CN115160237A - Fluorescent probe for detecting hydrogen sulfide and preparation method and application thereof - Google Patents
Fluorescent probe for detecting hydrogen sulfide and preparation method and application thereof Download PDFInfo
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- CN115160237A CN115160237A CN202210925215.9A CN202210925215A CN115160237A CN 115160237 A CN115160237 A CN 115160237A CN 202210925215 A CN202210925215 A CN 202210925215A CN 115160237 A CN115160237 A CN 115160237A
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- hydrogen sulfide
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- 239000007850 fluorescent dye Substances 0.000 title claims abstract description 73
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 title claims abstract description 62
- 229910000037 hydrogen sulfide Inorganic materials 0.000 title claims abstract description 62
- 238000002360 preparation method Methods 0.000 title abstract description 9
- -1 2, 4-dinitrophenoxy Chemical group 0.000 claims abstract description 34
- LISFMEBWQUVKPJ-UHFFFAOYSA-N quinolin-2-ol Chemical compound C1=CC=C2NC(=O)C=CC2=C1 LISFMEBWQUVKPJ-UHFFFAOYSA-N 0.000 claims abstract description 24
- 125000005504 styryl group Chemical group 0.000 claims abstract description 15
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 13
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 13
- IRFHMTUHTBSEBK-QGZVFWFLSA-N tert-butyl n-[(2s)-2-(2,5-difluorophenyl)-3-quinolin-3-ylpropyl]carbamate Chemical compound C1([C@H](CC=2C=C3C=CC=CC3=NC=2)CNC(=O)OC(C)(C)C)=CC(F)=CC=C1F IRFHMTUHTBSEBK-QGZVFWFLSA-N 0.000 claims abstract description 10
- 239000007864 aqueous solution Substances 0.000 claims abstract description 6
- 239000000126 substance Substances 0.000 claims abstract description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 72
- 239000002904 solvent Substances 0.000 claims description 33
- RGHHSNMVTDWUBI-UHFFFAOYSA-N 4-hydroxybenzaldehyde Chemical compound OC1=CC=C(C=O)C=C1 RGHHSNMVTDWUBI-UHFFFAOYSA-N 0.000 claims description 18
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 18
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 16
- 239000007787 solid Substances 0.000 claims description 14
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Natural products CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 238000001514 detection method Methods 0.000 claims description 12
- LOTKRQAVGJMPNV-UHFFFAOYSA-N 1-fluoro-2,4-dinitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(F)C([N+]([O-])=O)=C1 LOTKRQAVGJMPNV-UHFFFAOYSA-N 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 8
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 8
- 238000004440 column chromatography Methods 0.000 claims description 7
- POYSUXIHCXBJPN-UHFFFAOYSA-N 3-Methyl-quinolin-2-ol Chemical compound C1=CC=C2NC(=O)C(C)=CC2=C1 POYSUXIHCXBJPN-UHFFFAOYSA-N 0.000 claims description 6
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 238000000746 purification Methods 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 238000004821 distillation Methods 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 230000020477 pH reduction Effects 0.000 claims description 2
- 238000010992 reflux Methods 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 239000000523 sample Substances 0.000 abstract description 7
- 230000008859 change Effects 0.000 abstract description 6
- 230000003287 optical effect Effects 0.000 abstract description 4
- 150000001875 compounds Chemical class 0.000 abstract description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 30
- 150000001450 anions Chemical class 0.000 description 21
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 12
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 11
- 238000010521 absorption reaction Methods 0.000 description 9
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 8
- 229910020366 ClO 4 Inorganic materials 0.000 description 7
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 7
- 230000004044 response Effects 0.000 description 7
- 238000005481 NMR spectroscopy Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 238000002189 fluorescence spectrum Methods 0.000 description 5
- 238000000862 absorption spectrum Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 3
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical class [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 235000013305 food Nutrition 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 230000035945 sensitivity Effects 0.000 description 3
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000004809 thin layer chromatography Methods 0.000 description 3
- 238000004448 titration Methods 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000007405 data analysis Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000001506 fluorescence spectroscopy Methods 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 239000011550 stock solution Substances 0.000 description 2
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 2
- 201000010374 Down Syndrome Diseases 0.000 description 1
- 208000018737 Parkinson disease Diseases 0.000 description 1
- 206010044688 Trisomy 21 Diseases 0.000 description 1
- 239000012491 analyte Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 208000019425 cirrhosis of liver Diseases 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- XUJNEKJLAYXESH-UHFFFAOYSA-N cysteine Natural products SCC(N)C(O)=O XUJNEKJLAYXESH-UHFFFAOYSA-N 0.000 description 1
- 235000018417 cysteine Nutrition 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 210000002472 endoplasmic reticulum Anatomy 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000000338 in vitro Methods 0.000 description 1
- 238000001727 in vivo Methods 0.000 description 1
- 230000004054 inflammatory process Effects 0.000 description 1
- 230000003914 insulin secretion Effects 0.000 description 1
- 239000003550 marker Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 238000010534 nucleophilic substitution reaction Methods 0.000 description 1
- 125000001741 organic sulfur group Chemical group 0.000 description 1
- 238000012261 overproduction Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 230000035479 physiological effects, processes and functions Effects 0.000 description 1
- 230000035790 physiological processes and functions Effects 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 150000003248 quinolines Chemical class 0.000 description 1
- 125000002943 quinolinyl group Chemical group N1=C(C=CC2=CC=CC=C12)* 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 230000000946 synaptic effect Effects 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D241/00—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings
- C07D241/36—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings condensed with carbocyclic rings or ring systems
- C07D241/38—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings condensed with carbocyclic rings or ring systems with only hydrogen or carbon atoms directly attached to the ring nitrogen atoms
- C07D241/40—Benzopyrazines
- C07D241/44—Benzopyrazines with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to carbon atoms of the hetero ring
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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- 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"
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Abstract
The invention discloses a fluorescent probe for detecting hydrogen sulfide and a preparation method and application thereof. The chemical name of the fluorescent probe is (E) -3- (4- (2, 4-dinitrophenoxy) styryl) quinoline-2 (1H) -ketone, and the preparation method comprises the following steps: (1) Synthesis of (E) -3- (4-hydroxystyryl) quinolin-2 (1H) -one: (E) Synthesis of (E) -3- (4- (2, 4-dinitrophenoxy) styryl) quinolin-2 (1H) -one. The fluorescent probe is used for detecting hydrogen sulfide in an aqueous solution. Compared with the prior art, the invention has the following advantages: the fluorophore of the fluorescent probe is not designed for identifying hydrogen sulfide, so that the compound is novel; the probe has good specificity, and mainly has the characteristic that only hydrogen sulfide can cut ether bonds, thereby causing optical signal change.
Description
Technical Field
The invention relates to the field of fluorescent probes, in particular to a fluorescent probe for detecting hydrogen sulfide and a preparation method and application thereof.
Background
The fluorescent probe has the characteristics of simplicity, practicability, economy, cost-effectiveness, high sensitivity, specificity, easy identification and the like, and has good application in qualitative and quantitative detection and analysis as well as in-vivo and in-vitro detection. Therefore, the field of fluorescent probes is receiving much attention from researchers.
Hydrogen sulfide (H) 2 S) is an odorous gas endogenously produced by cysteine under the catalysis of cysteine- β -synthetase or cysteine- γ -lyase that regulates many physiological processes such as synaptic activity, endoplasmic reticulum stress, insulin release and inflammatory processes. Overproduction of hydrogen sulfide may lead to a variety of diseases, such as Parkinson's disease, down's syndrome, alzheimer's diseaseDiseases, liver cirrhosis, etc. In addition, hydrogen sulfide can be found in organic sulfur-rich foods and serves as a marker of food spoilage. Therefore, the development of a novel analysis method for detecting hydrogen sulfide in real time has important significance not only in physiology but also in food safety, and the design and synthesis of a fluorescent probe capable of qualitatively detecting hydrogen sulfide has irreplaceable significance for life health and environmental protection.
In conclusion, designing and synthesizing a fluorescent probe capable of qualitatively detecting hydrogen sulfide has irreplaceable significance for life health and environmental protection. Meanwhile, the development of a novel, simple, sensitive and economical method for detecting the concentration of hydrogen sulfide has become one of the urgent needs in human life and survival.
Disclosure of Invention
In view of the above, the present invention aims to provide a fluorescent probe with high sensitivity and strong selectivity, which can detect hydrogen sulfide in an aqueous solution, and a preparation method and an application thereof.
The purpose of the invention is realized by the following technical scheme:
the inventor knows that quinoline fluorophores are often used in the fields of drug synthesis, optical materials and the like because molecules of the quinoline fluorophores have semi-rigid structures, contain nitrogen heterocycles and have good water solubility. However, quinoline fluorophore has the defects of small conjugate plane, short excitation wavelength and the like, and the identification performance of detecting an analyte by using the quinoline fluorophore as a fluorescent probe is poor, so that the quinoline fluorophore cannot be directly used in actual life. A series of quinoline fluorescent probes are designed by carrying out molecular modification on a quinoline structure, a benzene ring is introduced between a fluorophore and a recognition site to increase a probe molecule conjugate plane, and hydroxyl with potential electron supply is selected as a probe precursor for modification to construct a push-pull conjugate system for recognizing anions, so that good fluorescence optical characteristics are generated. The following protocol then results:
a fluorescent probe for detecting hydrogen sulfide, wherein the chemical name of the fluorescent probe is (E) -3- (4- (2, 4-dinitrophenoxy) styryl) quinolin-2 (1H) -one, and the structural formula of the fluorescent probe is as follows:
the fluorescent probe provided by the invention takes 3-methylquinoline-2 (1H) -ketone as a fluorophore and 2, 4-dinitroether bond as a recognition site, and has no ultraviolet absorption peak at 550nm under the condition that acetonitrile is taken as a solvent, and after hydrogen sulfide is added, the absorption peak at 380nm is reduced, and a new peak at 550nm is generated. And when other anions are added, the ultraviolet absorption spectrum of the fluorescent probe is not obviously changed. In the fluorescence spectrum, initially no fluorescence was present, HS was added - After that, the fluorescence intensity at 490nm was significantly increased. Under 365nm UV light, addition of HS was observed - After which a fluorescent light is present, while the other anions are unchanged. Addition of HS in the presence of interference from other ions - After that, a new absorption peak still appears at 490nm, and is hardly interfered by other ions.
Correspondingly, the invention also provides a preparation method of the fluorescent probe, which comprises the following steps:
(1) Synthesis of (E) -3- (4-hydroxystyryl) quinolin-2 (1H) -one:
adding 3-methylquinoline-2 (1H) -ketone into a container, adding p-hydroxybenzaldehyde and a first solvent, heating, refluxing, recovering the room temperature after the reaction is completed, separating and purifying, and collecting light yellow powder (E) -3- (4-hydroxystyryl) quinoline-2 (1H) -ketone
(2) Synthesis of (E) -3- (4- (2, 4-dinitrophenoxy) styryl) quinolin-2 (1H) -one:
dissolving (E) -3- (4-hydroxystyryl) quinoline-2 (1H) -ketone in a second solvent, adding 2, 4-dinitrofluorobenzene and potassium carbonate, injecting into the second solvent, reacting at room temperature, separating and purifying after the reaction is completed, and collecting to obtain yellow solid (E) -3- (4- (2, 4-dinitrophenoxy) styryl) quinoline-2 (1H) -ketone.
Further, the molar volume ratio of the 3-methylquinolin-2 (1H) -one, the p-hydroxybenzaldehyde and the first solvent in the step (1) is (2-4) mmol, (2-4) mmol:150ml.
Further, the molar volume ratio of the (E) -3- (4-hydroxystyryl) quinolin-2 (1H) -one, the 2, 4-dinitrofluorobenzene, the potassium carbonate and the second solvent in the step (2) is (4-6) mmol; (6-8) mmol; (6-8) mmol; (35-40) ml.
Further, the first solvent is acetic acid; the second solvent is N, N-dimethylformamide.
Further, the reaction time in the step (1) is 5h, and the reaction time in the step (2) is 3h.
Further, the separation and purification mode comprises one or more of acidification, washing, reduced pressure distillation, column chromatography and column chromatography purification.
The application of the fluorescent probe for detecting hydrogen sulfide is characterized in that the fluorescent probe is applied to detecting hydrogen sulfide in an aqueous solution.
Further, in the detection, the hydrogen sulfide was tested by dissolving the fluorescent probe in acetonitrile.
Compared with the prior art, the invention has the following advantages:
(1) The fluorophore of the fluorescent probe is not designed for identifying hydrogen sulfide, so that the compound is novel;
(2) The probe has good specificity, and mainly has the characteristic that only hydrogen sulfide can cut ether bonds, thereby causing optical signal change.
Drawings
FIG. 1 is a graph showing fluorescence emission spectra of the fluorescent probe of example 1 when different HS-concentrations were added to the acetonitrile solution;
FIG. 2 is a graph showing the relationship between A-550nm and HS-concentration;
FIG. 3 is a photograph under fluorescent irradiation of different anions added to an acetonitrile solution of the fluorescent probe in example 1;
FIG. 4 is a bar graph of the change in fluorescence emission at 490nm for HS-response when different anions are added to and co-present with other anions in the acetonitrile solution of the fluorescent probe of example 1, showing that the other anions do not interfere with the response to hydrogen sulfide;
FIG. 5 is the UV-Vis spectra of the fluorescent probe of example 1 with different HS-concentrations added in the acetonitrile solution;
FIG. 6 bar graph of the UV absorption change at 550nm for HS-response when different anions are added and coexisted with other anions to acetonitrile solution of the fluorescent probe in example 1, showing that the other anions do not interfere with the response to hydrogen sulfide.
Detailed Description
To explain technical contents, structural features, and objects and effects of the technical solutions in detail, the following detailed description is given with reference to the accompanying drawings in conjunction with the embodiments.
The names, specifications and manufacturer information of the various raw materials used in the examples of the present invention are shown in Table 1.
TABLE 1
| Name of raw material | Manufacturer information |
| 3-methylquinolin-2 (1H) -ones | SHANGHAI TITAN TECHNOLOGY Co.,Ltd. |
| P-hydroxy benzaldehyde | SHANGHAI TITAN TECHNOLOGY Co.,Ltd. |
| 2, 4-dinitrofluorobenzene | SHANGHAI TITAN TECHNOLOGY Co.,Ltd. |
| Potassium carbonate | SHANGHAI TITAN TECHNOLOGY Co.,Ltd. |
| Ethyl acetate | SHANGHAI TITAN TECHNOLOGY Co.,Ltd. |
| Acetic acid | SHANGHAI TITAN TECHNOLOGY Co.,Ltd. |
| N, N-dimethylformamide | SHANGHAI TITAN TECHNOLOGY Co.,Ltd. |
The silica gel column used in each example of the present invention was a silica gel column having a length of 45cm and a diameter of 45mm, which was manufactured by Beijing Bihua glass instruments Co., ltd.
Example 1
The invention relates to synthesis of a fluorescent probe molecule for detecting hydrogen sulfide, which is prepared from 3-methylquinoline-2 (1H) -ketone, p-hydroxybenzaldehyde and 2, 4-dinitrofluorobenzene serving as raw materials through condensation and nucleophilic substitution
(1) Synthesis of (E) -3- (4-hydroxystyryl) quinolin-2 (1H) -one:
a mixture of 3-methylquinolin-2 (1H) -one (0.365g, 3mmol), p-hydroxybenzaldehyde (0.4g, 2.5mmol) in the first solvent (150 ml) was stirred at 120 ℃ for 5 hours. After completion of the reaction (monitored on thin layer chromatography), the reaction mixture was cooled to room temperature and then filtered with suction using a buchner funnel to afford the product. Washing with saturated sodium bicarbonate solution and drying gave the product (E) -3- (4-hydroxystyryl) quinolin-2 (1H) -one (0.48g, 73% yield) as a pale yellow solid; the first solvent is acetic acid; the yellowish solid powder obtained above was measured by means of a nuclear magnetic resonance instrument (Bruker AVANCE III 400 MHz) and the data are as follows:
1 H NMR(400MHz,DMSO-d6)δ[ppm]:12.43(d,J＝16.2Hz,1H),9.94(d,J＝16.2Hz,,1H),7.99(d,J＝16.2Hz,,1H),7.75(d,J＝16.2.0Hz,1H),7.58(d,J＝8.5Hz,2H),7.49-7.40(m,2H),7.33-7.26(m,2H),6.83(d,J＝8.4Hz,2H). 13 C NMR(101MHz,DMSO-d6)δ[ppm]:159.50,155.30,153.81,137.80,132.92,131.91,129.98,129.76,128.54,127.58,123.91,118.80,116.39,115.65,39.98.HRMS-ESI Calcd.For C 16 H 13 N 2 O 2 [M + H] + :265.0932；Found:265.0978. . the result of the nuclear magnetic resonance spectrum data analysis of the light yellow solid powder product shows that the light yellow solid powder product is (E) -3- (4-hydroxystyryl) quinoline-2 (1H) -ketone, and the structural formula is as follows:
(2) Synthesis of (E) -3- (4- (2, 4-dinitrophenoxy) styryl) quinolin-2 (1H) -one:
a mixture of (E) -3- (4-hydroxystyryl) quinolin-2 (1H) -one (0.40g, 1.51mmol) and 2, 4-dinitrofluorobenzene (0.56g, 3.03mmol), potassium carbonate (0.42g, 3.03mmol) in the second solvent (35 ml) was stirred at room temperature for 3 hours and TCL followed the progress of the reaction and the reaction was completed. Then, the solution was extracted with ethyl acetate, washed with an appropriate amount of saturated brine, and dried over anhydrous sodium sulfate. Finally, the dried solution was concentrated and purified by column chromatography (PE: EA = 12: 1) to give (E) -3- (4- (2, 4-dinitrophenoxy) styryl) quinolin-2 (1H) -one (0.65g, 70.0% yield) as a yellow solid; the second solvent is N, N-dimethylformamide; the yellow solid powder product obtained above was measured by means of a nuclear magnetic resonance instrument (Bruker AVANCE III 400 MHz) and the data are as follows:
1 H NMR(400MHz,DMSO-d6)δ:12.43(d,J＝16Hz,1H),8.32–8.29(m,1H),8.14(d,J＝16Hz,1H),8.06(d,J＝16Hz,1H),7.79(d,J＝16Hz,1H),7.73-7.64(m,4H),7.51(t,J＝16Hz,1H),7.37(d,J＝16Hz,1H),7.15(d,J＝12Hz,2H),7.08(d,J＝4Hz,1H). 13 C NMR(101MHz,DMSO-d6)δ:156.00,155.46,153.61,148.27,141.55,139.57,136.65,135.13,132.58,130.03,130.00,129.42,129.25,128.97,127.67,127.51,126.53,122.25,119.47,118.47.HRMS(ESI):m/z calcd for C 22 H 15 N 4 O 6 [M+H] + 431.0913; 431.0928. The yellow solid powder product is (E) -3- (4- (2, 4-dinitrophenoxy) styryl) quinolin-2 (1H) -one, and the structural formula is as follows according to the nuclear magnetic resonance spectrum data analysis of the yellow solid powder product:
identification performance of fluorescent probe for detecting hydrogen sulfide on anions
1. Fluorescent probe titration experiment of hydrogen sulfide
Dissolving the fluorescent probe in acetonitrile to prepare stock solution of 5000 mu mol L-1, and preparing HS in acetonitrile - Stock solution, concentration 50000. Mu. Mol. L-1. 100 mu L of 5000 mu mol/L-1 fluorescent probe solution is weighed into a 25mL volumetric flask, the volume is adjusted to 25mL by acetonitrile solution to prepare 25mL of the fluorescent probe solution with 20 mu mol/L-1 acetonitrile solvent.
Low concentration titration experiment: 25mL of a probe solution of 20. Mu. Mol/L-1 in acetonitrile solvent was poured into a 100mL wide-mouth flask, and 1.0. Mu.L of 50000. Mu. Mol/L-1 (0.1 eq) of HS was added dropwise each time - And (3) shaking the solution uniformly, detecting the ultraviolet absorption spectrum and the fluorescence emission spectrum of the solution, and repeating the operation until 2.5 equivalents of hydrogen sulfide solution is added.
The results showed that, as shown in FIG. 1, the fluorescence emission spectrum of the fluorescent probe was affected by the concentration of hydrogen sulfide, and the emission peak of the fluorescent probe at 490nm gradually increased with the gradual addition of hydrogen sulfide until 28. Mu. Mol. L-1 of HS was added - Equilibrium is reached.
Conclusion of titration experiment: from fig. 2, it can be seen that the detection limit LOD =54nM, and the detection limit is low, indicating that the probe has high sensitivity for detecting hydrogen sulfide.
Then measuring the ultraviolet visible spectrum, as shown in FIG. 5, the ultraviolet absorption of the fluorescent probe is very weak at 550nm, and with the addition of hydrogen sulfide, the ultraviolet absorption value gradually increases until 28. Mu. Mol. L-1 HS is added - Equilibrium is reached.
The fluorescent probe for detecting hydrogen sulfide is applied to detecting hydrogen sulfide in aqueous solution, and during detection, the fluorescent probe is dissolved in acetonitrile to test the hydrogen sulfide.
2. Selective study of fluorescent probes for hydrogen sulfide
Fluorescent probes were prepared to 20. Mu. Mol. L -1 Acetonitrile of (2): water =9: 1; separately preparing F - ,Cl - ,Br - ,I - ,NO 3 - ,ClO 4 - ,H 2 PO 4 - ,S 2 - ,OH - ,AcO - ,SCN - ,HSO 4 - ,CN - ,BF 4 - ,H 2 O 2 ,HSO 3 - ,S 2 O 3 2- 5000. Mu. Mol. L of -1 Acetonitrile: water =9:1, 0.4mL of 5000. Mu. Mol. L solution was measured -1 Fluorescent probe solution, with acetonitrile: water =9:1 constant volume to 100mL to prepare 20 mu mol.L -1 The probe solution of (4) was divided into 17 groups (5 mL each), and 2.5 equivalents (25. Mu.L, 5000. Mu. Mol. L) were added to each group -1 ) The response of the fluorescent probe to each anion is observed by fluorescence emission spectroscopy.
The results show that only HS was added as shown in FIG. 3 - Then, green fluorescence is turned on. As shown in FIG. 4, the fluorescence emission peak of the fluorescent probe is weak at 490nm under the condition of acetonitrile as a solvent, and HS is added - After that, the fluorescence emission peak at 490nm is enhanced, and the fluorescence emission peak of the fluorescent probe is not significantly changed by adding other anions. The fluorescent probe can specifically detect the hydrogen sulfide.
As shown in FIG. 6, the UV absorption value of the fluorescent probe at 550nm was low under the condition of acetonitrile as the solvent, and HS was added - After that, the ultraviolet absorption value at 550nm is increased, and the ultraviolet absorption peak of the fluorescent probe is not obviously changed by adding other anions. The fluorescent probe can specifically detect the hydrogen sulfide.
3. Interference test study on hydrogen sulfide in the presence of other anions
Mixing the prepared F - ,Cl - ,Br - ,I - ,NO 3 - ,ClO 4 - ,H 2 PO 4 - ,S 2 - ,OH - ,AcO - ,SCN - ,HSO 4 - ,CN - ,BF 4 - ,H 2 O 2 ,HSO 3 - ,S 2 O 3 2- The 17 groups of solutions were observed by fluorescence emission spectroscopy, and 2.5 equivalents (25. Mu.L, 5000. Mu. Mol. L) were added thereto, respectively -1 ) The response of the fluorescent probe to the hydrogen sulfide under the interference of various anions is observed through fluorescence emission spectrum.
The results show that, as shown in FIG. 4, the green bars of the fluorescent probe in acetonitrile as solvent respectively indicate the presence of F only - ,Cl - ,Br - ,I - ,NO 3 - ,ClO 4 - ,H 2 PO 4 - ,S 2 - ,OH - ,AcO - ,SCN - ,HSO 4 - ,CN - ,BF 4 - ,H 2 O 2 ,HSO 3 - ,S 2 O 3 2- Emission at 490nm for the anion. The orange bar represents the change that occurs when 2.5 equivalents of hydrogen sulfide are subsequently added. Is obtained at F - ,Cl - ,Br - ,I - ,NO 3 - ,ClO 4 - ,H 2 PO 4 - ,S 2 - ,OH - ,AcO - ,SCN - ,HSO 4 - ,CN - ,BF 4 - ,H 2 O 2 ,HSO 3 - ,S 2 O 3 2- In the presence of anions, the interference on the detection of hydrogen sulfide by a fluorescent probe in an acetonitrile solution is small, and the influence is almost zero.
Mixing the prepared F - ,Cl - ,Br - ,I - ,NO 3 - ,ClO 4 - ,H 2 PO 4 - ,S 2 - ,OH - ,AcO - ,SCN - ,HSO 4 - ,CN - ,BF 4 - ,H 2 O 2 ,HSO 3 - ,S 2 O 3 2- And 17 groups of solutions are observed through ultraviolet absorption spectrum, 2.5 equivalents (25 mu L and 5000 mu mol.L < -1 >) of hydrogen sulfide solution is added respectively, and the response of the fluorescent probe to the hydrogen sulfide under the interference of various anions is observed through the ultraviolet absorption spectrum.
The results showed that, as shown in FIG. 6, the green bars of the fluorescent probe in acetonitrile as the solvent respectively indicate the presence of F alone - ,Cl - ,Br - ,I - ,NO 3 - ,ClO 4 - ,H 2 PO 4 - ,S 2 - ,OH - ,AcO - ,SCN - ,HSO 4 - ,CN - ,BF 4 - ,H 2 O 2 ,HSO 3 - ,S 2 O 3 2- Emission at 490nm for the anion. The orange bar represents the change that occurs when 2.5 equivalents of hydrogen sulfide are subsequently added. Is obtained at F - ,Cl - ,Br - ,I - ,NO 3 - ,ClO 4 - ,H 2 PO 4 - ,S 2 - ,OH - ,AcO - ,SCN - ,HSO 4 - ,CN - ,BF 4 - ,H 2 O 2 ,HSO 3 - ,S 2 O 3 2- In the presence of anions, the interference on the detection of hydrogen sulfide by the fluorescent probe in the acetonitrile solution is small, and the influence is almost avoided.
Example 2
A preparation method of a fluorescent probe for detecting hydrogen sulfide comprises the following steps:
(1) Synthesizing (E) -3- (4-hydroxystyryl) quinoline-2 (1H) -ketone;
a mixture of 3-methylquinolin-2 (1H) -one (0.365g, 3mmol), p-hydroxybenzaldehyde (0.4g, 2.5mmol) in the first solvent (150 ml) was stirred at 120 ℃ for 5 hours. After completion of the reaction (monitored on thin layer chromatography), the reaction mixture was cooled to room temperature and then filtered with suction using a buchner funnel to afford the product. Washing with saturated sodium bicarbonate solution and drying gave the product (E) -3- (4-hydroxystyryl) quinolin-2 (1H) -one (0.48g, 73% yield) as a pale yellow solid; the first solvent is acetic acid;
(2) Synthesis of (E) -3- (4- (2, 4-dinitrophenoxy) styryl) quinolin-2 (1H) -one:
a mixture of (E) -3- (4-hydroxystyryl) quinolin-2 (1H) -one (0.40g, 1.51mmol) and 2, 4-dinitrofluorobenzene (0.56g, 3.03mmol), potassium carbonate (0.42g, 3.03mmol) in a second solvent (35 ml) was stirred at room temperature for 3 hours and TCL followed the progress of the reaction and the reaction was complete. Then, the solution was extracted with ethyl acetate, washed with an appropriate amount of saturated brine, and dried over anhydrous sodium sulfate. Finally, the dried solution was concentrated and purified by column chromatography (PE: EA = 12: 1) to give (E) -3- (4- (2, 4-dinitrophenoxy) styryl) quinolin-2 (1H) -one (0.65g, 70.0% yield) as a yellow solid; the second solvent is N, N-dimethylformamide;
example 3
A preparation method of a fluorescent probe for detecting hydrogen sulfide comprises the following steps:
(1) Synthesizing (E) -3- (4-hydroxystyryl) quinoline-2 (1H) -ketone;
a mixture of 3-methylquinolin-2 (1H) -one (0.365g, 3mmol), p-hydroxybenzaldehyde (0.4g, 2.5mmol) in the first solvent (150 ml) was stirred at 120 ℃ for 5 hours. After completion of the reaction (monitored on thin layer chromatography), the reaction mixture was cooled to room temperature and then suction filtered with a buchner funnel to give the product. Washing with saturated sodium bicarbonate solution and drying gave the product (E) -3- (4-hydroxystyryl) quinolin-2 (1H) -one (0.48g, 73% yield) as a pale yellow solid; the first solvent is acetic acid;
(2) Synthesis of (E) -3- (4- (2, 4-dinitrophenoxy) styryl) quinolin-2 (1H) -one:
a mixture of (E) -3- (4-hydroxystyryl) quinolin-2 (1H) -one (0.40g, 1.51mmol) and 2, 4-dinitrofluorobenzene (0.56g, 3.03mmol), potassium carbonate (0.42g, 3.03mmol) in a second solvent (35 ml) was stirred at room temperature for 3 hours and TCL followed the progress of the reaction and the reaction was complete. Then, the solution was extracted with ethyl acetate, washed with an appropriate amount of saturated brine, and dried over anhydrous sodium sulfate. Finally, the dried solution was concentrated and purified by column chromatography (PE: EA = 12: 1) to give (E) -3- (4- (2, 4-dinitrophenoxy) styryl) quinolin-2 (1H) -one (0.65g, 70.0% yield) as a yellow solid; the second solvent is N, N-dimethylformamide;
the fluorescent probe for detecting hydrogen sulfide is applied to detecting hydrogen sulfide in aqueous solution, and during detection, the fluorescent probe is dissolved in acetonitrile to test the hydrogen sulfide.
Although the embodiments have been described, once the basic inventive concept is obtained, other variations and modifications of these embodiments can be made by those skilled in the art, so that the above embodiments are only examples of the present invention, and not intended to limit the scope of the present invention, and all equivalent structures or equivalent processes using the contents of the present specification and drawings, or any other related technical fields, which are directly or indirectly applied thereto, are included in the scope of the present invention.
Claims (9)
1. A fluorescent probe for detecting hydrogen sulfide is characterized in that the chemical name of the fluorescent probe is (E) -3- (4- (2, 4-dinitrophenoxy) styryl) quinolin-2 (1H) -one, and the structural formula of the fluorescent probe is as follows:
2. a method for preparing a fluorescent probe for detecting hydrogen sulfide according to claim 1, comprising the steps of:
(1) Synthesis of (E) -3- (4-hydroxystyryl) quinolin-2 (1H) -one:
adding 3-methylquinoline-2 (1H) -ketone into a container, adding p-hydroxybenzaldehyde and a first solvent, heating, refluxing, recovering the room temperature after the reaction is completed, separating and purifying, and collecting light yellow powder (E) -3- (4-hydroxystyryl) quinoline-2 (1H) -ketone
(2) Synthesis of (E) -3- (4- (2, 4-dinitrophenoxy) styryl) quinolin-2 (1H) -one:
dissolving (E) -3- (4-hydroxystyryl) quinoline-2 (1H) -ketone in a second solvent, adding 2, 4-dinitrofluorobenzene and potassium carbonate, injecting into the second solvent, reacting at room temperature, separating and purifying after the reaction is completed, and collecting to obtain yellow solid (E) -3- (4- (2, 4-dinitrophenoxy) styryl) quinoline-2 (1H) -ketone.
3. The method for preparing a fluorescent probe for detecting hydrogen sulfide as claimed in claim 2, wherein the molar volume ratio of the 3-methylquinolin-2 (1H) -one, the p-hydroxybenzaldehyde and the first solvent in step (1) is (2-4) mmol, (2-4) mmol:150ml.
4. The method for preparing a fluorescent probe for detecting hydrogen sulfide as claimed in claim 2, wherein the molar volume ratio of the (E) -3- (4-hydroxystyryl) quinolin-2 (1H) -one, the 2, 4-dinitrofluorobenzene, the potassium carbonate and the second solvent in the step (2) is (4-6) mmol; (6-8) mmol; (6-8) mmol; (35-40) ml.
5. The method for preparing a fluorescent probe for detecting hydrogen sulfide as claimed in claim 2, 3 or 4, wherein the first solvent is acetic acid; the second solvent is N, N-dimethylformamide.
6. The method for preparing a fluorescent probe for detecting hydrogen sulfide as claimed in claim 2, 3 or 4, wherein the reaction time in step (1) is 5 hours, and the reaction time in step (2) is 3 hours.
7. The method for preparing a fluorescent probe for detecting hydrogen sulfide as claimed in claim 2, 3 or 4, wherein the separation and purification manner includes one or more of acidification, washing, reduced pressure distillation, column chromatography and column chromatography purification.
8. Use of a fluorescent probe for the detection of hydrogen sulfide as claimed in claim 1 for the detection of hydrogen sulfide in an aqueous solution.
9. The use of a fluorescent probe for the detection of hydrogen sulfide as claimed in claim 7, wherein the hydrogen sulfide is tested by dissolving the fluorescent probe in acetonitrile.
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