CN112480110A - Multi-response azacyclo-formaldehyde fluorescent probe molecule and preparation method and application thereof - Google Patents
Multi-response azacyclo-formaldehyde fluorescent probe molecule and preparation method and application thereof Download PDFInfo
- Publication number
- CN112480110A CN112480110A CN202011400550.4A CN202011400550A CN112480110A CN 112480110 A CN112480110 A CN 112480110A CN 202011400550 A CN202011400550 A CN 202011400550A CN 112480110 A CN112480110 A CN 112480110A
- Authority
- CN
- China
- Prior art keywords
- formaldehyde
- fluorescent probe
- response
- probe molecule
- azacyclo
- 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.)
- Granted
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
- C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
- C07D471/04—Ortho-condensed systems
-
- 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"
-
- 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
- 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
- G01N21/645—Specially adapted constructive features of fluorimeters
- G01N21/6456—Spatial resolved fluorescence measurements; Imaging
-
- 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
- C09K2211/1044—Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms
-
- 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"
- G01N2021/6439—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes" with indicators, stains, dyes, tags, labels, marks
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Immunology (AREA)
- General Physics & Mathematics (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Analytical Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Pathology (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Optics & Photonics (AREA)
- Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
- Investigating Or Analysing Materials By The Use Of Chemical Reactions (AREA)
Abstract
The invention discloses a multi-response azacyclo-formaldehyde fluorescent probe molecule with a structure shown as a formula I, a preparation method and an application thereof, the molecule realizes selective quantitative recognition of formaldehyde by a fluorescence analysis method, tests and evaluations of formaldehyde, copper ions and sulfur ions are carried out in the fields of automobile interior materials, healthy home, biological medicine and the like, can also be used for fluorescence imaging of biological samples, and can also be used as an ultraviolet absorbent in the technical fields of plastics, coatings, printing ink, display, illumination, glasses, daily chemical industry, textiles and the like.
Wherein R is H or Cl, and X is CH or N.
Description
The technical field is as follows:
the invention relates to the technical field of organic functional material synthesis and analysis testing, in particular to a multi-response azacyclo-formaldehyde fluorescent probe molecule and a preparation method thereof.
Background art:
the green travel, the healthy home decoration and the beauty life become a new consumption form and are gradually accepted by people. The automobile and the home are closely related to the daily life of people, whether automobile materials and home decoration materials are environment-friendly or not, the quality of air in the automobile and the indoor air is directly related to the physical and mental health of consumers, and the problem of air pollution in the automobile and the indoor air becomes a hot spot of general attention of the consumers.
Volatile Organic Compounds (VOC) are organic volatile matters with the boiling point of 50-260 ℃, are important factors influencing the quality of air in a vehicle and in a room, and are also important indexes for evaluating the quality of air in the vehicle and in the room. Formaldehyde is the simplest aldehyde substance and a widely used chemical raw material, is the most common volatile organic pollutant, mainly comes from automobile interior materials, buildings and interior decoration materials, and when the concentration of formaldehyde is higher than a normal level, the formaldehyde can cause serious damage to a nervous system, a respiratory system, a hematopoietic system and the like of people, so that diseases such as heart diseases, cancers and the like can be caused, and formaldehyde is listed as a human carcinogen by international cancer research institutions. In recent years, health problems caused by excessive formaldehyde in automobiles and home furnishings have attracted great attention. Therefore, the method has extremely important practical significance and social value for rapidly, efficiently, accurately and scientifically testing and evaluating the formaldehyde content.
At present, high performance liquid chromatography is generally adopted for testing the formaldehyde content in automobile materials and air in automobiles, and spectrophotometry is mainly adopted for testing the formaldehyde content in decorative and decorative materials such as carpets, artificial boards, coatings, adhesives and the like. Some European and American automobile enterprises generally adopt standard VDA 275, PV3925, GME60271 and GMW14236 to detect the content of formaldehyde in the automobile interior materials by spectrophotometry. However, the high performance liquid chromatography and the spectrophotometry have the disadvantages of large equipment investment, complicated method, long consumed time, large consumed derivatization reagent and the like.
The fluorescence analysis method is a detection method for detecting the change of a fluorescence signal of a target analyte by the action of a fluorescent probe and the target analyte so as to determine the content of the target analyte, has excellent selectivity, can realize real-time online detection and can carry out non-invasive detection on a biological sample. Although the formaldehyde fluorescent probe has been paid attention by researchers and widely researched, the formaldehyde fluorescent probe still has few varieties, has the defects of complex molecular structure, multiple preparation steps, expensive reagents, slow response speed and the like, and cannot meet the application requirements of testing and evaluating formaldehyde in materials, environments and complex systems, so that the development of the formaldehyde fluorescent probe which has good biological stability, simple structure, easy preparation, fast response speed and good selectivity is urgently needed.
The invention content is as follows:
the invention aims to provide a multi-response azacyclo-formaldehyde fluorescent probe molecule and a preparation method and application thereof, which realize the selective quantitative recognition of formaldehyde by a fluorescence analysis method, carry out the test and evaluation of formaldehyde, copper ions and sulfur ions in the fields of automobile interior materials, healthy home, biomedicine and the like, can be used for the fluorescent imaging of biological samples, and can also be used as an ultraviolet absorbent in the technical fields of plastics, coatings, printing ink, display, illumination, glasses, daily chemicals, textiles and the like.
The invention is realized by the following technical scheme:
the structure of the multi-response azacyclo-formaldehyde fluorescent probe molecule is shown as formula I:
wherein R is H or Cl, and X is CH or N.
Further, when R is H, X is CH or N; when R is Cl, X is CH.
Preferably, the probe molecule is the following compound:
the preparation method of the multi-response azacyclo-formaldehyde fluorescent probe molecule shown in the formula I comprises the following synthetic route:
wherein R is H or Cl, and X is CH or N.
The preparation method comprises the following steps:
(1) dissolving disubstituted ketone shown in a formula II, methyl 4-formylbenzoate shown in a formula III and ammonium acetate in glacial acetic acid, and carrying out reflux reaction for 7-9 hours under rapid stirring; after the reaction is finished, cooling the reaction liquid to room temperature, pouring the reaction liquid into ice water under stirring, adjusting the pH value to 7 by using an alkali solution, decompressing and filtering the obtained solid matter, washing the solid matter by using water for a plurality of times, recrystallizing the crude product by using an ethanol-acetone mixed solvent, and drying the crude product in vacuum to obtain an intermediate IV;
(2) dissolving the intermediate IV and hydrazine hydrate in an alcohol organic solvent, refluxing and reacting for 7-9 hours under rapid stirring, cooling to room temperature after the reaction is finished, carrying out vacuum filtration on the obtained solid matter, washing with water for several times, and recrystallizing the crude product with ethanol to obtain a yellow solid product I.
Preferably, in the step (1), the molar ratio of the disubstituted ketone, the methyl 4-formylbenzoate and the ammonium acetate is 1: 1-1.2: 10-17.
Preferably, in the step (1), the alkali solution is ammonia water or a 10-40 wt% sodium hydroxide aqueous solution or a potassium hydroxide aqueous solution.
Further, in the step (2), the weight ratio of the reaction material intermediate IV to hydrazine hydrate is 1: 5-9, the mass concentration of the hydrazine hydrate is 90%, and the alcohol solvent is methanol or ethanol.
The invention also aims to protect the application of the multi-response azacyclo-formaldehyde fluorescent probe molecule, which is characterized in that the multi-response azacyclo-formaldehyde fluorescent probe molecule has the characteristics of multi-response and relay identification, a plurality of identification sites and high response speed, and can be used as a fluorescent probe for testing and evaluating trace formaldehyde, copper ions and sulfur ions in vehicle materials, decorative materials and environmental systems. Meanwhile, the probe molecule has good ultraviolet absorption characteristic, wide absorption range and good transparency, can effectively absorb ultraviolet rays of 270nm-430nm, and can be used as an ultraviolet absorbent in the technical fields of plastics, coatings, printing ink, display, illumination, glasses, daily chemical industry, textiles and the like. In addition, the multi-response azacyclo-formaldehyde fluorescent probe molecule provided by the invention has stronger fluorescence emission performance under the conditions of solution and solid state, and can also be used as a fluorescent material for the aspects of anti-counterfeiting technology, light conversion materials, fluorescent labels, fluorescent imaging and the like.
The invention has the following beneficial effects:
(1) the multi-response azacyclo-formaldehyde fluorescent probe molecule provided by the invention has the characteristics of multi-response and in-situ relay identification, has a stable molecular structure, a plurality of identification sites, short response time and no need of an acid environment, can be quickly and quantitatively identified with formaldehyde, and the fluorescence of the system is red-shifted, so that the fluorescence emission color of the system is changed from blue to blue-green; meanwhile, the probe can react with copper ions to generate fluorescence quenching, and when sulfur ions are added, the fluorescence of the system can be quickly recovered, so that relay fluorescence identification and detection of the two ions are realized. Therefore, the fluorescent probe provided by the invention provides a method for naked eye identification and fluorescence visual monitoring of formaldehyde molecules, copper ions and sulfur ions under an ultraviolet lamp, can be used for testing and evaluating trace formaldehyde, copper ions and sulfur ions in vehicle materials, decorative materials and environmental systems, screening and quality control of materials, and can also be used for fluorescence imaging of biological samples.
(2) The multi-response azacyclo-formaldehyde fluorescent probe molecule provided by the invention has good ultraviolet absorption characteristic and strong fluorescence emission performance, and can be used as an ultraviolet absorbent or a fluorescent material in the related technical field.
(3) The preparation method of the probe molecule provided by the invention has the advantages of simple process, convenient operation, easy control, high production efficiency and low cost.
Description of the drawings:
FIG. 1 is a NMR spectrum of compound Ia;
FIG. 2 shows Compound Ia at a concentration of 1X 10-5An ultraviolet-visible absorption spectrogram in the N, N-dimethylformamide solution of M;
FIG. 3 shows Compound Ia at a concentration of 1X 10-5(ii) the transmittance profile in N, N-dimethylformamide solution of M;
FIG. 4 shows the concentration of Compound Ia at 1X 10-5Fluorescence spectra before and after adding formaldehyde into the N, N-dimethylformamide solution of M.
The specific implementation mode is as follows:
the following is a further description of the invention and is not intended to be limiting.
The reagents and materials described in the following examples are commercially available, unless otherwise specified.
Experimental apparatus and model: bruker AVANCE-300 nuclear magnetic resonance spectrometer; HORIBA Jobin-YvonAquog absorption and three-dimensional fluorescence scanning spectrometer.
Example 1: preparation of Probe molecule Ia
(1) Bis (2-pyridyl) methanone (1mmol) and methyl 4-formylbenzoate (1mmol) and ammonium acetate (10mmol) were dissolved in 30 ml of glacial acetic acid in a 100 ml round bottom flask and reacted under reflux with rapid stirring for 9 hours; after the reaction is finished, cooling to room temperature, pouring the reaction liquid into ice water while stirring, adjusting the pH value to be 7 by using ammonia water, decompressing and filtering the obtained solid matter, washing for 3 times by using water, recrystallizing the crude product by using an ethanol-acetone mixed solvent, and drying in vacuum to obtain a yellow solid, namely the intermediate IVa.
1H NMR(300MHz,CDCl3/TMS)δ:3.97(s,3H),6.71(t,J＝7.5Hz,1H),6.93-6.99(m,1H),7.09-7.14(m,1H),7.70-7.76(m,1H),7.94-7.98(m,2H),8.15-8.31(m,4H),8.65(m,1H),8.75(d,J＝7.5,Hz,1H)；13C NMR(75MHz,CDCl3/TMS)δ:52.28,114.54,120.04,120.73,121.51,121.55,122.06,127.83,129.94,130.29,130.83,131.31,134.41,136.34,136.81,148.98,154.72,166.61.
(2) Dissolving intermediate IVa and hydrazine hydrate (the mass concentration is 90 wt%) in 50 ml of methanol according to the weight ratio of 1:5 in a 100 ml round-bottom flask, refluxing and reacting for 9 hours under rapid stirring, cooling to room temperature after the reaction is finished, performing suction filtration on the obtained solid matter under reduced pressure, washing 3 times with water, and drying at room temperature. Recrystallizing with ethanol, and vacuum drying to obtain yellow solid, namely the probe molecule Ia, with the yield of 76%.
1H NMR(300MHz,DMSO-d6/TMS)δ:4.65(s,2H),6.73(t,J＝6.9Hz,1H),7.11-7.16(m,1H),7.21-7.25(m,1H),7.82-7.88(m,1H),7.99-8.07(m,4H),8.17(t,J＝7.8Hz,1H),8.59-8.68(m,3H),9.96(s,1H)；13C NMR(75MHz,DMSO-d6/TMS)δ:117.37,121.90,123.47,130.31,130.34,132.76,134.62,135.68,139.32,151.79,157.03,167.88.
Example 2
Preparation of Probe molecule Ia
(1) Bis (2-pyridyl) methanone (1mmol) and methyl 4-formylbenzoate (1.2mmol) and ammonium acetate (17mmol) were dissolved in 30 ml of glacial acetic acid in a 100 ml round bottom flask and reacted under reflux with rapid stirring for 7 hours; after the reaction is finished, cooling to room temperature, pouring the reaction solution into ice water while stirring, adjusting the pH to 7 by using 10 wt% of sodium hydroxide or potassium hydroxide aqueous solution, carrying out vacuum filtration on the obtained solid matter, washing for 3 times by using water, recrystallizing the crude product by using an ethanol-acetone mixed solvent, and carrying out vacuum drying to obtain the intermediate IVa.
(2) Dissolving the intermediate IVa and hydrazine hydrate (the mass concentration is 90 wt%) in 50 ml of ethanol according to the weight ratio of 1:9 in a 100 ml round-bottom flask, refluxing and reacting for 7 hours under rapid stirring, cooling to room temperature after the reaction is finished, performing suction filtration on the obtained solid matter under reduced pressure, washing 3 times with water, and drying at room temperature. Recrystallizing with ethanol, and vacuum drying to obtain the probe molecule Ia.
Example 3
Ultraviolet-visible absorption and fluorescence property test of probe molecules
Compound Ia was formulated at a concentration of 1X 10-5The UV absorption and fluorescence properties of the M solution in N, N-dimethylformamide were measured on a HORIBA JobinYvonAqualog absorption and three-dimensional fluorescence scanning spectrometer using a 1 cm cell and the results are shown in FIGS. 2-4.
As shown in FIG. 2, compound Ia has a broad-band strong absorption characteristic in the wavelength band of 270nm-430nm, exhibits a strong absorption band, and has two absorption peaks, which are respectively located at 330nm and 366nm, the absorption wavelength of the maximum absorption peak is 366nm, and no significant absorption is observed in the wavelength band above 430 nm. As can be seen from FIG. 3, in the spectral region of more than 430nm, the transmittance of the molecules is more than 98%, and the molecules have better transparency. The result shows that the compound Ia has good ultraviolet absorption characteristic, wide absorption range, good transparency and strong protective effect, and can be used as an ultraviolet absorbent in the technical fields of plastics, coatings, printing ink, display, illumination, glasses, textiles and the like.
The fluorescence property test result of the probe molecule shows that the nitrogen heterocyclic probe molecule Ia shows strong blue fluorescence emission in the N, N-dimethylformamide solution, and the maximum fluorescence emission wavelength is 461 nm. The probe has good recognition effect on formaldehyde, the fluorescence emission wavelength of probe molecules gradually generates red shift along with the addition of the formaldehyde, and when the addition amount of the formaldehyde reaches 0.253 multiplied by 10-3μ g, the emission wavelength was 475nm, giving a 14nm red shift, see FIG. 4. And meanwhile, the change condition of the fluorescence emission color of the N, N-dimethylformamide solution of the probe molecule under the irradiation of 365nm ultraviolet lamp is observed. Under white light, the probeThe molecular solution is colorless liquid or light yellow liquid, and the color of the solution is not obviously changed after different amounts of formaldehyde are added; under the irradiation of a 365nm ultraviolet lamp, the probe molecule solution shows strong blue fluorescence, and after a certain amount of formaldehyde is added, the solution shows strong blue-green fluorescence. The result shows that the probe molecules have better recognition characteristic on formaldehyde and can rapidly act with formaldehyde, the addition of the formaldehyde can not quench the fluorescence of the formaldehyde, but can cause the red shift of the fluorescence of the system, and the fluorescence emission color of the formaldehyde is changed from blue to blue-green, so that the naked eye recognition and fluorescence visual monitoring of the formaldehyde molecules under an ultraviolet lamp are realized. In addition, the research shows that a certain amount of Cu is added into the N, N-dimethylformamide solution of the probe molecule2+Then, the blue fluorescence is rapidly quenched, the system has no fluorescence, and a certain amount of S is further added into the system2-After that, it was observed that the solution became brown and that CuS precipitation occurred, and at the same time, the fluorescence of the solution was recovered. Therefore, the probe has the in-situ relay identification characteristic, so that relay fluorescence identification and detection of two ions can be realized. Therefore, the fluorescent probe provided by the invention provides a method for naked eye identification and fluorescence visual monitoring of formaldehyde molecules, copper ions and sulfur ions under an ultraviolet lamp, can be used for testing and evaluating trace formaldehyde, copper ions and sulfur ions in vehicle materials, decorative materials and environmental systems, and can also be used for fluorescence imaging of biological samples.
Further experiments found that compound Ia also has solid-state fluorescence emission characteristics. The fluorescent color of the solid material of the target compound under the irradiation of white light and 365nm ultraviolet lamps is observed, and the result shows that the target compound is yellow solid powder under the irradiation of white light and can emit strong yellow fluorescent light under the irradiation of 365nm ultraviolet lamps. Therefore, the multi-response azacyclo-formaldehyde fluorescent probe molecule provided by the invention can also be used as a fluorescent material for the aspects of anti-counterfeiting technology, light conversion material, fluorescent marking, fluorescent imaging and the like.
Claims (9)
1. The structure of the multi-response azacyclo-formaldehyde fluorescent probe molecule is shown as formula I:
wherein R is H or Cl, and X is CH or N.
2. The multi-responsive azacyclo-formaldehyde fluorescent probe molecule of claim 1, characterized by the following compounds:
3. the preparation method of the multi-response azacyclo-formaldehyde fluorescent probe molecule shown in the formula I in the claim 1 is characterized in that the synthetic route is as follows:
wherein R is H or Cl, and X is CH or N; the preparation method comprises the following steps:
(1) dissolving disubstituted ketone shown in a formula II, methyl 4-formylbenzoate shown in a formula III and ammonium acetate in glacial acetic acid, and carrying out reflux reaction for 7-9 hours under rapid stirring; after the reaction is finished, cooling the reaction liquid to room temperature, pouring the reaction liquid into ice water under stirring, adjusting the pH value to 7 by using an alkali solution, decompressing and filtering the obtained solid matter, washing the solid matter by using water for a plurality of times, recrystallizing the crude product by using an ethanol-acetone mixed solvent, and drying the crude product in vacuum to obtain an intermediate IV;
(2) dissolving the intermediate IV and hydrazine hydrate in an alcohol organic solvent, refluxing and reacting for 7-9 hours under rapid stirring, cooling to room temperature after the reaction is finished, carrying out vacuum filtration on the obtained solid matter, washing with water for several times, and recrystallizing the crude product with ethanol to obtain a yellow solid product I.
4. The preparation method of the multi-response azacyclo-formaldehyde fluorescent probe molecule according to claim 3, wherein in the step (1), the molar ratio of the disubstituted ketone, the methyl 4-formylbenzoate and the ammonium acetate is 1: 1-1.2: 10-17.
5. The preparation method of the multi-response azacyclo-formaldehyde fluorescent probe molecule according to claim 3 or 4, wherein in the step (1), the alkali solution is ammonia water or a sodium hydroxide aqueous solution or a potassium hydroxide aqueous solution with a mass fraction of 10-40 wt%.
6. The preparation method of the multi-response azacyclo-formaldehyde fluorescent probe molecule according to claim 3 or 4, wherein in the step (2), the weight ratio of the reaction material intermediate IV to hydrazine hydrate is 1: 5-9, the mass concentration of the hydrazine hydrate is 90%, and the alcohol solvent is methanol or ethanol.
7. The application of the multi-response azacyclic formaldehyde fluorescent probe molecule of claim 1, wherein the multi-response azacyclic formaldehyde fluorescent probe molecule is used as a fluorescent probe for testing and evaluating trace formaldehyde, copper ions or sulfur ions in vehicle materials, decorative materials and environmental systems.
8. The use of the multi-response azacyclic formaldehyde fluorescent probe molecule of claim 1, characterized in that it is used as an ultraviolet absorber in plastics, paints, inks, displays, lighting, glasses, household chemicals, textiles.
9. The application of the multi-response azacyclo-formaldehyde fluorescent probe molecule as claimed in claim 1, which is characterized in that the multi-response azacyclo-formaldehyde fluorescent probe molecule is used as a fluorescent material for anti-counterfeiting technology, light conversion materials, fluorescent labels and fluorescent imaging.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011400550.4A CN112480110B (en) | 2020-12-02 | 2020-12-02 | Multi-response azacyclo-formaldehyde fluorescent probe molecule and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011400550.4A CN112480110B (en) | 2020-12-02 | 2020-12-02 | Multi-response azacyclo-formaldehyde fluorescent probe molecule and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112480110A true CN112480110A (en) | 2021-03-12 |
| CN112480110B CN112480110B (en) | 2021-10-26 |
Family
ID=74939203
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011400550.4A Active CN112480110B (en) | 2020-12-02 | 2020-12-02 | Multi-response azacyclo-formaldehyde fluorescent probe molecule and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112480110B (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105669708A (en) * | 2016-01-18 | 2016-06-15 | 新乡医学院 | Coumarin schiff-base copper ion complex-based fluorescent probe for thiol as well as preparation method and application thereof |
| CN108373916A (en) * | 2018-05-24 | 2018-08-07 | 泰山医学院 | Imidazo [1,5-a] pyridine hydrazide derivatives class mercury ion fluorescence probe and its application |
| CN108395889A (en) * | 2018-05-25 | 2018-08-14 | 泰山医学院 | Mercury ion fluorescence probe and its application of benzimidazole [1,2-a] and pyridine derivatives |
| CN108484582A (en) * | 2018-01-17 | 2018-09-04 | 南通大学 | A kind of cumarin hydroxyacyl hydroxyacyl hydrazine class schiff bases Al3+Fluorescence probe prepares and application |
| CN110257055A (en) * | 2019-07-29 | 2019-09-20 | 齐齐哈尔医学院 | Highly selective detection glutathione Ratiometric fluorescent probe and synthetic method and application |
| CN111499629A (en) * | 2020-04-14 | 2020-08-07 | 曲阜师范大学 | Fluorescent probe for detecting phosgene, and preparation method and application thereof |
-
2020
- 2020-12-02 CN CN202011400550.4A patent/CN112480110B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105669708A (en) * | 2016-01-18 | 2016-06-15 | 新乡医学院 | Coumarin schiff-base copper ion complex-based fluorescent probe for thiol as well as preparation method and application thereof |
| CN108484582A (en) * | 2018-01-17 | 2018-09-04 | 南通大学 | A kind of cumarin hydroxyacyl hydroxyacyl hydrazine class schiff bases Al3+Fluorescence probe prepares and application |
| CN108373916A (en) * | 2018-05-24 | 2018-08-07 | 泰山医学院 | Imidazo [1,5-a] pyridine hydrazide derivatives class mercury ion fluorescence probe and its application |
| CN108395889A (en) * | 2018-05-25 | 2018-08-14 | 泰山医学院 | Mercury ion fluorescence probe and its application of benzimidazole [1,2-a] and pyridine derivatives |
| CN110257055A (en) * | 2019-07-29 | 2019-09-20 | 齐齐哈尔医学院 | Highly selective detection glutathione Ratiometric fluorescent probe and synthetic method and application |
| CN111499629A (en) * | 2020-04-14 | 2020-08-07 | 曲阜师范大学 | Fluorescent probe for detecting phosgene, and preparation method and application thereof |
Non-Patent Citations (3)
| Title |
|---|
| SELVARASU PRIYANGA等: "Coordination geometry-induced optical imaging of l-cysteine in cancer cells using imidazopyridine-based copper(ii) complexes", 《DALTON TRANSACTIONS》 * |
| SONG CHEN等: "Imidazo[1,5-a]pyridine-based fluorescent probe with a large stokes shift for specific recognition of sulfite", 《SPECTROCHIMICA ACTA PART A: MOLECULAR AND BIOMOLECULAR SPECTROSCOPY》 * |
| VOLPI,G.等: "New substituted imidazo[1,5-a]pyridine and imidazo[5,1-a]isoquinoline derivatives and their application in fluorescence cell imaging", 《DYES AND PIGMENTS》 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112480110B (en) | 2021-10-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108675990B (en) | Detect Cu2+Fluorescent probe, preparation method and preparation and use method of fluorescent test strip | |
| CN109879776B (en) | Water-soluble squarylium cyanine derivative, synthesis method thereof and application of water-soluble squarylium cyanine derivative in detection of aldehyde compounds | |
| CN113621081B (en) | Dialdehyde cellulose-based Schiff base fluorescent probe for detecting Al3+, and preparation method and application thereof | |
| CN113121576B (en) | Molecular sensor with different detection signals for acid and alkali environments and application | |
| CN103992292A (en) | Schiff base sensor molecule, its synthesis, and its application in fluorescent colorimetric detection of CN<-> in water | |
| CN108088828A (en) | A kind of twin columns aromatic hydrocarbons mercury ion fluorescent sensor and its preparation and application | |
| CN108516979B (en) | Compound based on naphthalimide-rhodamine and application thereof | |
| CN113004256B (en) | Ratio type probe for detecting mercury ions and preparation method and application thereof | |
| CN107652309B (en) | A kind of fluorescein for open hole detection-ultraviolet molecular probe of rhodamine B copper ion and its synthesis and application method | |
| CN108640867B (en) | Fluorescent probe compound containing cyano-carbazolyl Schiff base as well as preparation method and application thereof | |
| CN112480110B (en) | Multi-response azacyclo-formaldehyde fluorescent probe molecule and preparation method and application thereof | |
| CN105968098B (en) | A kind of quinoline substituted containing carbazole, benzimidazole and its preparation method and application | |
| CN117165284A (en) | Ratio fluorescent probe and test strip for detecting tetracycline as well as preparation methods and applications thereof | |
| CN115521308B (en) | Photosensitive compound, preparation and application thereof and formaldehyde spectrochemical sensor | |
| CN115322262B (en) | Be used for detecting Fe 3+ Dialdehyde cellulose coumarin fluorescent probe and preparation method and application thereof | |
| CN114805613B (en) | For detecting Fe 3+ Ethyl cellulose base flavonol fluorescent probe and preparation method and application thereof | |
| CN106008971B (en) | Preparation method of fluorescent probe polyimide | |
| CN111233885B (en) | Fluorescent probe for detecting methanol and application thereof | |
| CN108191760B (en) | Fluorescent probe for detecting Cu (II) and preparation method and application thereof | |
| CN107831165A (en) | A kind of binary channels copper ion test paper and preparation method thereof | |
| CN110590784B (en) | Derivative based on pyrrolopyrroledione and preparation method and application thereof | |
| CN106967025A (en) | A kind of preparation and its application of 6 chlorine 3 [(the diethylin benzylidene of 2 hydroxyl 4) amino] cumarins | |
| CN109574875B (en) | Fluorescent probe for detecting iron ions and preparation method and application thereof | |
| CN108949159B (en) | Fluorescent probe for detecting palladium ions and synthetic method and application thereof | |
| CN114605388B (en) | Stimulus-responsive nitrogen heterocyclic compound, 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 | ||
| CP01 | Change in the name or title of a patent holder |
Address after: 510070 Guangzhou City, Guangzhou, Guangdong, No. 34 Patentee after: Institute of testing and analysis, Guangdong Academy of Sciences (Guangzhou analysis and testing center, China) Address before: 510070 Guangzhou City, Guangzhou, Guangdong, No. 34 Patentee before: GUANGDONG INSTITUTE OF ANALYSIS (CHINA NATIONAL ANALYTICAL CENTER, GUANGZHOU) |
|
| CP01 | Change in the name or title of a patent holder |