3mL of water (pH=5) to prepare a solution having a concentration of 1mM to obtain solution I
(2) 1.33mg of cucurbit [8]]Adding urea molecule into 1mL solution I, and ultrasonic preparing into calabash [8]]Urea-luminescent molecules (luminescent molecules and cucurbits [8]]Urea to concentration ratio of 1: 2) The dispersion liquid is obtained as a solution II, a certain amount of solution I and solution II are taken and mixed to obtain a solution I and solution II with the proportion of 1:0. 1:0.1, 1:0.2, 1:0.3, 1:0.4, 1:0.5, 1:0.6, 1:0.7, 1:1.0, 1:1.3 and 1:1.5 and diluting the CPDB concentration in the solution with water to a concentration of 4X 10 -5 M, obtaining the hierarchical self-assembly liquid A with different proportions, namely 11 multicolor luminous systems.
The multicolor light-emitting system prepared in this example was subjected to a test of light-emitting effect by fluorescence spectrum, and the results are shown in fig. 4 to 5. FIG. 4 is a graph of fluorescence spectra of CPDB and cucurbituril [8] urils in different molar ratios at excitation light wavelengths of 330nm,365nm and 400nm, wherein (a) is 330nm, (b) is 365nm, and (c) is 400nm. As can be seen from FIG. 4, the CPDB maximum emission wavelength was eventually shifted from 540nm and 440nm to 580nm as the cucurbit [8] uril concentration increased.
FIG. 5 is a photograph of the fluorescent color of CPDB and different molar ratios of cucurbit [8] urils under different excitation lights. From FIG. 5, it can be seen that CPDB fluorescence color exhibits a blue-to-orange transition at 330nm excitation light with increasing cucurbituril [8] urea concentration, a white-to-orange transition at 365nm excitation light with increasing cucurbituril [8] urea concentration, and a yellow-green-to-orange transition at 400nm excitation light with increasing cucurbituril [8] urea concentration.
EXAMPLE 6 preparation of multicolor light-emitting System
The preparation process is the same as in example 5, wherein 3.49mg of cucurbit [7]]The urea molecule is dissolved in 3mL of water (pH=5) to prepare a solution with the concentration of 1mM to obtain a solution II, and a certain amount of the solution I and the solution II are taken and mixed to obtain a solution with the proportion of 1:0. 1:0.2, 1:0.4, 1:0.6, 1:0.8, 1:1.0, 1:1.6, 1:2.0, 1:2.6 and 1:3.0 and diluting the CPDB concentration in the solution with water to a concentration of 4X 10 -5 M, obtaining hierarchical self-assembly liquid B with different proportions, namely 10 multi-color hairsA light system.
The 11 multicolor light-emitting systems prepared in this example were tested for light-emitting effect by fluorescence spectroscopy, and the results are shown in fig. 6 to 7. FIG. 6 is a graph of fluorescence spectra of CPDB and cucurbituril [7] urils in different molar ratios at excitation light wavelengths of 330nm,365nm and 400nm, wherein (a) is 330nm, (b) is 365nm, and (c) is 400nm. As can be seen from FIG. 6, the CPDB maximum emission wavelength eventually shifted from 540nm and 440nm to 530nm as the cucurbit [7] urils concentration increased.
FIG. 7 is a photograph of the fluorescent color of CPDB and different molar ratios of cucurbit [7] urils under different excitation lights. From FIG. 7, it can be seen that CPDB fluorescence exhibits a blue to green transition at 330nm excitation light with increasing cucurbit [7] urea concentration, a white to green transition at 365nm excitation light with increasing cucurbit [7] urea concentration, and a yellow to green transition at 400nm excitation light with increasing cucurbit [7] urea concentration.
CPDB and different molar ratios of cucurbit [8] urils and cucurbit [7] urils the CIE chromatograms of the fluorescent colors under different excitation are shown in FIG. 8, wherein (a) is the multicolor luminous system obtained in example 5 and (b) is the multicolor luminous system obtained in example 6. As can be seen from fig. 8, by adjusting the ratio between the excitation light and CPDB and cucurbituril, different emission lights of blue, yellow, orange, green, etc. can be obtained.
Example 7 application of multicolor light-emitting System in anti-counterfeiting technology
(1) Preparing a die, wherein the die is a 248mm multiplied by 5mm cuboid PVE plastic plate, and 31 multiplied by 31 cuboid cells with the interval of 3mm are processed on the plastic plate, and each cell is provided with 5mm multiplied by 3mm;
(2) The fluorescent molecules CPDE, CPDB and CPDO obtained in examples 1-3, respectively, were selected and formulated as 4X 10 with water (pH=5) -5 A solution of M; then, the mixture ratio in the example 5 is 1:1 and 1.5:1, the ratio of the hierarchical self-assembly body solution a in example 6 is 1:1 and 2: the hierarchical self-assembly solution B of 1 was prepared for later experiments.
(3) According to the set pattern 'IAMSER', dropwise adding the CPDB solution in the step (2) into small grooves with the patterns of lower-case English words 'E' and 'r' on a die in the step (1), dropwise adding the CPDE solution in the step (2) into upper-case English letters 'S', 'E' and 'U', and mixing the CPDB solution in the step (2) into a ratio of 1:1.0, in a small groove with the dripping pattern of English letter A, the mixture ratio in the step (2) is 1: 1.5-level self-assembly liquid is dripped into a small groove with an English letter M, and the proportion in the step (2) is 1: the dropping pattern of the 2.0-level self-assembly liquid is in a small groove with capital English letter I. And (3) taking the CPDO solution dripping pattern in the step (2) as a background, namely dripping the CPDO solution into small grooves of other parts where letters are not set.
(4) Light sources with wavelengths of 365nm and 400nm are selected as excitation light sources. CPDE and CPDB are different from CPDO fluorescent colors at 365nm excitation light source, so that the first information can be displayed together with the level self-assembled body solutions A and B, and CPDE and CPDB are the same as CPDO fluorescent colors at the excitation light source wavelength of 400nm, the level self-assembled body solution A and the level self-assembled body solution B are unchanged in fluorescence, and the second information is displayed, and the result is shown in FIG. 9.
Fig. 9 is a diagram showing the effect of the multicolor illuminant system applied to anti-counterfeiting. CPDE and CPDB are used as responsive encryption ink for expressing misleading information, CPDO is used as background ink for hiding information, and hierarchical self-assembly solution A and hierarchical self-assembly solution B are used as non-responsive encryption ink for expressing real information. As can be seen from fig. 9, when the display information is "IAMSEUer" under 365nm light excitation and the light is switched to 400nm light, "SEUer" and the background are both yellowish green, and the final display information is "IAM", the dual anti-counterfeit function is enabled.
Claims (10)
1. The fluorescent molecule is formed by coupling a carbazolyl structural unit and an alkylpyridinium salt structural unit, and has the following structure:
wherein n is an integer of 0 to 12.
2. The fluorescent molecule of claim 1, wherein n is 1, 3 or 7.
3. A method of preparing a fluorescent molecule according to claim 1 or 2, comprising the steps of:
(1) Adding 2, 7-dibromocarbazole, 4-pyridine boric acid and potassium carbonate into a mixed solution of DMF and water from which dissolved oxygen is removed, adding tetrakis (triphenylphosphine) palladium, heating for reaction, collecting an organic layer after the reaction is finished, and purifying the organic layer to obtain a product 2, 7-bis (4-pyridyl) carbazole;
(2) Adding 2, 7-bis (4-pyridyl) carbazole and halogenated hydrocarbon into DMF, and reacting under the protection of nitrogen; and after the reaction is finished, acetone is added into the reaction liquid and is filtered, and the filter cake is washed with acetone, dichloromethane and n-hexane for multiple times in sequence to obtain fluorescent molecules.
4. The method of claim 3, wherein in the step (1), the molar ratio of 2, 7-dibromocarbazole, 4-pyridineboronic acid and potassium carbonate is 1:1.2 to 1.5: 2-3, wherein the temperature of the heating reaction is 70-120 ℃, the time of the heating reaction is 12-18 hours, and in the step (2), the molar ratio of the 2, 7-bis (4-pyridyl) carbazole to the halogenated hydrocarbon is 1: 20-30, wherein the reaction temperature is 80-110 ℃, and the reaction time is 12-48 hours; the halohydrocarbon is bromoethane, 1-bromobutane or 1-bromooctane.
5. A hierarchical self-assembly comprising the fluorescent molecule of claim 1 or 2 and cucurbituril.
6. The hierarchical self-assembly of claim 5, wherein the cucurbituril is cucurbituril [7] uril or cucurbituril [8] uril.
7. The method of preparing a hierarchical self-assembly according to claim 5 or 6, comprising the steps of: preparing the fluorescent molecules according to claim 1 or 2 into an aqueous solution by using water to obtain a solution I, adding cucurbituril into part of the solution I to prepare a cucurbituril-luminescent molecule solution, and obtaining a solution II, namely the hierarchical self-assembly body.
8. The method for preparing a hierarchical self-assembly according to claim 7, wherein the solution I and the solution II are mixed according to different proportions to obtain mixed solutions with different proportions, namely a plurality of hierarchical self-assemblies.
9. The method for preparing the hierarchical self-assembly body according to claim 8, wherein when cucurbit [7] uril is adopted, the ratio of the solution I to the solution II in the hierarchical self-assembly body is 1:0.2-3.0; when cucurbituril [8] urils are adopted, the ratio of solution I to solution II in the hierarchical self-assembly is 1:0.1-1.5; the pH of the water is 0-7.
10. Use of the hierarchical self-assembly of claim 5 or 6 in anti-counterfeiting technology.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210507670.7A CN114957220B (en) | 2022-05-11 | 2022-05-11 | Fluorescent molecule, multicolor system, and preparation method and application thereof |
| PCT/CN2023/092957 WO2023217124A1 (en) | 2022-05-11 | 2023-05-09 | Fluorescent molecule, and multicolor system and preparation method therefor and use thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210507670.7A CN114957220B (en) | 2022-05-11 | 2022-05-11 | Fluorescent molecule, multicolor system, and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114957220A CN114957220A (en) | 2022-08-30 |
| CN114957220B true CN114957220B (en) | 2023-04-25 |
Family
ID=82980920
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210507670.7A Active CN114957220B (en) | 2022-05-11 | 2022-05-11 | Fluorescent molecule, multicolor system, and preparation method and application thereof |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN114957220B (en) |
| WO (1) | WO2023217124A1 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114957220B (en) * | 2022-05-11 | 2023-04-25 | 东南大学 | Fluorescent molecule, multicolor system, and preparation method and application thereof |
| CN116102740B (en) * | 2023-02-21 | 2024-04-09 | 河南农业大学 | Photosensitive photoluminescent supermolecule nanoparticle, and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010026957A1 (en) * | 2008-09-03 | 2010-03-11 | 国立大学法人 富山大学 | Water-soluble rotaxane-type fluorescent dye and fluorescent organic molecule |
| CN106083816A (en) * | 2016-07-06 | 2016-11-09 | 山西大学 | A kind of extremely acid carbazoles pH fluorescent probe and its preparation method and application |
| CN113150770A (en) * | 2021-02-24 | 2021-07-23 | 武汉纺织大学 | Molecular assembly fluorescent probe and preparation method and application thereof |
| CN113563351A (en) * | 2021-07-13 | 2021-10-29 | 昆明理工大学 | Water-soluble ring-opening cucurbituril fluorescent probe and application thereof |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113755155A (en) * | 2021-09-09 | 2021-12-07 | 湖南师范大学 | Photochromic material and preparation method thereof |
| CN113896904B (en) * | 2021-11-16 | 2023-03-24 | 曲阜师范大学 | Quaternary supermolecule anti-counterfeiting system of cucurbituril [8] -diarylethene derivative-terpyridyl imidazole-europium and preparation method thereof |
| CN114957220B (en) * | 2022-05-11 | 2023-04-25 | 东南大学 | Fluorescent molecule, multicolor system, and preparation method and application thereof |
-
2022
- 2022-05-11 CN CN202210507670.7A patent/CN114957220B/en active Active
-
2023
- 2023-05-09 WO PCT/CN2023/092957 patent/WO2023217124A1/en unknown
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010026957A1 (en) * | 2008-09-03 | 2010-03-11 | 国立大学法人 富山大学 | Water-soluble rotaxane-type fluorescent dye and fluorescent organic molecule |
| CN106083816A (en) * | 2016-07-06 | 2016-11-09 | 山西大学 | A kind of extremely acid carbazoles pH fluorescent probe and its preparation method and application |
| CN113150770A (en) * | 2021-02-24 | 2021-07-23 | 武汉纺织大学 | Molecular assembly fluorescent probe and preparation method and application thereof |
| CN113563351A (en) * | 2021-07-13 | 2021-10-29 | 昆明理工大学 | Water-soluble ring-opening cucurbituril fluorescent probe and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| CHEN, Xiao等.Hierarchical self-assembly of an excitation-wavelength-dependent emissive fluorophore and cucurbiturils for secondary encryption.《Matter》.2022,第5卷(第11期),3883-3900. * |
| Yi Tan等.Construction of cluster-based supramolecular wire and rectangle.《Dalton Trans》.2022,(第51期),6358–6365. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114957220A (en) | 2022-08-30 |
| WO2023217124A1 (en) | 2023-11-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN114957220B (en) | Fluorescent molecule, multicolor system, and preparation method and application thereof | |
| CN106008318B (en) | A kind of chiral organic dye molecule and the preparation method and application thereof with circular polarised luminescence property | |
| Wang et al. | Rational design of novel near-infrared fluorescent DCM derivatives and their application in bioimaging | |
| CN110818743B (en) | Preparation method and application of cyclometalated platinum complex with aggregation-induced emission property | |
| CN113429963B (en) | Continuous color-changing fluorescent anti-counterfeiting material and preparation method and application thereof | |
| CN104151326A (en) | Perylene diimide-rhodamine fluorescent probe, and preparation method and application thereof | |
| CN110256218A (en) | A kind of aggregation-induced emission dye molecule and its synthetic method | |
| CN106632063B (en) | Compound I and compound II based on phenanthro- imidazoles and its preparation method and application | |
| Feng et al. | Employing metformin-directed carbon dots with room-temperature phosphorescent towards the dual-channel detection of L-tryptophan | |
| CN105400506A (en) | [2.2]cyclophane-based rhodamine Hg<2+> fluorescent probe and preparation method thereof | |
| Fischer et al. | Configurationally stable atropisomeric acridinium fluorophores | |
| CN108484479B (en) | Carbazolyl two-photon fluorescent probe and preparation method and application thereof | |
| Baleeva et al. | Conformationally locked chromophores of CFP and Sirius protein | |
| CN105198910A (en) | Turn-on-type BODIPY fluorescent sensor and its preparation method and use | |
| Das et al. | Triphenylamine substituted dipyrrinato metal complexes: Synthesis, optical and electrochemical studies | |
| Duan et al. | Slight substituent modification in coumarin molecular structures for strong solid emission and application in light-emitting devices | |
| CN105837568B (en) | A kind of fluorenyl β carbolines class compound, its application and preparation method as luminous organic material and aggregation inducing Fluorescence Increasing material | |
| CN114853656B (en) | Carbazole derivative with AEE characteristic, preparation method and application | |
| CN106833009A (en) | Coumarins green glow dyestuff containing triphenylamine ethylene lateral chain | |
| Coppo et al. | Unraveling the luminescence of new heteroleptic Ir (III) cyclometalated series | |
| CN108424425A (en) | Four ring gear metal palladium complexes, preparation method and application containing the disubstituted pyrazoles of 4- aryl -3,5- | |
| Elgemeie et al. | Microwave synthesis, photophysical properties of novel fluorescent iminocoumarins and their application in textile printing | |
| CN111333618B (en) | 488nm excited wash-free SNAP-tag probe and preparation method thereof | |
| Bao et al. | Er (OTf) 3-catalyzed synthesis of fluorescent 7-aminocoumarins | |
| CN109053815B (en) | Iridium (III) complex and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |