CN111337465B - Solid-state fluorescence anti-counterfeiting method based on reversible response of amine steam - Google Patents
Solid-state fluorescence anti-counterfeiting method based on reversible response of amine steam Download PDFInfo
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- 150000001412 amines Chemical class 0.000 title claims abstract description 28
- 230000004044 response Effects 0.000 title claims abstract description 21
- 230000002441 reversible effect Effects 0.000 title claims abstract description 21
- 238000000034 method Methods 0.000 title claims abstract description 17
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 69
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims abstract description 24
- MVVGSPCXHRFDDR-UHFFFAOYSA-N 2-(1,3-benzothiazol-2-yl)phenol Chemical class OC1=CC=CC=C1C1=NC2=CC=CC=C2S1 MVVGSPCXHRFDDR-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000007787 solid Substances 0.000 claims abstract description 18
- 239000000126 substance Substances 0.000 claims abstract description 18
- 239000000463 material Substances 0.000 claims abstract description 12
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims abstract description 12
- 230000001678 irradiating effect Effects 0.000 claims abstract description 6
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 claims description 48
- 239000007788 liquid Substances 0.000 claims description 17
- NTSGEVXMOPCWCT-UHFFFAOYSA-N chembl1806516 Chemical group OC1=CC=C(Cl)C=C1C1=NC2=CC=CC=C2S1 NTSGEVXMOPCWCT-UHFFFAOYSA-N 0.000 claims description 16
- FWKHLHXATSAQBY-UHFFFAOYSA-N chembl1356622 Chemical compound OC1=C(Br)C=C(Br)C=C1C1=NC2=CC=CC=C2S1 FWKHLHXATSAQBY-UHFFFAOYSA-N 0.000 claims description 15
- YQIRLDMXXRINIJ-UHFFFAOYSA-N chembl1408767 Chemical compound OC1=CC(O)=CC=C1C1=NC2=CC=CC=C2S1 YQIRLDMXXRINIJ-UHFFFAOYSA-N 0.000 claims description 15
- JJWLVOIRVHMVIS-UHFFFAOYSA-N isopropylamine Chemical compound CC(C)N JJWLVOIRVHMVIS-UHFFFAOYSA-N 0.000 claims description 7
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 claims description 6
- 238000006862 quantum yield reaction Methods 0.000 claims description 5
- -1 phenol oxygen anions Chemical class 0.000 claims description 2
- 230000005281 excited state Effects 0.000 claims 1
- 238000005516 engineering process Methods 0.000 abstract description 7
- 238000001035 drying Methods 0.000 abstract description 5
- 238000002189 fluorescence spectrum Methods 0.000 description 14
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 8
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 239000000975 dye Substances 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- 239000010453 quartz Substances 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- 238000007639 printing Methods 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000012043 crude product Substances 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 239000007850 fluorescent dye Substances 0.000 description 3
- 239000000499 gel Substances 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 230000000391 smoking effect Effects 0.000 description 3
- 238000001308 synthesis method Methods 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- VRVRGVPWCUEOGV-UHFFFAOYSA-N 2-aminothiophenol Chemical compound NC1=CC=CC=C1S VRVRGVPWCUEOGV-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000002761 deinking Substances 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003480 eluent Substances 0.000 description 2
- 238000003958 fumigation Methods 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 150000002910 rare earth metals Chemical class 0.000 description 2
- 230000001953 sensory effect Effects 0.000 description 2
- 238000010898 silica gel chromatography Methods 0.000 description 2
- 238000004809 thin layer chromatography Methods 0.000 description 2
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- LDXJRKWFNNFDSA-UHFFFAOYSA-N 2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound C1CN(CC2=NNN=C21)CC(=O)N3CCN(CC3)C4=CN=C(N=C4)NCC5=CC(=CC=C5)OC(F)(F)F LDXJRKWFNNFDSA-UHFFFAOYSA-N 0.000 description 1
- JHZOXYGFQMROFJ-UHFFFAOYSA-N 3,5-dibromo-2-hydroxybenzaldehyde Chemical compound OC1=C(Br)C=C(Br)C=C1C=O JHZOXYGFQMROFJ-UHFFFAOYSA-N 0.000 description 1
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 1
- FUGKCSRLAQKUHG-UHFFFAOYSA-N 5-chloro-2-hydroxybenzaldehyde Chemical compound OC1=CC=C(Cl)C=C1C=O FUGKCSRLAQKUHG-UHFFFAOYSA-N 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 230000006399 behavior Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 238000007667 floating Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 238000001093 holography Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 description 1
- 229940001584 sodium metabisulfite Drugs 0.000 description 1
- 235000010262 sodium metabisulphite Nutrition 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
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- 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
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
- C07D277/60—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings condensed with carbocyclic rings or ring systems
- C07D277/62—Benzothiazoles
- C07D277/64—Benzothiazoles with only hydrocarbon or substituted hydrocarbon radicals attached in position 2
- C07D277/66—Benzothiazoles with only hydrocarbon or substituted hydrocarbon radicals attached in position 2 with aromatic rings or ring systems directly attached in position 2
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- 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
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- 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
- C09K2211/1037—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom with sulfur
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Abstract
The invention relates to a solid-state fluorescence anti-counterfeiting method based on reversible response of amine steam, which adopts a 2- (2-benzothiazolyl) phenol derivative as a fluorescence anti-counterfeiting material, arranges a tetrahydrofuran solution of the fluorescence anti-counterfeiting material on an anti-counterfeiting commodity, and adopts ultraviolet irradiation after drying, wherein the part provided with the anti-counterfeiting material emits green or blue-green fluorescence; then placing the anti-counterfeiting commodity in an organic amine steam atmosphere, and irradiating the anti-counterfeiting commodity by adopting ultraviolet light to ensure that the part provided with the anti-counterfeiting substance emits blue fluorescence; and the fluorescent material is placed in the air for a period of time or in an acetic acid steam atmosphere to recover green or blue-green fluorescence, so that the reversible response of solid fluorescence is realized. The method of the invention has simple and convenient operation, time and labor saving, quick and reversible fluorescence response, realizes double-color fluorescence display, has high fluorescence color contrast, can be distinguished by naked eyes, can be quickly distinguished, and improves the efficiency and the safety of the anti-counterfeiting technology.
Description
Technical Field
The invention relates to a solid-state fluorescence anti-counterfeiting method based on reversible response of amine steam, belonging to the technical field of fluorescence anti-counterfeiting.
Background
With the continuous development of global economy, counterfeit commodities frequently appear, and the economic loss caused each year is serious, but consumers cannot clearly distinguish the authenticity of the commodities, so that the counterfeiting behavior is more and more intense. In today's society, important and expensive commodities, including paper money, securities, checks, documents, invoices, medicines, cosmetics, and foods, etc., are almost counterfeited. Counterfeit and shoddy goods have become a common concern of countries in the world as a social phenomenon, and many countries in the world, especially some developed countries, invest a great deal of force in developing various anti-counterfeiting technologies.
The current common anti-counterfeiting technologies include: laser holography, fluorescence anti-counterfeiting, watermarking, bar codes, magnetic codes, two-dimensional codes and the like; the problems of high cost, complex operation and easy duplication exist in magnetic anti-counterfeiting, laser holographic anti-counterfeiting and two-dimensional code anti-counterfeiting. The fluorescent anti-counterfeiting has the advantages of simple and convenient operation, time saving, strong anti-counterfeiting performance and the like, so that the fluorescent anti-counterfeiting has wide application in the aspect of high-tech anti-counterfeiting technology.
For the fluorescent materials for anti-counterfeiting, the most studied at present are rare earth metal complexes, and the compounds have the following defects: 1) The fluorescence intensity is attenuated more quickly after the long-time placement; 2) The organic rare earth fluorescent complex is easy to cause emulsification to generate floating dirt or ink roller deinking phenomenon in printing due to low viscosity of the fluorescent ink, especially colorless transparent ink needs to be checked frequently to prevent missing printing phenomenon generated due to deinking, the effect of the fluorescent ink for lithographic printing is not ideal, the fluorescent ink is generally not applied in lithographic printing, and the application range is narrow; 3) The fluorescent ink has high fluidity and is relatively slow to dry, which is extremely inconvenient. In addition, most of the currently applied fluorescent anti-counterfeiting materials are monochromatic fluorescence. Thus, the effectiveness and security of conventional fluorescent security face serious challenges.
In order to further enhance the anti-counterfeiting effect, a novel fluorescent anti-counterfeiting technology needs to be developed.
Disclosure of Invention
Aiming at the defects of the existing fluorescent anti-counterfeiting technology, the invention provides a solid-state fluorescent anti-counterfeiting method based on reversible response of amine steam.
The invention is realized by the following technical scheme:
a solid-state fluorescence anti-counterfeiting method based on reversible response of amine steam adopts 2- (2-benzothiazolyl) phenol derivatives as fluorescent anti-counterfeiting materials, and comprises the following steps:
(1) Preparing tetrahydrofuran solution of 2- (2-benzothiazolyl) phenol derivative to obtain anti-fake liquid;
(2) The anti-counterfeiting liquid is arranged on the anti-counterfeiting commodity, after being dried, the anti-counterfeiting liquid is irradiated by ultraviolet light, and the part provided with the anti-counterfeiting substance emits green or blue-green fluorescence;
(3) Placing the anti-counterfeiting commodity in an organic amine steam atmosphere, and then irradiating by adopting ultraviolet light to enable the part provided with the anti-counterfeiting substance to emit blue fluorescence;
(4) The anti-counterfeiting commodity is placed in the air for a period of time or in an acetic acid steam atmosphere, green or blue-green fluorescence is recovered, and solid fluorescence reversible response is realized.
Preferably, in step (1), the 2- (2-benzothiazolyl) phenol derivative is 2- (2-benzothiazolyl) -4-chlorophenol, 2- (2-benzothiazolyl) -4, 6-dibromophenol or 4- (2-benzothiazolyl) -1, 3-benzenediol.
2- (2-benzothiazolyl) -4-chlorophenol having a chemical structure according to formula i:
2- (2-benzothiazolyl) -4, 6-dibromophenol, the chemical structural formula of which is shown in formula II:
4- (2-benzothiazolyl) -1, 3-benzenediol, the chemical structural formula of which is shown in formula III:
preferably, in step (1), the concentration of the 2- (2-benzothiazolyl) phenol derivative in the anti-counterfeiting liquid is 40-60 mu M.
According to the invention, in the step (2) and the step (3), the wavelength of the ultraviolet light is preferably 365nm.
Preferably, in the step (2), when the 2- (2-benzothiazolyl) phenol derivative is 2- (2-benzothiazolyl) -4-chlorophenol or 2- (2-benzothiazolyl) -4, 6-dibromophenol, the portion where the forgery-preventing substance is provided emits green fluorescence, and when the 2- (2-benzothiazolyl) phenol derivative is 4- (2-benzothiazolyl) -1, 3-benzenediol, the portion where the forgery-preventing substance is provided emits blue-green fluorescence.
Preferably, in step (3), the organic amine is one of piperidine, isopropylamine and pyrrolidine.
Preferably, in step (3), the anti-counterfeit goods are kept in the organic amine steam atmosphere for 20 to 30 seconds.
Preferably, in the step (4), the air is kept for 5 minutes to 5 hours, and the acetic acid vapor atmosphere is kept for 20 to 30 seconds.
The 2- (2-benzothiazolyl) phenol derivative emits green or blue-green fluorescence through an excited intramolecular proton transfer mechanism after being irradiated by ultraviolet light, generates phenoxide anions after reacting with organic amine, emits blue fluorescence after being irradiated by the ultraviolet light, and can recover initial fluorescence in a short time after being separated from an organic amine steam environment, thereby realizing rapid, cyclic and visible detection by naked eyes.
The invention has the advantages and beneficial effects that:
1. the method of the invention has simple and convenient operation, time and labor saving, quick and reversible fluorescence response, realizes double-color fluorescence display, has high fluorescence color contrast, can be distinguished by naked eyes, can be quickly distinguished, and improves the efficiency and the safety of the anti-counterfeiting technology.
2. The 2- (2-benzothiazolyl) phenol derivative selected by the invention has strong fluorescence intensity and stable material property, can be placed for a long time and can be recycled for multiple times.
Drawings
FIG. 1: the fluorescence spectrum change caused by repeatedly placing the filter paper strip loaded with 2- (2-benzothiazolyl) -4-chlorophenol in piperidine steam and acetic acid steam.
FIG. 2 is a schematic diagram: the fluorescence ratio change patterns caused by repeated exposure of the 2- (2-benzothiazolyl) -4-chlorophenol-loaded filter paper strips to piperidine vapor and to acetic acid vapor.
FIG. 3: the application of the compound 2- (2-benzothiazolyl) -4-chlorophenol in anti-counterfeiting comprises the following steps: a. pictures under sunlight, pictures under a 365nm ultraviolet lamp, pictures under sunlight after being fumigated by piperidine steam, pictures under a 365nm ultraviolet lamp after being fumigated by piperidine steam, pictures under sunlight after being exposed in air for 5 minutes, and pictures under a 365nm ultraviolet lamp after being exposed in air for 5 minutes.
FIG. 4 is a schematic view of: the fluorescence spectrum change caused by repeatedly placing the filter paper strip loaded with 2- (2-benzothiazolyl) -4, 6-dibromophenol in isopropylamine steam and acetic acid steam.
FIG. 5 is a schematic view of: the fluorescence ratio change patterns caused by exposure of the 2- (2-benzothiazolyl) -4, 6-dibromophenol-loaded filter strips to isopropylamine vapor and to acetic acid vapor were repeated.
FIG. 6: the application of the compound 2- (2-benzothiazolyl) -4, 6-dibromophenol in anti-counterfeiting comprises the following steps: a. pictures under sunlight, pictures under a 365nm ultraviolet lamp, pictures under sunlight after being fumigated by piperidine steam, pictures under a 365nm ultraviolet lamp after being fumigated by piperidine steam, pictures under sunlight after being exposed in air for 5 minutes, and pictures under a 365nm ultraviolet lamp after being exposed in air for 5 minutes.
FIG. 7: graph showing the change in fluorescence spectrum caused by repeated exposure of the 4- (2-benzothiazolyl) -1, 3-benzenediol-loaded filter strips to piperidine vapor and acetic acid vapor.
FIG. 8: the fluorescence ratio change patterns caused by repeated exposure of the 4- (2-benzothiazolyl) -1, 3-benzenediol-loaded filter strips to piperidine vapor and acetic acid vapor.
FIG. 9: the application of the compound 4- (2-benzothiazolyl) -1, 3-benzenediol in anti-counterfeiting comprises the following steps: a. the pictures are taken under sunlight, b under a 365nm ultraviolet lamp, c, under sunlight after fumigation by piperidine steam, d, under a 365nm ultraviolet lamp after fumigation by piperidine steam, e, under sunlight after exposure in air for 5 minutes, and f, under a 365nm ultraviolet lamp after exposure in air for 5 minutes.
The specific implementation mode is as follows:
for a better understanding of the invention, the invention will be described in more detail below with reference to examples and the accompanying drawings, to which, however, the invention is not restricted.
In the examples:
the synthesis method of 2- (2-benzothiazolyl) -4-chlorophenol comprises the following steps:
in a 25mL round-bottom flask, 126mg of 2-aminobenzenethiol (1.0 mmol) and 171mg of 5-chlorosalicylaldehyde (1.1 mmol) were dissolved in 10mL of ethanol. Then 0.5mL of hydrochloric acid (3 mmol) with the concentration of 37% is slowly added into the reaction system, and then 0.63mL of hydrogen peroxide (6 mmol) with the concentration of 30% is added into the reaction solution, and the reaction is carried out at room temperature until the thin layer chromatography detection reaction is completed. The reaction mixture was quenched by adding 10mL of distilled water, extracted three times with ethyl acetate, and the organic layer was collected, concentrated and dried. The crude product was purified by silica gel chromatography (eluent: petroleum ether/ethyl acetate = 30: 1) to give the desired compound as a white solid (210 mg, yield 79.8%).
1 H NMR(400MHz,DMSO-d6)δ11.69(s,1H),8.25(d,J＝2.4Hz,1H),8.15(d,J＝7.9Hz,1H),8.07(d,J＝8.1Hz,1H),7.55(t,J＝7.6Hz,1H),7.49–7.40(m,2H),7.11(d,J＝8.8Hz,1H)。
2- (2-benzothiazolyl) -4-chlorophenol solid fluorescenceQuantum yield phi f [％]Is 82.
The synthesis method of 2- (2-benzothiazolyl) -4, 6-dibromophenol comprises the following steps:
in a 25mL round bottom flask, 126mg of 2-aminobenzenethiol (1.0 mmol) and 308mg of 3, 5-dibromosalicylaldehyde (1.1 mmol) are dissolved in 10mL of ethanol. Then 0.5mL of hydrochloric acid (3 mmol) with the concentration of 37% is slowly added into the reaction system, and then 0.63mL of hydrogen peroxide (6 mmol) with the concentration of 30% is added into the reaction solution, and the reaction is carried out at room temperature until the thin layer chromatography detection reaction is completed. The reaction mixture was quenched by adding 10mL of distilled water, extracted three times with ethyl acetate, and the organic layer was collected, concentrated and dried. The crude product was purified by silica gel chromatography (eluent: petroleum ether/ethyl acetate = 25: 1) to give the desired compound as a white solid (270 mg, yield 63.8%).
1 H NMR(400MHz,DMSO-d6)δ12.80(s,1H),8.23(d,J＝7.9Hz,1H),8.19–8.07(m,2H),7.96(m,1H),7.62(t,J＝7.2Hz,1H),7.54(t,J＝7.5Hz,1H)。
2- (2-benzothiazolyl) -4, 6-dibromophenol solid fluorescence quantum yield phi f [％]Is 31.
The synthesis method of the 4- (2-benzothiazolyl) -1, 3-benzenediol comprises the following steps:
a50 mL round-bottomed flask equipped with a magnetic stirrer was charged with 0.22mL2-aminothiophenol (2 mmol), 304mg2, 4-dihydroxybenzaldehyde (2.2 mmol) and 465mg sodium metabisulfite (Na) 2 S 2 O 5 2.4 mmol) was dissolved in 10mL of anhydrous DMF solution. After stirring at reflux for 2 hours, the reaction mixture was cooled and 20mL of water was added slowly. The precipitate was filtered off, washed with water (20 mL × 3) and dried to give the crude product, which was further purified by recrystallization from methanol to give a white solid (405 mg, yield 83.3%).
1 H NMR(400MHz,DMSO-d6)δ11.67(s,1H),10.17(s,1H),8.08(d,J＝7.6Hz,1H),7.94(dd,J＝8.7Hz,2H),7.50(t,J＝7.2Hz,1H),7.39(t,J＝7.5Hz,1H),6.49–6.43(m,2H)。
4- (2-benzothiazolyl) -1, 3-benzenediol solid fluorescence quantum yield phi f [％]Is 25.
Example 1
A solid-state fluorescence anti-counterfeiting method based on reversible response of amine steam adopts 2- (2-benzothiazolyl) -4-chlorophenol as a fluorescence anti-counterfeiting material, and comprises the following steps:
(1) Preparing tetrahydrofuran solution of 2- (2-benzothiazolyl) -4-chlorophenol with the concentration of 50 mu M to obtain anti-counterfeiting liquid;
(2) The anti-counterfeiting liquid is arranged on the anti-counterfeiting commodity, and after the anti-counterfeiting liquid is dried, 365nm ultraviolet light is adopted for irradiation, and the part provided with the anti-counterfeiting substance emits green fluorescence;
(3) Placing the anti-counterfeiting commodity in an amine steam atmosphere for 30 seconds, and then irradiating the anti-counterfeiting commodity by 365nm ultraviolet light to enable the part provided with the anti-counterfeiting substance to emit blue fluorescence;
(4) And (3) smoking the anti-counterfeiting commodity in an acetic acid steam atmosphere for 30 seconds to recover green fluorescence, so that solid fluorescence reversible response is realized.
Experimental example 1-1:2- (2-benzothiazolyl) -4-chlorophenol sensing property test
The test method comprises the following steps: dripping 10 mu L of tetrahydrofuran solution of 2- (2-benzothiazolyl) -4-chlorophenol with the concentration of 50 mu M on a filter paper strip of 0.8cm multiplied by 1.5cm, and then drying in the air for 24 hours to prepare a filter paper strip loaded with fluorescent dye;
piperidine (15. Mu.L) was charged into a 1 cm. Times.1 cm. Times.4 cm quartz cuvette, which was then sealed and allowed to stand at room temperature for 30 minutes to saturate to prepare an amine vapor. Acetic acid vapor was prepared in the same manner.
The dye-loaded filter paper strips were fixed to a glass plate, which was placed in a quartz cuvette. The cuvette with the glass plate placed thereon was placed on a solid sample holder of a fluorescence spectrometer and the fluorescence spectrum thereof was measured. The filter paper strips were placed in piperidine vapor for 30 seconds and then tested for fluorescence spectra. The filter paper strip was removed, dried for 1 minute with a blower, then placed in acetic acid vapor for 30 seconds, and tested for fluorescence spectra. Repeat 5 times.
The fluorescence spectrum change and fluorescence ratio change spectra caused by repeated exposure of the dye-loaded filter paper to piperidine vapor and acetic acid vapor are shown in fig. 1 and 2.
EXAMPLES 1-2 anti-counterfeiting application test
2- (2-benzothiazolyl) -4-chlorophenol was prepared as a tetrahydrofuran solution at a concentration of 50. Mu.M.
The solution is injected into a clean gel pen, HBT characters are written on the power coupon, and the power coupon is photographed under sunlight and a 365nm ultraviolet lamp respectively.
And (4) putting the written exercise ticket into a piperidine steam atmosphere for 30 seconds, and taking a picture under sunlight and a 365nm ultraviolet lamp.
Taking out the exercise ticket from the piperidine steam atmosphere, drying the exercise ticket for one minute by a blower, standing the exercise ticket in the air for 5 minutes, and taking pictures under sunlight and a 365nm ultraviolet lamp respectively.
The test results are shown in fig. 3.
Example 2
A solid-state fluorescence anti-counterfeiting method based on reversible response of amine steam adopts 2- (2-benzothiazolyl) -4, 6-dibromophenol as a fluorescence anti-counterfeiting material, and comprises the following steps:
(1) Preparing tetrahydrofuran solution of 2- (2-benzothiazolyl) -4, 6-dibromophenol with the concentration of 50 mu M to obtain anti-counterfeiting liquid;
(2) The anti-counterfeiting liquid is arranged on an anti-counterfeiting commodity, after being dried, 365nm ultraviolet light is adopted for irradiation, and the part provided with the anti-counterfeiting substance emits green fluorescence;
(3) Placing the anti-counterfeiting commodity in an amine steam atmosphere for 30 seconds, and then irradiating the anti-counterfeiting commodity by 365nm ultraviolet light to enable the part provided with the anti-counterfeiting substance to emit blue fluorescence;
(4) And (3) smoking the anti-counterfeiting commodity in an acetic acid steam atmosphere for 30 seconds to recover green fluorescence, so that reversible response of solid fluorescence is realized.
Experimental example 2-1- (2-benzothiazolyl) -4, 6-dibromophenol sensory properties test
The test method comprises the following steps: mu.L of a 50. Mu.M solution of 2- (2-benzothiazolyl) -4, 6-dibromophenol in tetrahydrofuran was added dropwise to a 0.8cm X1.5 cm strip of filter paper and then dried in air for 24 hours to produce a strip of filter paper carrying a fluorescent dye.
Isopropylamine (15. Mu.L) was charged to a 1cm X4 cm quartz cuvette, which was then sealed and allowed to saturate at room temperature for 30 minutes to prepare an amine vapor. Acetic acid vapor was prepared in the same manner.
The dye-loaded filter paper strips were fixed to a glass plate, which was placed in a quartz cuvette. The cuvette with the glass plate mounted was placed on the solid sample holder of the fluorescence spectrometer and its fluorescence spectrum was measured. The filter paper strips were placed in isopropyl amine vapor for 30 seconds and then tested for fluorescence spectra. The filter paper strip was removed, dried for 1 minute with a blower, then placed in acetic acid vapor for 30 seconds, and tested for fluorescence spectra. Repeat 5 times.
The fluorescence change spectrum and the fluorescence ratio change spectrum caused by repeatedly placing the dye-loaded filter paper in the isopropyl amine vapor and the acetic acid vapor are shown in fig. 4 and 5.
Experimental example 2-2 anti-counterfeiting application test
The 2- (2-benzothiazolyl) -4, 6-dibromophenol was prepared as a 50. Mu.M solution in tetrahydrofuran.
The solution is injected into a clean gel pen, HBT characters are written on the power coupon, and the power coupon is photographed under sunlight and a 365nm ultraviolet lamp respectively.
And (4) putting the written exercise ticket into a piperidine steam atmosphere for 30 seconds, and taking a picture under sunlight and a 365nm ultraviolet lamp.
Taking out the exercise ticket from the piperidine steam atmosphere, drying the exercise ticket for one minute by a blower, standing the exercise ticket in the air for 5 minutes, and taking pictures under sunlight and a 365nm ultraviolet lamp respectively.
The test results are shown in fig. 6.
Example 3
A solid-state fluorescence anti-counterfeiting method based on reversible response of amine steam adopts 4- (2-benzothiazolyl) -1, 3-benzenediol as a fluorescence anti-counterfeiting material, and comprises the following steps:
(1) Preparing tetrahydrofuran solution of 4- (2-benzothiazolyl) -1, 3-benzenediol with the concentration of 50 mu M to obtain anti-counterfeiting liquid;
(2) The anti-counterfeiting liquid is arranged on the anti-counterfeiting commodity, and after the anti-counterfeiting liquid is dried, the anti-counterfeiting liquid is irradiated by 365nm ultraviolet light, and the part provided with the anti-counterfeiting substance emits blue-green fluorescence;
(3) Placing the anti-counterfeiting commodity in an amine steam atmosphere for 30 seconds, and then irradiating the anti-counterfeiting commodity by 365nm ultraviolet light to enable the part provided with the anti-counterfeiting substance to emit blue fluorescence;
(4) And (3) smoking the anti-counterfeiting commodity in an acetic acid steam atmosphere for 30 seconds to recover blue-green fluorescence, so that solid fluorescence reversible response is realized.
Experimental example 3-1- (2-benzothiazolyl) -1, 3-benzenediol sensory Properties
The test method comprises the following steps: 10 μ L of a 50 μ M solution of 4- (2-benzothiazolyl) -1, 3-benzenediol in tetrahydrofuran was dropped onto a 0.8cm X1.5 cm strip of filter paper, which was then dried in air for 24 hours, to prepare a strip of filter paper carrying a fluorescent dye.
Piperidine (15. Mu.L) was charged into a 1 cm. Times.1 cm. Times.4 cm quartz cuvette, which was then sealed and allowed to stand at room temperature for 30 minutes to saturate to prepare an amine vapor. Acetic acid vapor was prepared in the same manner.
The dye-loaded filter paper strips were fixed to a glass plate, which was placed in a quartz cuvette. The cuvette with the glass plate was placed on the solid sample holder of the fluorescence spectrometer and its fluorescence spectrum was measured. The filter paper strips were placed in piperidine vapor for 30 seconds and then tested for fluorescence spectra. The filter paper strip was removed, dried for 1 minute with a hair dryer, then placed in acetic acid vapor for 30 seconds, and tested for fluorescence spectra. Repeat 5 times.
The fluorescence spectrum change and fluorescence ratio change spectra caused by repeated exposure of the dye-loaded filter paper to piperidine vapor and acetic acid vapor are shown in fig. 7 and 8.
Experimental example 3-2 anti-counterfeit application test
4- (2-benzothiazolyl) -1, 3-benzenediol was prepared as a 50. Mu.M tetrahydrofuran solution.
The solution is injected into a clean gel pen, HBT characters are written on a practice coupon, and the practice coupon is photographed under sunlight and a 365nm ultraviolet lamp respectively.
The written practice coupon is put into piperidine steam atmosphere for 30 seconds, and a picture is taken under sunlight and a 365nm ultraviolet lamp.
Taking out the exercise ticket from the piperidine steam atmosphere, drying the exercise ticket for one minute by a blower, standing the exercise ticket in the air for 5 minutes, and taking pictures under sunlight and a 365nm ultraviolet lamp respectively.
The test results are shown in fig. 9.
Claims (4)
1. A solid-state fluorescence anti-counterfeiting method based on reversible response of amine steam adopts 2- (2-benzothiazolyl) phenol derivatives as fluorescent anti-counterfeiting materials, realizes two-color fluorescence display, has high contrast of fluorescence color, and can be distinguished by naked eyes;
the method comprises the following steps:
(1) Preparing tetrahydrofuran solution of 2- (2-benzothiazolyl) phenol derivative to obtain anti-fake liquid; the 2- (2-benzothiazolyl) phenol derivative is 2- (2-benzothiazolyl) -4-chlorophenol, 2- (2-benzothiazolyl) -4, 6-dibromophenol or 4- (2-benzothiazolyl) -1, 3-benzenediol;
the solid fluorescence quantum yield phi f [% ] of the 2- (2-benzothiazolyl) -4-chlorophenol is 82;
the solid fluorescence quantum yield phi f [% ] of the 2- (2-benzothiazolyl) -4, 6-dibromophenol is 31;
the solid fluorescence quantum yield phi f [% ] of the 4- (2-benzothiazolyl) -1, 3-benzenediol is 25;
the concentration of the 2- (2-benzothiazolyl) phenol derivative in the anti-counterfeiting liquid is 40-60 mu M;
(2) The anti-counterfeiting liquid is arranged on an anti-counterfeiting commodity, after being dried, ultraviolet light is adopted for irradiation, and the part of the anti-counterfeiting liquid, which is provided with the anti-counterfeiting substance through an excited state intramolecular proton transfer mechanism, emits green or blue-green fluorescence; when the 2- (2-benzothiazolyl) phenol derivative is 2- (2-benzothiazolyl) -4-chlorophenol or 2- (2-benzothiazolyl) -4, 6-dibromophenol, the part with the anti-counterfeiting substance emits green fluorescence, and when the 2- (2-benzothiazolyl) phenol derivative is 4- (2-benzothiazolyl) -1, 3-benzenediol, the part with the anti-counterfeiting substance emits blue-green fluorescence;
(3) Placing the anti-counterfeiting commodity in an organic amine steam atmosphere, then irradiating by adopting ultraviolet light to generate phenol oxygen anions, and emitting blue fluorescence from the part provided with the anti-counterfeiting substance after being irradiated by the ultraviolet light; the organic amine is one of piperidine, isopropylamine and pyrrolidine;
(4) The anti-counterfeiting commodity is placed in the air for a period of time or in an acetic acid steam atmosphere, green or blue-green fluorescence is recovered, and reversible response of solid fluorescence is realized.
2. The solid-state fluorescence anti-counterfeiting method based on reversible amine vapor response according to claim 1, wherein in the step (2) and the step (3), the wavelength of ultraviolet light is 365nm.
3. The solid-state fluorescence anti-counterfeiting method based on reversible amine vapor response according to claim 1, wherein in the step (3), the anti-counterfeiting commodity is placed in the organic amine vapor atmosphere for 20-30 seconds.
4. The solid-state fluorescence anti-counterfeiting method based on reversible amine vapor response according to claim 1, wherein in the step (4), the solid-state fluorescence anti-counterfeiting method is placed in the air for 5 minutes to 5 hours and placed in the acetic acid vapor atmosphere for 20 to 30 seconds.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107353243A (en) * | 2017-02-14 | 2017-11-17 | 湖州师范学院 | The method for manufacturing thin film and application of a kind of triphenylamine derivative and its doping |
| CN110117253A (en) * | 2018-02-05 | 2019-08-13 | 三峡大学 | A kind of organic fluorescent dye with piezallochromy characteristic, preparation method and applications |
| CN110627800A (en) * | 2019-09-24 | 2019-12-31 | 吉林大学 | Light reversible stimulus response fluorescent material and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105038766A (en) * | 2015-06-25 | 2015-11-11 | 中国科学院合肥物质科学研究院 | Visible and reversible ratiometric fluorescent probe as well as preparation method and application thereof |
| CN107353243A (en) * | 2017-02-14 | 2017-11-17 | 湖州师范学院 | The method for manufacturing thin film and application of a kind of triphenylamine derivative and its doping |
| CN110117253A (en) * | 2018-02-05 | 2019-08-13 | 三峡大学 | A kind of organic fluorescent dye with piezallochromy characteristic, preparation method and applications |
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