CN114380964A - Ternary covalent organic framework material and application thereof in ratio pH fluorescence sensing - Google Patents
Ternary covalent organic framework material and application thereof in ratio pH fluorescence sensing Download PDFInfo
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- 239000013310 covalent-organic framework Substances 0.000 title claims abstract description 57
- 239000000463 material Substances 0.000 title claims abstract description 40
- IIQLVLWFQUUZII-UHFFFAOYSA-N 2-amino-5-(4-amino-3-carboxyphenyl)benzoic acid Chemical compound C1=C(C(O)=O)C(N)=CC=C1C1=CC=C(N)C(C(O)=O)=C1 IIQLVLWFQUUZII-UHFFFAOYSA-N 0.000 claims abstract description 8
- QEIRCDAYPQFYBI-UHFFFAOYSA-N 6-(5-aminopyridin-2-yl)pyridin-3-amine Chemical compound N1=CC(N)=CC=C1C1=CC=C(N)C=N1 QEIRCDAYPQFYBI-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims abstract description 8
- 238000001917 fluorescence detection Methods 0.000 claims abstract description 7
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims abstract 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 23
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 claims description 10
- 239000007864 aqueous solution Substances 0.000 claims description 7
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 5
- 230000005284 excitation Effects 0.000 claims description 5
- 238000007710 freezing Methods 0.000 claims description 5
- 230000008014 freezing Effects 0.000 claims description 5
- 239000012452 mother liquor Substances 0.000 claims description 5
- 239000000243 solution Substances 0.000 claims description 4
- 238000010257 thawing Methods 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 3
- 238000007789 sealing Methods 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000010413 mother solution Substances 0.000 claims description 2
- 238000000967 suction filtration Methods 0.000 claims description 2
- 238000000265 homogenisation Methods 0.000 claims 1
- 238000002360 preparation method Methods 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 4
- 238000001139 pH measurement Methods 0.000 abstract 1
- 230000035440 response to pH Effects 0.000 abstract 1
- 238000010189 synthetic method Methods 0.000 abstract 1
- 239000011148 porous material Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 3
- 238000000634 powder X-ray diffraction Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000004088 simulation Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000002336 sorption--desorption measurement Methods 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- JGLMVXWAHNTPRF-CMDGGOBGSA-N CCN1N=C(C)C=C1C(=O)NC1=NC2=CC(=CC(OC)=C2N1C\C=C\CN1C(NC(=O)C2=CC(C)=NN2CC)=NC2=CC(=CC(OCCCN3CCOCC3)=C12)C(N)=O)C(N)=O Chemical compound CCN1N=C(C)C=C1C(=O)NC1=NC2=CC(=CC(OC)=C2N1C\C=C\CN1C(NC(=O)C2=CC(C)=NN2CC)=NC2=CC(=CC(OCCCN3CCOCC3)=C12)C(N)=O)C(N)=O JGLMVXWAHNTPRF-CMDGGOBGSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 239000003708 ampul Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000000295 emission spectrum Methods 0.000 description 1
- 150000002085 enols Chemical class 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000005311 nuclear magnetism Effects 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 238000001350 scanning transmission electron microscopy Methods 0.000 description 1
- 238000000527 sonication Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003419 tautomerization reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G12/00—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
- C08G12/02—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes
- C08G12/04—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with acyclic or carbocyclic compounds
- C08G12/06—Amines
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- C—CHEMISTRY; METALLURGY
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- C08G12/00—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
- C08G12/02—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes
- C08G12/04—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with acyclic or carbocyclic compounds
- C08G12/06—Amines
- C08G12/08—Amines aromatic
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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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Abstract
The invention discloses a synthetic method of a ratio pH sensor based on a ternary covalent organic framework material, wherein the covalent organic framework material is constructed by utilizing a ternary doping strategy of 2-hydroxybenzene-1, 3, 5-trimethyl aldehyde, 5,5 '-diamino-2, 2' -bipyridine and 4,4 '-diamino-3, 3' -biphenyldicarboxylic acid, and has ratio response to pH within a range of 2-5.5. Fills the gap that the pH sensor without multi-covalent organic framework ratio is not available before. The method has low requirement on equipment and simple preparation method. The prepared ternary covalent organic framework material has stronger chemical stability and higher application value in the aspect of fluorescence detection. The invention also discloses application of the ternary covalent organic framework material in ratio pH sensing.
Description
Technical Field
The invention relates to the field of organic crystalline porous materials and ratio fluorescence sensors, in particular to a ternary covalent organic framework material and application thereof in ratio pH fluorescence sensing.
Background
The traditional fluorescence sensor usually only displays one emission peak, and the intensity of the traditional fluorescence sensor is easily interfered by external factors such as excitation intensity, temperature, instruments and the like, and the result is possibly inaccurate. The ratio fluorescence sensor detects according to the ratio of the two emission signals, has a self-calibration function, and can overcome the defects of a monochromatic fluorescence sensor, thereby obtaining a more reliable detection result. How to build accurate, efficient and stable rf sensors has been a popular research topic and remains challenging, involving the fine arrangement of fluorescence modules with the same excitation wavelength but different emission signals. The Covalent Organic Frameworks (COFs) material is a pure organic crystalline porous material and has the characteristics of diversity of composition and structure, larger specific surface area, regular pore channel structure, adjustable pore channel size and the like. COFs are constructed by completely relying on covalent bond connection, and have better mechanical stability and chemical stability. Based on the characteristics, the COFs material has wide application value in the aspects of fluorescence sensing and the like.
Ratiometric fluorescent sensors based on COFs materials are still in the infancy and there is an urgent need to develop new strategies for manufacturing sensors based on COF materials.
Disclosure of Invention
In view of the above problems, the present invention provides a ratiometric pH sensor based on a ternary covalent organic framework material, a preparation method thereof, and an application in fluorescence sensing.
In order to achieve the above object, the present invention provides a ternary covalent organic framework based material, named COFHDBThe structural formula is shown as a formula (1),
further, the ternary covalent organic framework material is prepared from 2-hydroxybenzene-1, 3, 5-trimethylaldehyde, 5,5 '-diamino-2, 2' -bipyridine and 4,4 '-diamino-3, 3' -biphenyldicarboxylic acid.
The invention also provides a preparation method of the ternary covalent organic framework material, which comprises the following steps:
adding o-dichlorobenzene into a container filled with 2-hydroxybenzene-1, 3, 5-trimethyl aldehyde, 5,5 '-diamino-2, 2' -bipyridine and 4,4 '-diamino-3, 3' -biphenyldicarboxylic acid, ultrasonically dispersing uniformly, adding acetic acid as a catalyst, freezing, vacuumizing, thawing, and sealing and heating after three cycles; and cooling to room temperature, carrying out suction filtration on the system, and washing with tetrahydrofuran to obtain the catalyst.
Further, the molar ratio of 2-hydroxybenzene-1, 3, 5-trimethylaldehyde, 5,5 '-diamino-2, 2' -bipyridine and 4,4 '-diamino-3, 3' -biphenyldicarboxylic acid was 1:0.75: 0.75.
Further, the concentration of the acetic acid aqueous solution was 6M.
Further, the volume ratio of the o-dichlorobenzene to the acetic acid aqueous solution is 10: 1.
Further, the heating temperature is 120 ℃.
Further, the heating time was 3 days.
Further, freezing, vacuumizing, unfreezing, and sealing the tube under vacuum after three cycles.
The invention also provides an application of the ternary covalent organic framework material in ratio pH fluorescence sensing.
Specifically, a COFHDBDispersing in water solution, ultrasonic homogenizing, and preparing COFHBDMother liquor; a COFHBDAnd mixing the mother solution with aqueous solutions with different pH values, carrying out fluorescence detection, and collecting a fluorescence spectrogram.
Further, COFHBDThe concentration of the mother liquor was 0.1 mg/mL.
Further, the excitation wavelength for fluorescence detection was 320 nm.
Further, the pH range with the ratio response is 2-5.5.
Compared with the prior art, the invention has the following advantages and beneficial effects:
1. according to the invention, the ternary covalent organic framework material is constructed by a monomer doping strategy, has good fluorescence property, crystallinity and chemical stability, and can be applied to a ratio pH sensor.
2. The ternary covalent organic framework material prepared by the method is applied to a ratio pH sensor, the intensity of fluorescence peaks at 420nm and 490nm shows ratio change along with the change of pH, and COFHBDThe fluorescence intensity and the pH value of the compound are in a linear relation, the linear range is 2-5.5, and the fact that the ternary covalent organic framework material can be applied to a ratio pH sensor is fully demonstrated.
3. The invention fills the gap that no multi-covalent organic framework ratio pH sensor exists before. The method has low requirement on equipment and simple preparation method; the ternary covalent organic framework material prepared by the invention has stronger chemical stability and higher application value in the aspect of fluorescence detection.
Drawings
The accompanying drawings, which are included to provide a further understanding of the disclosure, illustrate embodiments of the disclosure and together with the description serve to explain the disclosure and are not to limit the disclosure.
Embodiments of the present disclosure are described in detail below with reference to the attached drawing figures, wherein:
FIG. 1 shows ternary covalent organic framework material COF prepared by the inventionHBDSynthetic roadmaps of (a);
FIG. 2 is a powder X-ray diffraction pattern of a ternary covalent organic framework material made in accordance with the present invention;
FIG. 3 is a solid nuclear magnetic carbon spectrum of the ternary covalent organic framework material prepared by the invention;
FIG. 4 is a nitrogen adsorption/desorption graph and a pore size distribution graph of a ternary covalent organic framework material prepared by the method;
FIG. 5 is a scanning electron microscope and transmission electron microscope image of a ternary covalent organic framework material prepared according to the present invention;
FIG. 6 is a ratiometric pH sensor plot of ternary covalent organic framework materials made in accordance with the present invention;
FIG. 7 is a linear plot of fluorescence intensity versus pH for ternary covalent organic framework materials made in accordance with the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Example 1 ternary covalent organic framework materials and their use as ratiometric pH sensors
COFHBDThe structure of (A) is shown as formula (1):
(a) FIG. 1 shows ternary covalent organic framework material COF prepared by the inventionHBDThe synthesis route map of (1), the specific synthesis steps are as follows:
to a 5mL ampoule, 2-hydroxybenzene-1, 3, 5-triformal (0.08mmol, 14.4mg), 5,5 '-diamino-2, 2' -bipyridine (0.06mmol,11.2mg), and 4,4 '-diamino-3, 3' -biphenyldicarboxylic acid (0.06mmol, 16.32mg) were added in this order, 2mL o-dichlorobenzene was added, the mixture was dispersed uniformly by sonication, 0.2mL of an aqueous acetic acid solution was added as a catalyst (6M), freezing, vacuum-pumping, thawing, and after three cycles, the mixture was heated with a sealed tube. Cooling to room temperature, filtering the system and washing with tetrahydrofuran to obtain COFHBDThe yield was 81%.
(b) Ratio fluorescence detection:
0.1mg/mL of COF HBD200 microliters of the mother liquor was mixed with aqueous solutions of different pH (1.8 ml) with excitation light of 320nm and the emission spectrum was recorded.
In FIG. 2, the COF is shown by a powder X-ray diffraction patternHBDA strong diffraction peak was observed at about 3.42 °, and small peaks were observed at 5.96 °, 6.83 ° and 25.98 °, belonging to the (100), (110), (200) and (001) crystal planes, respectively. Experimental PXRD results and AA accumulation simulation results (Green line)) Agreement indicating COFHBDThe covalent organic framework material is formed by AA stacking. In FIG. 3, the solid nuclear magnetism peaks at 186.59ppm,143.17ppm, and 110.37ppm, indicating enol to ketone tautomerism in the structure. The adsorption-desorption curves shown in FIG. 4 indicate COFHBDHas a specific surface area of 166m2The pore diameter of the nonlinear density functional function simulation is 2 nm. In fig. 5, scanning electron microscopy and transmission electron microscopy showed that the morphology of the material was irregular stripe structures on the micron scale. FIG. 6 is a fluorescence sensing diagram of the ratio of the pH of the material, and the intensity of fluorescence peaks at 420nm and 490nm shows the ratio change along with the change of the pH. FIG. 7 is a COFHBDThe linear range of the fluorescence intensity and pH of (1) is 2-5.5.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. A ternary covalent organic framework material is characterized in that the structural formula is shown as formula (1):
2. the ternary covalent organic framework material of claim 1, characterized in that it is prepared from 2-hydroxybenzene-1, 3, 5-trimethylaldehyde, 5,5 '-diamino-2, 2' -bipyridine and 4,4 '-diamino-3, 3' -biphenyldicarboxylic acid.
3. A method of preparing a ternary covalent organic framework material according to any of the preceding claims, comprising the steps of:
adding o-dichlorobenzene into a container filled with 2-hydroxybenzene-1, 3, 5-trimethyl aldehyde, 5,5 '-diamino-2, 2' -bipyridine and 4,4 '-diamino-3, 3' -biphenyldicarboxylic acid, ultrasonically dispersing uniformly, adding acetic acid as a catalyst, freezing, vacuumizing, thawing, and sealing and heating after three cycles; and cooling to room temperature, carrying out suction filtration on the system, and washing with tetrahydrofuran to obtain the catalyst.
4. The process according to claim 3, wherein the molar ratio of 2-hydroxybenzene-1, 3, 5-trimethylaldehyde, 5,5 '-diamino-2, 2' -bipyridine and 4,4 '-diamino-3, 3' -biphenyldicarboxylic acid is 1:0.75: 0.75.
5. The method according to claim 3, wherein the concentration of the aqueous acetic acid solution is 6M; the volume ratio of the o-dichlorobenzene to the acetic acid aqueous solution is 10: 1.
6. The production method according to claim 3, wherein the heating temperature is 120 degrees Celsius; the heating time was 3 days.
7. The method of claim 3, wherein the freezing, evacuating and thawing are performed after three cycles, and the tube is sealed under vacuum.
8. Use of a ternary covalent organic framework material based on claim 1 or 2 in ratiometric pH fluorescence sensing.
9. The application according to claim 8, characterized in that it is specifically: dispersing the ternary covalent organic framework material into an aqueous solution, and performing ultrasonic homogenization to prepare a ternary covalent organic framework material mother solution; and mixing the ternary covalent organic framework material mother liquor with aqueous solutions with different pH values, carrying out fluorescence detection, and collecting a fluorescence spectrogram.
10. The use of claim 9, wherein the concentration of the ternary covalent organic framework material mother liquor is 0.1 mg/mL; the excitation wavelength of fluorescence detection is 320 nm; the pH range with the ratio response is 2-5.5.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110240683A (en) * | 2019-06-11 | 2019-09-17 | 山东大学 | A kind of covalent organic frame material and preparation method thereof and the application in fluorescent optical sensor |
| CN111607051A (en) * | 2020-06-08 | 2020-09-01 | 江南大学 | Three-dimensional fluorescent covalent organic framework material and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110240683A (en) * | 2019-06-11 | 2019-09-17 | 山东大学 | A kind of covalent organic frame material and preparation method thereof and the application in fluorescent optical sensor |
| CN111607051A (en) * | 2020-06-08 | 2020-09-01 | 江南大学 | Three-dimensional fluorescent covalent organic framework material and preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| JIE-YU YUE等: ""Novel enzyme-functionalized covalent organic frameworks for the colorimetric sensing of glucose in body fluids and drinks"", MATERIALS CHEMISTRY FRONTIERS, no. 5, 19 March 2021 (2021-03-19), pages 3859 - 3866 * |
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