CN113788816B - Dehydroabietic acid based quinoxaline mercury ion fluorescent probe and preparation method and application thereof - Google Patents
Dehydroabietic acid based quinoxaline mercury ion fluorescent probe and preparation method and application thereof Download PDFInfo
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- CN113788816B CN113788816B CN202110906426.3A CN202110906426A CN113788816B CN 113788816 B CN113788816 B CN 113788816B CN 202110906426 A CN202110906426 A CN 202110906426A CN 113788816 B CN113788816 B CN 113788816B
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- Prior art keywords
- methyl ester
- bromo
- dehydroabietic acid
- quinoxaline
- reaction
- Prior art date
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- -1 quinoxaline mercury Chemical compound 0.000 title claims abstract description 129
- 239000007850 fluorescent dye Substances 0.000 title claims abstract description 48
- QUUCYKKMFLJLFS-UHFFFAOYSA-N Dehydroabietan Natural products CC1(C)CCCC2(C)C3=CC=C(C(C)C)C=C3CCC21 QUUCYKKMFLJLFS-UHFFFAOYSA-N 0.000 title claims abstract description 45
- NFWKVWVWBFBAOV-UHFFFAOYSA-N Dehydroabietic acid Natural products OC(=O)C1(C)CCCC2(C)C3=CC=C(C(C)C)C=C3CCC21 NFWKVWVWBFBAOV-UHFFFAOYSA-N 0.000 title claims abstract description 45
- NFWKVWVWBFBAOV-MISYRCLQSA-N dehydroabietic acid Chemical compound OC(=O)[C@]1(C)CCC[C@]2(C)C3=CC=C(C(C)C)C=C3CC[C@H]21 NFWKVWVWBFBAOV-MISYRCLQSA-N 0.000 title claims abstract description 45
- 229940118781 dehydroabietic acid Drugs 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- PGZCJOPTDHWYES-UHFFFAOYSA-N methyl 1,4a-dimethyl-7-propan-2-yl-2,3,4,9,10,10a-hexahydrophenanthrene-1-carboxylate Chemical compound CC(C)C1=CC=C2C3(C)CCCC(C(=O)OC)(C)C3CCC2=C1 PGZCJOPTDHWYES-UHFFFAOYSA-N 0.000 claims abstract description 85
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 57
- 229910052753 mercury Inorganic materials 0.000 claims abstract description 41
- 239000002253 acid Substances 0.000 claims abstract description 38
- 150000004702 methyl esters Chemical class 0.000 claims abstract description 36
- 238000001514 detection method Methods 0.000 claims abstract description 18
- 230000035484 reaction time Effects 0.000 claims abstract description 14
- 235000014102 seafood Nutrition 0.000 claims abstract description 12
- 238000005886 esterification reaction Methods 0.000 claims abstract description 10
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 9
- RIIPFHVHLXPMHQ-UHFFFAOYSA-N [4-(dimethylamino)phenyl]boronic acid Chemical compound CN(C)C1=CC=C(B(O)O)C=C1 RIIPFHVHLXPMHQ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 230000007613 environmental effect Effects 0.000 claims abstract description 8
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- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 84
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 57
- 238000006243 chemical reaction Methods 0.000 claims description 52
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 49
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 48
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- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 32
- 238000000034 method Methods 0.000 claims description 28
- 125000004105 2-pyridyl group Chemical group N1=C([*])C([H])=C([H])C([H])=C1[H] 0.000 claims description 27
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 26
- 238000005406 washing Methods 0.000 claims description 24
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 23
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 18
- 239000007787 solid Substances 0.000 claims description 17
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Chemical compound BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-UHFFFAOYSA-N 0.000 claims description 16
- 239000003208 petroleum Substances 0.000 claims description 16
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 14
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 14
- BQPIGGFYSBELGY-UHFFFAOYSA-N mercury(2+) Chemical compound [Hg+2] BQPIGGFYSBELGY-UHFFFAOYSA-N 0.000 claims description 14
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims description 14
- 238000010992 reflux Methods 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
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- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 10
- 229920006395 saturated elastomer Polymers 0.000 claims description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- 238000006396 nitration reaction Methods 0.000 claims description 9
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical class [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 8
- 238000000605 extraction Methods 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 238000012544 monitoring process Methods 0.000 claims description 8
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 7
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- XHFLOLLMZOTPSM-UHFFFAOYSA-M sodium;hydrogen carbonate;hydrate Chemical class [OH-].[Na+].OC(O)=O XHFLOLLMZOTPSM-UHFFFAOYSA-M 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 5
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical class [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 150000002500 ions Chemical class 0.000 claims description 4
- CDXSJGDDABYYJV-UHFFFAOYSA-N acetic acid;ethanol Chemical compound CCO.CC(O)=O CDXSJGDDABYYJV-UHFFFAOYSA-N 0.000 claims description 3
- 230000031709 bromination Effects 0.000 claims description 3
- 238000005893 bromination reaction Methods 0.000 claims description 3
- 239000007795 chemical reaction product Substances 0.000 claims description 3
- 238000002425 crystallisation Methods 0.000 claims description 3
- 230000008025 crystallization Effects 0.000 claims description 3
- 239000005457 ice water Substances 0.000 claims description 3
- 238000004090 dissolution Methods 0.000 claims description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 230000009467 reduction Effects 0.000 claims description 2
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 claims description 2
- 230000003595 spectral effect Effects 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims 2
- 150000003839 salts Chemical class 0.000 claims 1
- 239000000523 sample Substances 0.000 abstract description 22
- 150000001875 compounds Chemical class 0.000 abstract description 21
- XSCHRSMBECNVNS-UHFFFAOYSA-N quinoxaline Chemical compound N1=CC=NC2=CC=CC=C21 XSCHRSMBECNVNS-UHFFFAOYSA-N 0.000 abstract description 8
- 235000013305 food Nutrition 0.000 abstract description 6
- 125000002252 acyl group Chemical group 0.000 abstract description 3
- 238000005660 chlorination reaction Methods 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 3
- 229930014626 natural product Natural products 0.000 abstract description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052794 bromium Inorganic materials 0.000 abstract description 2
- 238000005303 weighing Methods 0.000 description 18
- 229910021645 metal ion Inorganic materials 0.000 description 11
- 239000000047 product Substances 0.000 description 8
- PBCJIPOGFJYBJE-UHFFFAOYSA-N acetonitrile;hydrate Chemical compound O.CC#N PBCJIPOGFJYBJE-UHFFFAOYSA-N 0.000 description 7
- 229960000583 acetic acid Drugs 0.000 description 6
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- 230000002194 synthesizing effect Effects 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 4
- 239000012043 crude product Substances 0.000 description 4
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- 229910000029 sodium carbonate Inorganic materials 0.000 description 4
- 239000011550 stock solution Substances 0.000 description 4
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 4
- ZXVONLUNISGICL-UHFFFAOYSA-N 4,6-dinitro-o-cresol Chemical group CC1=CC([N+]([O-])=O)=CC([N+]([O-])=O)=C1O ZXVONLUNISGICL-UHFFFAOYSA-N 0.000 description 3
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- 239000003054 catalyst Substances 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000012362 glacial acetic acid Substances 0.000 description 3
- 125000001567 quinoxalinyl group Chemical group N1=C(C=NC2=CC=CC=C12)* 0.000 description 3
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- 238000003756 stirring Methods 0.000 description 3
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 2
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- BYEAHWXPCBROCE-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropan-2-ol Chemical compound FC(F)(F)C(O)C(F)(F)F BYEAHWXPCBROCE-UHFFFAOYSA-N 0.000 description 1
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
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- DWDURZSYQTXVIN-UHFFFAOYSA-N 4-[(4-aminophenyl)-(4-methyliminocyclohexa-2,5-dien-1-ylidene)methyl]aniline Chemical compound C1=CC(=NC)C=CC1=C(C=1C=CC(N)=CC=1)C1=CC=C(N)C=C1 DWDURZSYQTXVIN-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
- C07D401/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing three or more hetero rings
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- 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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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
- G01N21/643—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes" non-biological material
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- C09K2211/10—Non-macromolecular compounds
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- C09K2211/1044—Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms
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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"
- G01N2021/6432—Quenching
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- Investigating Or Analysing Biological Materials (AREA)
Abstract
The invention discloses a dehydroabietic acid-based quinoxaline mercury ion fluorescent probe and a preparation method and application thereof, wherein a natural product dehydroabietic acid is used as a raw material, and is subjected to acyl chlorination and methyl esterification to synthesize dehydroabietic acid methyl ester, then the dehydroabietic acid methyl ester reacts with NBS to generate a product 12-bromine dehydroabietic acid methyl ester, the product is subjected to double nitrification to synthesize a key intermediate 12-bromine-13, 14-dinitrodehydroabietic acid methyl ester, the intermediate is subjected to Fe/HCl reduction reaction to generate 12-bromine-13, 14-diamino dehydroabietic acid methyl ester, the product is condensed with 2, 2-bipyridyl diketone to generate a quinoxaline intermediate, and the intermediate is continuously reacted with 4-dimethylamino phenylboronic acid to generate a target compound. The compound can be selectively complexed with mercury ions, orange fluorescence is quenched within 10s of reaction time, the effect of detecting the mercury ions in real time is achieved, the lowest detection limit reaches 10.3nM, and meanwhile, the compound is applied to detecting the mercury ions in an environmental water sample and seafood food, and has a good application prospect.
Description
Technical Field
The invention belongs to the technical field of fine organic synthesis, and particularly relates to a dehydroabietic acid based quinoxaline mercury ion fluorescent probe, and a preparation method and application thereof.
Background
The mercury ions are highly toxic heavy metal ions which seriously harm human health, are widely distributed in various environment media such as air, water, soil and the like, are easily enriched and converted into organic mercury in human bodies in a food chain mode and the like, are not easy to degrade, can form chelate with certain functional groups in cells to destroy the normal functions of corresponding enzymes or proteins in the bodies, and cause the generation of a plurality of diseases such as water sickness, developmental delay, neurological dysfunction and the like.
At present, although there are many traditional metal ion detection methods, such as inductively coupled plasma mass spectrometry, atomic absorption spectrometry, gas chromatography, high performance liquid chromatography, cyclic voltammetry, etc., these methods not only require expensive instruments and equipment, but also have the problems of complicated sample pretreatment, high operation specialty, etc.
Compared with the traditional analysis and detection method, the fluorescence probe method has the advantages of simple operation, high detection speed, wide detection range, high sensitivity, good biocompatibility and the like, and is currently applied to the detection of metal ions such as mercury ions.
In recent years, many organic fluorescent probes are researched for detecting mercury ions, such as rhodamine lactam fluorescent probes and coumarin fluorescent probes, but the organic fluorescent probes still have many defects, such as strong ionic interference, long reaction time and the like.
Disclosure of Invention
This section is for the purpose of summarizing some aspects of embodiments of the invention and to briefly introduce some preferred embodiments. In this section, as well as in the abstract and title of the application, simplifications or omissions may be made to avoid obscuring the purpose of the section, the abstract and the title, and such simplifications or omissions are not intended to limit the scope of the invention.
The present invention has been made keeping in mind the above and/or other problems occurring in the prior art.
Therefore, the invention aims to overcome the defects in the prior art and provide a dehydroabietic acid based quinoxaline mercury ion fluorescent probe.
In order to solve the technical problems, the invention provides the following technical scheme: a dehydroabietic acid based quinoxaline mercury ion fluorescent probe is disclosed, and the name of the fluorescent probe is as follows: 12- (4- (dimethylamino) phenyl) -7,10 a-dimethyl-2, 3-di (pyridin-2-yl) -5,6,6a,7,8,9,10,10 a-octahydronaphthalene [2,1-f ] quinoxaline-7-methyl ester having the formula:
the invention further aims to overcome the defects in the prior art and provide a preparation method of the dehydroabietic acid based quinoxaline mercury ion fluorescent probe.
In order to solve the technical problems, the invention provides the following technical scheme: a preparation method of a dehydroabietic acid based quinoxaline mercury ion fluorescent probe comprises the steps of carrying out methyl esterification, bromination and double nitration on dehydroabietic acid to prepare 12-bromine-13, 14-dinitrodehydroabietic acid methyl ester; reducing the 12-bromo-13, 14-dinitrodehydroabietic acid methyl ester by Fe/HCl to prepare 12-bromo-13, 14-diamino isopropyl dehydroabietic acid methyl ester; 12-bromo-13, 14-diamino-deisopropyldehydroabietic acid methyl ester reacts with 2, 2' -pyridone to generate 12-bromo-7, 10 a-dimethyl-2, 3-di (pyridin-2-yl) -5,6,6a,7,8,9,10,10 a-octahydronaphthalene [2,1-f ] quinoxaline-7-methyl ester; reacting 12-bromo-7, 10 a-dimethyl-2, 3-di (pyridine-2-yl) -5,6,6a,7,8,9,10,10 a-octahydronaphthalene [2,1-f ] quinoxaline-7-methyl ester with 4-dimethylaminobenzeneboronic acid to generate 12- (4- (dimethylamino) phenyl) -7,10 a-dimethyl-2, 3-di (pyridine-2-yl) -5,6,6a,7,8,9,10,10 a-octahydronaphthalene [2,1-f ] quinoxaline-7-methyl ester, and obtaining the mercury ion fluorescent probe.
As a preferred scheme of the preparation method of the dehydroabietic acid based quinoxaline mercury ion fluorescent probe, the method comprises the following steps: the preparation method of the 12-bromo-13, 14-dinitro dehydroabietic acid methyl ester comprises the steps of dissolving dehydroabietic acid in toluene, adding excessive thionyl chloride for reaction, carrying out vacuum spin-drying after the reaction is finished, adding excessive methanol for methyl esterification reaction, carrying out vacuum spin-drying after the reaction is finished, adding ethanol for dissolution, and standing for crystallization to obtain a dehydroabietic acid methyl ester solid; the method comprises the following steps of preparing dehydroabietic acid and methyl benzene, wherein the dosage ratio of the dehydroabietic acid to the methyl benzene is 1g: 1.5-3 mL, the dosage ratio of the dehydroabietic acid to the thionyl chloride is 1g: 0.3-0.4 mL, the dosage ratio of the dehydroabietic acid to the methyl alcohol is 1g: 1-3 mL, the reaction temperature of the dehydroabietic acid to the thionyl chloride is 75-80 ℃, the reaction time is 3-5 hours, the methyl esterification reaction temperature is 75-80 ℃, and the reaction time is 3-5 hours;
dissolving the dehydroabietic acid methyl ester solid in acetonitrile, adding N-bromosuccinimide, reacting at normal temperature in a dark place, performing vacuum spin-drying after the reaction is finished, washing twice with dichloromethane, spin-drying, adding methanol, heating for dissolving, standing, cooling and crystallizing to obtain 12-bromodehydroabietic acid methyl ester solid; the method comprises the following steps of (1) preparing dehydroabietic acid methyl ester, wherein the dosage ratio of dehydroabietic acid methyl ester to acetonitrile is 1g: 5-8 mL, the reaction time is 22-25 h, the heating methanol temperature is 60-65 ℃, and the mass ratio of dehydroabietic acid methyl ester to N-bromosuccinimide is 1.0-1.5: 1;
adding 12-bromo-dehydroabietic acid methyl ester into a mixed acid of fuming nitric acid and concentrated sulfuric acid, carrying out double nitration reaction under an ice bath condition, pouring into a proper amount of ice-water mixture after the reaction is finished, extracting with ethyl acetate for three times, washing with water for three times, washing with a saturated sodium bicarbonate aqueous solution and a saturated saline solution for one time respectively, drying with anhydrous sodium sulfate, spin-drying, and recrystallizing with a proper amount of methanol to obtain a light yellow needle-shaped solid of 12-bromo-13, 14-dinitrodehydroabietic acid methyl ester; wherein the dosage ratio of the 12-bromo dehydroabietic acid methyl ester to fuming nitric acid is 1g: 6-7 mL, the dosage ratio of the 12-bromo dehydroabietic acid methyl ester to concentrated sulfuric acid is 1-3 g:1mL, and the reaction time of the nitration reaction under the ice bath condition is 0.5-1.5 h.
As a preferred scheme of the preparation method of the dehydroabietic acid based quinoxaline mercury ion fluorescent probe, the method comprises the following steps: the preparation method of the 12-bromo-13, 14-diamino dehydroabietic acid methyl ester comprises the following steps,
dissolving 12-bromo-13, 14-dinitrodehydroabietic acid methyl ester in ethanol, adding excessive iron powder, adding distilled water and concentrated hydrochloric acid, and carrying out reduction reaction under a heating condition, wherein petroleum ether: TLC monitoring is carried out on acetone 2:1, after the reaction is finished, ethyl acetate is used for extraction three times, water washing is carried out for three times, saturated sodium bicarbonate water solution and saturated saline solution are respectively washed once, anhydrous sodium sulfate is dried, and vacuum spin drying is carried out to obtain oily crude 12-bromo-13, 14-diamino dehydroabietic acid methyl ester; wherein,
the dosage ratio of the 12-bromo-13, 14-dinitrodehydroabietic acid methyl ester to HFIP is 1g: 4-5 mL, the mass ratio of the 12-bromo-13, 14-dinitrodehydroabietic acid methyl ester to iron powder is 1: 1.2-1.3, and the dosage ratio of the 12-bromo-13, 14-dinitrodehydroabietic acid methyl ester to hydrochloric acid is 0.1-0.12 g:1 mL;
the dosage ratio of the 12-bromo-13, 14-dinitrodehydroabietic acid methyl ester to the distilled water is 1g: 44-46 mL;
the reduction temperature of the Fe/HCl is 40-50 ℃, and the reaction time is 2-3 h.
As a preferred scheme of the preparation method of the dehydroabietic acid based quinoxaline mercury ion fluorescent probe, the method comprises the following steps: the 12-bromo-7, 10 a-dimethyl-2, 3-di (pyridin-2-yl) -5,6,6a,7,8,9,10,10 a-octahydronaphthalene [2,1-f ] quinoxalin-7-methyl ester is prepared by a process comprising,
dissolving 2, 2' -pyridone in ethanol, dissolving 12-bromo-13, 14-diamino dehydroabietic acid methyl ester in acetic acid, mixing an acetic acid-ethanol reaction system, performing reflux reaction at 85-95 ℃ for about 12 hours under the protection of nitrogen, and mixing petroleum ether: TLC monitoring was performed at 2:1, and after the reaction was completed, vacuum spin-drying, extraction three times with ethyl acetate, washing three times with water, extraction once each of saturated sodium carbonate solution and saturated brine, drying over anhydrous sodium sulfate, extraction with petroleum ether: purifying the ethyl acetate by a column at a ratio of 100:1-20:1 to obtain off-white solid 12-bromo-7, 10 a-dimethyl-2, 3-di (pyridin-2-yl) -5,6,6a,7,8,9,10,10 a-octahydronaphthalene [2,1-f ] quinoxaline-7-methyl ester; wherein,
the molar ratio of the 12-bromo-13, 14-diamino dehydroabietic acid methyl ester to the 4-dimethylamino phenylboronic acid is 1: 1.5-2;
the 12-bromo-13, 14-diamino dehydroabietic acid methyl ester was reacted with pd (pph)3)4The molar ratio of (A) to (B) is 9-10: 1;
the molar ratio of the 12-bromo-13, 14-diamino dehydroabietic acid methyl ester to the 2, 2' -pyridone is 1.1-1.2: 1.
As a preferred scheme of the preparation method of the dehydroabietic acid based quinoxaline mercury ion fluorescent probe, the method comprises the following steps: the preparation method of the 12- (4- (dimethylamino) phenyl) -7,10 a-dimethyl-2, 3-di (pyridine-2-yl) -5,6,6a,7,8,9,10,10 a-octahydronaphthalene [2,1-f ] quinoxaline-7-methyl ester comprises the following steps,
the 12-bromo-7, 10 a-dimethyl-2, 3-di (pyridine-2-yl) -5,6,6a,7,8,9,10,10 a-octahydronaphthalene [2,1-f ]]Dissolving quinoxaline-7-methyl ester in toluene and ethanol, and adding 4-dimethylamino phenylboronic acid and K2CO3Solution, pd (pph)3)4Carrying out reflux reaction for 12h at 80-100 ℃ under the protection of nitrogen, and carrying out TLC monitoring on petroleum ether and acetone in a ratio of 2: 1;
after the reaction is finished, the reaction product is dried in vacuum, extracted three times by ethyl acetate and washed three times by water, saturated sodium carbonate solution is extracted and extracted once by saturated saline water respectively, dried by anhydrous sodium sulfate and purified by petroleum ether and ethyl acetate which are 50:1-10:1 through a column, and pure orange-red solid 12- (4- (dimethylamino) phenyl) -7,10 a-dimethyl-2, 3-di (pyridine-2-yl) -5,6,6a,7,8,9,10,10 a-octahydronaphthalene [2,1-f ] quinoxaline-7-methyl ester is obtained.
The invention also aims to overcome the defects in the prior art and provide the application of the dehydroabietic acid based quinoxaline mercury ion fluorescent probe in the detection of mercury ions.
As a preferable aspect of the application of the present invention, wherein: the 12- (4- (dimethylamino) phenyl) -7,10 a-dimethyl-2, 3-di (pyridine-2-yl) -5,6,6a,7,8,9,10,10 a-octahydronaphthalene [2,1-f ] quinoxaline-7-methyl ester is used as a fluorescent probe for the spectral reaction for detecting mercury ions, the fluorescent probe reduces the fluorescence intensity to quenching under the action of the mercury ions, and the lowest limit of detection (LOD) of the mercury ions is as low as nM level and reaches 10.3 nM.
As a preferable aspect of the application of the present invention, wherein: the detection of the 12- (4- (dimethylamino) phenyl) -7,10 a-dimethyl-2, 3-di (pyridine-2-yl) -5,6,6a,7,8,9,10,10 a-octahydronaphthalene [2,1-f ] quinoxaline-7-methyl ester as a fluorescent probe to mercury ions is not interfered by other coexisting ions.
As a preferable aspect of the application of the present invention, wherein: the application of the 12- (4- (dimethylamino) phenyl) -7,10 a-dimethyl-2, 3-di (pyridine-2-yl) -5,6,6a,7,8,9,10,10 a-octahydronaphthalene [2,1-f ] quinoxaline-7-methyl ester as a fluorescent probe in detecting mercury ions in environmental water samples and seafood food.
The invention has the beneficial effects that:
the dehydroabietic acid-based quinoxaline compound prepared by using dehydroabietic acid extracted from natural product renewable resource disproportionated rosin as a raw material generates orange-red fluorescence under 365nM ultraviolet irradiation, can be specifically complexed with mercury ions, rapidly quenches orange fluorescence, has response time as low as 10s and minimum detection limit of 10.3nM, and can also be used as a fluorescent probe for detecting mercury ions in environmental water and seafood food.
The invention provides a dehydroabietic acid based quinoxaline mercury ion fluorescent probe, which can be specifically complexed with mercury ions, and then orange fluorescence is quenched under the irradiation of 365nm ultraviolet rays and the like, and can be used for detecting the content of the mercury ions.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the description of the embodiments will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without inventive exercise. Wherein:
FIG. 1 shows 12- (4- (dimethylamino) phenyl) -7,10 a-dimethyl-2, 3-di (pyridin-2-yl) -5,6,6a,7,8,9,10,10 a-octahydronaphthalene [2,1-f ] according to the present invention]Ultraviolet absorption spectrum and fluorescence emission spectrum of quinoxaline-7-methyl ester and mercury ion, and comparison graph before and after action with mercury ion under sunlight and 365nm ultraviolet lamp irradiation; wherein, in figure 1, (a) is added Hg2+Ultraviolet absorption spectra before and after ionization and a photograph under sunlight, in FIG. 1, (b) shows the addition of Hg2+Fluorescence emission spectrograms before and after the ion and a photograph under a 365nm ultraviolet lamp.
FIG. 2 is a graph showing the sensitivity results and standard curve of the action of 12- (4- (dimethylamino) phenyl) -7,10 a-dimethyl-2, 3-di (pyridin-2-yl) -5,6,6a,7,8,9,10,10 a-octahydronaphthalene [2,1-f ] quinoxaline-7-methyl ester with mercury ions according to the present invention; in fig. 2, (a) is a sensitivity result graph, and in fig. 2, (b) is a standard curve graph.
FIG. 3 is a graph showing the results of selectivity of 12- (4- (dimethylamino) phenyl) -7,10 a-dimethyl-2, 3-di (pyridin-2-yl) -5,6,6a,7,8,9,10,10 a-octahydronaphthalene [2,1-f ] quinoxaline-7-methyl ester of the present invention with different metal ions.
FIG. 4 is a graph showing the results of the interference of 12- (4- (dimethylamino) phenyl) -7,10 a-dimethyl-2, 3-di (pyridin-2-yl) -5,6,6a,7,8,9,10,10 a-octahydronaphthalene [2,1-f ] quinoxaline-7-methyl ester with mercury ions, and other metal ions on the probe according to the present invention.
FIG. 5 is a graph showing the results of the reaction time of 12- (4- (dimethylamino) phenyl) -7,10 a-dimethyl-2, 3-di (pyridin-2-yl) -5,6,6a,7,8,9,10,10 a-octahydronaphthalene [2,1-f ] quinoxaline-7-methyl ester of the present invention with respect to mercury ions as a fluorescent probe.
FIG. 6 shows 12- (4- (dimethylamino) phenyl) -7,10 a-dimethyl-2, 3-di (pyridin-2-yl) -5,6,6a,7,8,9,10,10 a-octahydronaphthalene [2,1-f ] according to the present invention]Quinoxaline-7-methyl ester as fluorescent probe for detecting Hg in environmental water and seafood food2+Application diagram of (1).
Detailed Description
In order to make the aforementioned objects, features and advantages of the present invention more comprehensible, specific embodiments thereof are described in detail below with reference to examples of the specification.
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention, but the present invention may be practiced in other ways than those specifically described and will be readily apparent to those of ordinary skill in the art without departing from the spirit of the present invention, and therefore the present invention is not limited to the specific embodiments disclosed below.
Furthermore, reference herein to "one embodiment" or "an embodiment" means that a particular feature, structure, or characteristic described in connection with the embodiment is included in at least one implementation of the invention. The appearances of the phrase "in one embodiment" in various places in the specification are not necessarily all referring to the same embodiment, nor are separate or alternative embodiments mutually exclusive of other embodiments. The raw materials in the invention are all common commercial products without special description.
Example 1
The synthesis method of the dehydroabietic acid based quinoxaline compound comprises the following steps:
the method comprises the following specific steps:
(1) preparation of 12-bromo-13, 14-dinitrodehydroabietic acid methyl ester: the dehydroabietic acid is prepared by methyl esterification, bromination and double nitration, and the specific process is as follows:
accurately weighing 30g of dehydroabietic acid, dissolving in 60mL of toluene, adding 11mL of thionyl chloride, carrying out reflux reaction at 78-82 ℃ for 3h, carrying out vacuum spin-drying after the reaction is finished, adding 60mL of methanol, continuing reflux reaction at 78-82 ℃ for 3h, carrying out vacuum spin-drying after the reaction is finished, adding 60mL of ethanol for dissolving, and standing for crystallization to obtain a dehydroabietic acid methyl ester solid;
accurately weighing 5g of dehydroabietic acid methyl ester, dissolving in 30mL of acetonitrile, adding 4g of N-bromosuccinimide, reacting for 24h in a dark place at normal temperature, carrying out vacuum rotation and dare, washing twice by using dichloromethane and carrying out rotary evaporation, heating and dissolving 100mL of methanol, standing, cooling and crystallizing to obtain a white solid of 12-bromodehydroabietic acid methyl ester;
accurately weighing 3g of 12-bromo-dehydroabietic acid methyl ester, dissolving in a mixed acid of 19mL fuming nitric acid and 1.5mL concentrated sulfuric acid, reacting for 1h under an ice bath condition, pouring into an ice-water mixture after the reaction is finished, extracting with ethyl acetate for three times, washing with water for three times, washing with saturated sodium bicarbonate aqueous solution and saturated salt solution once respectively, drying with anhydrous sodium sulfate, spin-drying, dissolving with a proper amount of methanol, standing and recrystallizing to obtain light yellow needle-shaped 12-bromo-13, 14-dinitrodehydroabietic acid methyl ester solid with the yield of 88.2%.
(2) Preparation of 12-bromo-13, 14-diamino dehydroabietic acid methyl ester
Accurately weighing 0.44g of 12-bromo-13, 14-dinitrodehydroabietic acid methyl ester, dissolving in 2.105mL of ethanol, sequentially adding 0.56g of iron powder, 4mL of hydrochloric acid and 20mL of distilled water, stirring and reacting at 45 ℃ for 2.5h in a 50mL round-bottom flask, extracting with ethyl acetate for three times after the reaction is finished, washing with distilled water for three times, washing with saturated sodium bicarbonate water solution and saturated saline water solution respectively for one time, drying with anhydrous sodium sulfate, and performing vacuum spin drying to obtain oily crude products, namely 12-bromo-13, 14-diamino dehydroabietic acid methyl ester, wherein the yield is 85.16%.
(3) Preparation of 12-bromo-7, 10 a-dimethyl-2, 3-di (pyridin-2-yl) -5,6,6a,7,8,9,10,10 a-octahydronaphthalene [2,1-f ] quinoxalin-7-methyl ester
Accurately weighing 0.424g of 2, 2' -pyridone and 0.382g of 12-bromo-13, 14-diamino dehydroabietic acid methyl ester, respectively dissolving in 40mL of anhydrous ethanol and 10mL of glacial acetic acid, sequentially adding into a 100mL three-neck flask provided with a stirrer, a thermometer and a reflux condenser tube, reacting under the protection of nitrogen in a reaction system, heating to reflux at 85-95 ℃, reacting for about 12 hours till completion (TLC tracking monitoring). Extracting with ethyl acetate for three times after the reaction is finished, combining organic phases, washing with distilled water for three times, washing with saturated sodium bicarbonate water solution and saturated saline solution for one time respectively, drying the organic phase with anhydrous sodium sulfate, filtering, performing vacuum spin drying, and performing vacuum spin drying by using petroleum ether: purifying the ethyl acetate by a column at a ratio of 100:1-20:1 to obtain a grey white solid crude product 12-bromo-7, 10 a-dimethyl-2, 3-di (pyridin-2-yl) -5,6,6a,7,8,9,10,10 a-octahydronaphthalene [2,1-f ] quinoxaline-7-methyl ester, wherein the yield is 75.25%.
(4) Preparation of 12- (4- (dimethylamino) phenyl) -7,10 a-dimethyl-2, 3-di (pyridin-2-yl) -5,6,6a,7,8,9,10,10 a-octahydronaphthalene [2,1-f ] quinoxaline-7-methyl ester
Accurately weighing 12-bromo-7, 10 a-dimethyl-2, 3-di (pyridine-2-yl) -5,6,6a,7,8,9,10,10 a-octahydronaphthalene [2,1-f ]]0.557g of quinoxaline-7-methyl ester is dissolved in 30mL of toluene and 15mL of ethanol, and 0.33g of 4-dimethylamino phenylboronic acid and 2mol/L K are sequentially added2CO3Solution 6mL, pd (pph)3)40.115g of the reaction mixture is heated to 90 ℃ in a 100mL three-neck flask with a stirrer, a thermometer and a reflux condenser under the protection of nitrogen and refluxed for about 12 hours until the reaction is completed (TLC tracking monitoring);
extracting with ethyl acetate for three times after the reaction is finished, combining organic phases, washing with distilled water for three times, washing with saturated sodium bicarbonate water solution and saturated saline solution for one time respectively, drying the organic phase with anhydrous sodium sulfate, filtering, performing vacuum spin drying, and performing vacuum spin drying by using petroleum ether: purifying the ethyl acetate by a column at a ratio of 50:1-10:1 to obtain pure orange red solid 12- (4- (dimethylamino) phenyl) -7,10 a-dimethyl-2, 3-di (pyridine-2-yl) -5,6,6a,7,8,9,10,10 a-octahydronaphthalene [2,1-f ] quinoxaline-7-methyl ester, wherein the yield is 78.62%.
Product characterization data were: m.p 229.5.5-231 ℃; IR (KBr, cm-1): 819,1161,1250,1523,1609,1724,2856,2927,3430, respectively; 1H NMR (600MHz, DMSO-d6) δ 8.26(d, J ═ 4.44Hz,1H),8.22(d, J ═ 4.44Hz,1H),8.08(d, J ═ 7.74Hz,1H),8.00(d, J ═ 7.74Hz,1H), 7.97-7.91 (m,2H),7.82(s,1H),7.67(d, J ═ 8.64Hz,2H),7.34(dd, J ═ 7.4,4.9Hz,1H),7.30(dd, J ═ 7.4,4.9Hz,1H),6.87(d, J ═ 8.7Hz,2H),3.65(s,3H),3.61(dd, J ═ 18.5,6.5, 1H), 3.95 (d, J ═ 8.7Hz,2H),3.65(s,3H),3.61(dd, J ═ 18.5,6.5, 1H), 3.5 (1H), 3.95 (1.7, 1H), 1H (1H), 8.46 (dd, 1H), 8.46H, 1H); 13C NMR (150MHz, DMSO-d6) delta 177.95,157.50,157.31,150.55,150.20,150.13,149.84,147.87,138.90,137.31,136.75,136.06,131.27,130.61,126.80,125.76,123.85,123.63,123.09,122.97,111.83,51.93,47.10,44.99,40.11,37.52,37.22,35.96,25.37,24.13,20.65,18.04, 16.31; ESI-MS M/z [ M + H ] + calcd for C38H39N5O2598.3182, found [ M + H ] +598.3183.
Example 2
Accurately weighing 12- (4- (dimethylamino) phenyl) -7,10 a-dimethyl-2, 3-di (pyridine-2-yl) -5,6,6a,7,8,9,10,10 a-octahydronaphthalene [2,1-f ]]Quinoxaline-7-methyl ester 59.7mg dissolved in 10mL acetonitrile to prepare 1X 10-3M stock solution, 100. mu.L of the mother liquor was diluted with an acetonitrile-water solution (acetonitrile: water: 1:9) to 10mL of 1X 10-5M probe solution, 100. mu.M Hg was added2+The color of the solution under sunlight is changed from light yellow to colorless, and the ultraviolet absorption spectrum of the solution is measured, while the probe is changed from orange to colorless when observed under an ultraviolet lamp of 365nm, and the fluorescence emission spectrum of the probe is measured.
As shown in fig. 1,1 a: addition of Hg to compounds under sunlight2+Front and back photographs; 1 b: hg is added into the compound under a 365nm ultraviolet lamp2+Front and rear photographs, adding Hg2+The orange fluorescence of the solution of (a) was quenched, indicating that the compound was capable of reacting with Hg2+This action causes quenching of the fluorescence.
Example 3
Accurately weighing 12- (4- (dimethylamino) phenyl) -7,10 a-dimethyl-2, 3-di (pyridine-2-yl) -5,6,6a,7,8,9,10,10 a-octahydronaphthalene [2,1-f ]]Quinoxaline-7-methyl ester 59.7mg dissolved in 10mL acetonitrile to prepare 1X 10-3M stock solution, 100. mu.L of the mother liquor was diluted with an acetonitrile-water solution (acetonitrile: water: 1:9) to 10mL of 1X 10-5In the probe solution of M, mercury ions are dissolved in an acetonitrile-water solution (acetonitrile: water: 1:9) to prepare a solution having a concentration of 0 to 100 μ M.
The effect of different mercury ion concentrations on the fluorescence emission spectra of 12- (4- (dimethylamino) phenyl) -7,10 a-dimethyl-2, 3-di (pyridin-2-yl) -5,6,6a,7,8,9,10,10 a-octahydronaphthalene [2,1-f ] quinoxaline-7-methyl ester was determined by a spectrofluorometer and the results are shown in FIG. 2.
The results show that the fluorescence intensity of the compound is gradually weakened until the compound is completely quenched with the continuous increase of the concentration of the mercury ions in the system, thereby indicating that the compound can be used as a fluorescent probe for sensitively detecting the mercury ions.
Example 4
Accurately weighing 12- (4- (dimethylamino) phenyl) -7,10 a-dimethyl-2, 3-di (pyridine-2-yl) -5,6,6a,7,8,9,10,10 a-octahydronaphthalene [2,1-f ]]Quinoxaline-7-methyl ester 59.7mg dissolved in 10mL acetonitrile to prepare 1X 10-3M was diluted to 10mL of 1X 10 concentration with 100. mu.L of acetonitrile-water solution (acetonitrile: water: 1:9)-5M probe solution, and various metal ions were dissolved in an acetonitrile-water solution (acetonitrile: water: 1:9) at the same time to prepare a 1X 10 probe solution-4M, measuring the different metal ion pairs of 12- (4- (dimethylamino) phenyl) -7,10 a-dimethyl-2, 3-di (pyridine-2-yl) -5,6,6a,7,8,9,10,10 a-octahydronaphthalene [2,1-f ] by a fluorescence spectrophotometer]The fluorescence emission spectrum of quinoxaline-7-methyl ester was influenced and the results are shown in FIG. 3.
The results show that only the addition of mercury ions can significantly reduce the fluorescence intensity of the solution system to quenching, while other metal ions such as Na are added+，Zn2+，Ca2+，Cu2+，Fe2+，Mn2+，Mg2+，Co2+，Cs2+，Cd2+，K+，Sn2+，Ni2+，La3+，In3+，Cu+，Pb2+，Ga3+，Fe3+，Al3+，Ag+，Cr3+According to the comparative reference observation, the fluorescence spectrum of the solution is not obviously changed, and other metal ions do not cause the quenching of the fluorescence of the compound, so that the compound can be used as an effective fluorescent probe for specifically recognizing mercury ions.
Example 5
Accurately weighing 12- (4- (dimethylamino) phenyl) -7,10 a-dimethyl-2, 3-di (pyridine-2-yl) -5,6,6a,7,8,9,10,10 a-octahydronaphthalene [2,1-f ]]Quinoxaline-7-methyl ester 59.7mg dissolved in 10mL acetonitrile to prepare 1X 10-3M was added to 100. mu.L of the mother liquor, and the mixture was diluted with an acetonitrile-water solution (acetonitrile: water: 1:9) to 10mL of a 1X 10 concentration-5M, and adding 100 mu M of mercury ions to react with the probe.
At probe (10. mu.M) + Hg2+To each of the reaction solutions (100. mu.M), 100. mu.M of Na was added+，Zn2+，Ca2+，Cu2+，Fe2+，Mn2+，Mg2+，Co2+，Cs2+，Cd2+，K+，Sn2+，Ni2+，La3+，In3+，Cu+，Pb2+，Ga3+，Fe3+，Al3+，Ag+，Cr3+The fluorescence emission spectrum of the metal ions was measured at an excitation wavelength of 425nm, and the results are shown in FIG. 4.
The result shows that when other metal ions are added, the fluorescence intensity of the 12- (4- (dimethylamino) phenyl) -7,10 a-dimethyl-2, 3-di (pyridine-2-yl) -5,6,6a,7,8,9,10,10 a-octahydronaphthalene [2,1-f ] quinoxaline-7-methyl ester after the action with mercury ions is not obviously influenced, so that the other metal ions do not influence the detection of the mercury ions by the compound, and the compound has strong anti-interference capability on the detection of the mercury ions.
Example 6
Accurately weighing 12- (4- (dimethylamino) phenyl) -7,10 a-dimethyl-2, 3-di (A)Pyridin-2-yl) -5,6,6a,7,8,9,10,10 a-octahydronaphthalene [2,1-f]Quinoxaline-7-methyl ester 59.7mg dissolved in 10mL acetonitrile to prepare 1X 10-3M was added to 100. mu.L of the mother liquor, and the mixture was diluted with an acetonitrile-water solution (acetonitrile: water: 1:9) to 10mL of a 1X 10 concentration-5M probe solution.
100 μ M Hg was added2+To the probe solution, 12- (4- (dimethylamino) phenyl) -7,10 a-dimethyl-2, 3-di (pyridin-2-yl) -5,6,6a,7,8,9,10,10 a-octahydronaphthalene [2,1-f ] was measured at various times]Fluorescence emission intensity of quinoxaline-7-methyl ester, the results are shown in FIG. 5.
The results show that the fluorescence is quenched rapidly after the addition of mercury ions, and the reaction time is 10 s.
Therefore, the compound can be used as a fluorescent probe for rapidly detecting mercury ions.
Example 7
Three water samples, namely basalt lake water in Nanjing, purple lake stream of Nanjing forestry university and tap water in a laboratory are collected, and suspended particles are removed by filtering through slow qualitative filter paper.
Purchasing seafood samples including large yellow croaker and prawn, pretreating by digestion, soaking 1g of seafood sample in 5mL of concentrated nitric acid overnight, boiling at 85 ℃, cooling, adjusting pH to 7.0 by using 2mol/LNaOH solution, and finally diluting the sample to 100mL by using deionized water.
Accurately weighing 12- (4- (dimethylamino) phenyl) -7,10 a-dimethyl-2, 3-di (pyridine-2-yl) -5,6,6a,7,8,9,10,10 a-octahydronaphthalene [2,1-f ]]Quinoxaline-7-methyl ester 59.7mg dissolved in 10mL acetonitrile to prepare 1X 10-3M was diluted to 10mL of a 1X 10 concentration stock solution by using 100. mu.L of a stock solution diluted with a mixed solution of acetonitrile and a pretreated sample (v/v. 1:9)-5M probe solution.
Adding Hg with different concentrations2+(0, 10, 30, 70. mu.M), 12- (4- (dimethylamino) phenyl) -7,10 a-dimethyl-2, 3-di (pyridin-2-yl) -5,6,6a,7,8,9,10,10 a-octahydronaphthalene [2,1-f ] was measured in actual water samples and seafood samples]Fluorescence emission intensity of quinoxaline-7-methyl ester, and a standard curve is drawn for the fluorescence intensity of different samples, and the result is shown in FIG. 6.
The recovery was calculated according to a linear fit equation and the results are shown in table 1.
TABLE 1 determination of Hg in ambient water and seafood foods by Compounds2+Application of
The results show that the fluorescence intensity and Hg at 600nm of 5 actual samples2+There is a good linear relationship between the concentrations.
And to Hg in environmental water samples and seafood foods2+Has good fluorescence recovery rate, thereby showing that the compound can be used for effectively detecting Hg in environmental water samples and seafood foods2+The fluorescent probe of (1).
Example 8
Optimization of the preparation method of the dehydroabietic acid based quinoxaline derivative:
test 1: accurately weighing 0.381g of 12-bromo-13, 14-diamino dehydroabietic acid methyl ester, dissolving in 40mL of absolute ethanol, adding 0.424g of 2, 2' -pyridone, introducing N2, and carrying out reflux reaction at 85 ℃ for 12 h;
after the reaction is finished, extracting for three times by ethyl acetate, washing for three times by water, and using saturated Na2CO3Extracting the solution and saturated salt solution once respectively, and extracting with anhydrous NaSO3Drying, vacuum spin-drying, petroleum ether: purifying the ethyl acetate by a column at a ratio of 100: 1-10:1 to obtain the off-white pure 12-bromo-7, 10 a-dimethyl-2, 3-di (pyridin-2-yl) -5,6,6a,7,8,9,10,10 a-octahydronaphthalene [2, 1-f: (1-1)]Quinoxaline-7-methyl ester, yield 51%.
Test 2: accurately weighing 0.381g of 12-bromo-13, 14-diamino dehydroabietic acid methyl ester, dissolving in 40mL of absolute ethanol, adding 0.424g of 2, 2' -pyridone and 19mg of p-toluenesulfonic acid, introducing N2, and carrying out reflux reaction at 85 ℃ for 12 h;
after the reaction is finished, the mixture is extracted by ethyl acetate for three times, washed by water for three times and saturated Na2CO3Extracting the solution and saturated salt solution once respectively, and extracting with anhydrous NaSO3Drying, vacuum spin-drying, petroleum ether: purifying the ethyl acetate by a column at a ratio of 100: 1-10:1 to obtain the gray-white pure 12-bromo-7, 10 a-dimethyl-2, 3-Bis (pyridin-2-yl) -5,6,6a,7,8,9,10,10 a-octahydronaphthalene [2,1-f]Quinoxaline-7-methyl ester, yield 68%.
Test 3: accurately weighing 0.381g of 12-bromo-13, 14-diamino dehydroabietic acid methyl ester and 0.424g of 2, 2' -pyridone, dissolving in 40mL of absolute ethanol, adding 10mL of acetic acid, mixing an acetic acid-ethanol system, introducing N2, and carrying out reflux reaction at 90 ℃ for 12 hours;
after the reaction is finished, the mixture is extracted by ethyl acetate for three times, washed by water for three times and saturated Na2CO3The solution and saturated salt solution were extracted once each with anhydrous Na2SO4Drying, vacuum spin-drying, petroleum ether: purifying the ethyl acetate by a column at a ratio of 100: 1-10:1 to obtain the off-white pure 12-bromo-7, 10 a-dimethyl-2, 3-di (pyridin-2-yl) -5,6,6a,7,8,9,10,10 a-octahydronaphthalene [2, 1-f: (1-1)]Quinoxaline-7-methyl ester, yield 75%.
Test 4: accurately weighing 0.381g of 12-bromo-13, 14-diamino dehydroabietic acid methyl ester and 0.424g of 2, 2' -pyridone, dissolving in 40mL of glacial acetic acid, introducing N2, and carrying out reflux reaction at 120 ℃ for 12 h;
after the reaction is finished, the mixture is extracted by ethyl acetate for three times, washed by water for three times and saturated Na2CO3The solution and saturated salt solution are extracted once respectively, anhydrous Na2SO4Drying, vacuum spin-drying, petroleum ether: purifying the ethyl acetate by a column at a ratio of 100: 1-10:1 to obtain the off-white pure 12-bromo-7, 10 a-dimethyl-2, 3-di (pyridin-2-yl) -5,6,6a,7,8,9,10,10 a-octahydronaphthalene [2, 1-f: (1-1)]Quinoxaline-7-methyl ester, yield 60%.
TABLE 2 yield of 2-bromo-4-arylbenzimidazoles under different conditions
Note: and/means no catalyst.
As can be seen from Table 2, the conditions of test 3 gave higher reaction yields relative to the other reaction conditions, and therefore the reaction was carried out using this preferred condition.
Example 9
Optimization of preparation method of 12-bromo-13, 14-diamino dehydroabietic acid methyl ester (ethanol replaces HFIP)
(A) Accurately weighing 0.44g of 12-bromo-13, 14-dinitrodehydroabietic acid methyl ester, dissolving in 2.105mL of ethanol, sequentially adding 0.56g of iron powder, 4mL of hydrochloric acid and 20mL of distilled water, stirring and reacting at 45 ℃ for 2.5h in a 50mL round-bottom flask, extracting with ethyl acetate for three times after the reaction is finished, washing with distilled water for three times, washing with saturated sodium bicarbonate water solution and saturated saline water solution once respectively, drying with anhydrous sodium sulfate, and performing vacuum spin drying to obtain an oily crude product, namely 12-bromo-13, 14-diamino dehydroabietic acid methyl ester. The yield was 85.16%.
(B) Accurately weighing 0.44g of 12-bromo-13, 14-dinitrodehydroabietic acid methyl ester, dissolving the methyl ester in 2.105mL of HFIP (1,1,1,3,3, 3-hexafluoro-2-propanol), sequentially adding 0.56g of iron powder, 4mL of hydrochloric acid and 20mL of distilled water, stirring and reacting for 2.5 hours in a 50mL round-bottomed flask at 45 ℃, extracting for three times by using ethyl acetate after the reaction is finished, washing for three times by using the distilled water, washing a saturated sodium bicarbonate aqueous solution and a saturated saline solution once respectively, drying by using anhydrous sodium sulfate, and performing vacuum spin-drying to obtain an oily crude product, namely 12-bromo-13, 14-diaminodehydroabietic acid methyl ester. The yield was 83.24%.
It can be seen that the intermediate product 12-bromo-13, 14-diamino dehydroabietic acid methyl ester is prepared by using ethanol instead of HFIP, the contrast change of the product yield is small, the reaction conditions are more environment-friendly, and the harm to experimenters can be reduced by using ethanol with less toxicity.
The method comprises the steps of using dehydroabietic acid extracted from natural renewable resource disproportionated rosin as a raw material, synthesizing dehydroabietic acid methyl ester with methanol through acyl chlorination of the dehydroabietic acid, generating 12-bromo-dehydroabietic acid methyl ester with NBS (N-bromosuccinimide), reacting the 12-bromo-dehydroabietic acid methyl ester with concentrated sulfuric acid and fuming nitric acid, nitrating and synthesizing 12-bromo-13, 14-dinitrodehydroabietic acid methyl ester, reducing the 12-bromo-13, 14-dinitrodehydroabietic acid methyl ester into 12-bromo-13, 14-diaminodehydroabietic acid methyl ester under the action of hydrochloric acid and iron powder, condensing the 12-bromo-13, 14-diaminodehydroabietic acid methyl ester and 2, 2' -pyridone to introduce a quinoxaline structure, and continuously coupling with 4-dimethylaminobenzene boric acid to generate a target product 12- (4- (dimethylamino) phenyl) -7,10 a-dimethyl-2, 3-bis (pyridin-2-yl) -5,6,6a,7,8,9,10,10 a-octahydronaphthalene [2,1-f ] quinoxalin-7-methyl ester; the compound can rapidly identify Hg2+, can be used as a probe for detecting Hg2+, and is presumed to be quenched by the fact that probe fluorescence is quenched due to complexation of Hg2+ and N on pyridine and quinoxaline.
The nitration separation and purification method of the invention is changed into recrystallization by methanol, the purification operation is simple, the purity and the yield are improved, and the material cost of silica gel solvent and other consumables is also saved.
According to the invention, ethanol is used to replace HFIP in the dinitro reduction reaction process by using iron powder and hydrochloric acid, so that an organic solvent with lower toxicity is replaced on the premise of ensuring the yield, and the harm to experimenters is reduced.
In the process of preparing 12-bromo-7, 10 a-dimethyl-2, 3-di (pyridine-2-yl) -5,6,6a,7,8,9,10,10 a-octahydronaphthalene [2,1-f ] quinoxaline-7-methyl ester, mild acetic acid is used as a catalyst, so that the yield of the product is improved.
The invention aims at reducing dinitro on a key intermediate 12-bromo-13, 14-dinitrodehydroabietic acid methyl ester, reacting with 2, 2-dipyridyl diketone, introducing a quinoxaline structure on a dehydroabietic acid parent structure, designing the structure, and finally synthesizing a target compound 12- (4- (dimethylamino) phenyl) -7,10 a-dimethyl-2, 3-di (pyridine-2-yl) -5,6,6a,7,8,9,10,10 a-octahydronaphthalene [2,1-f ] quinoxaline-7-methyl ester. When the fluorescent probe is prepared, some research experiments are made aiming at the preparation process of the fluorescent probe, which are mainly reflected in that:
(1) the method for separating and purifying the double nitration reaction product abandons the prior column chromatography method and adopts methanol recrystallization, thereby not only improving the purity of the product, but also saving the cost of a silica gel solvent and the like.
(2) In the reduction reaction process of the esterification dinitro, anhydrous ethanol is used for replacing HFIP with high toxicity as a solvent, so that the method is more environment-friendly and reduces the harm to experimenters.
(3) When 12-bromo-7, 10 a-dimethyl-2, 3-di (pyridine-2-yl) -5,6,6a,7,8,9,10,10 a-octahydronaphthalene [2,1-f ] quinoxaline-7-methyl ester is prepared, a proper amount of glacial acetic acid is adopted to replace a p-toluenesulfonic acid catalyst, so that not only can the acidic environment be improved for the reaction, but also the yield is improved to a certain extent.
(4) Quinoxaline structure is introduced by condensation, and then the final probe is synthesized by coupling reaction, thereby improving the yield of the product in each step.
Compared with the existing mercury ion detection technology, such as atomic absorption spectrometry, inductively coupled plasma mass spectrometry and the like, the fluorescent probe technology has the advantages of high sensitivity, strong selectivity, simplicity and convenience in operation and the like.
The method comprises the steps of using natural product dehydroabietic acid as a raw material, synthesizing dehydroabietic acid methyl ester through acyl chlorination and methyl esterification, reacting with NBS to generate a product 12-bromine dehydroabietic acid methyl ester, synthesizing a key intermediate 12-bromine-13, 14-dinitrodehydroabietic acid methyl ester through double nitrification, carrying out Fe/HCl reduction reaction on the intermediate to generate 12-bromine-13, 14-diamino dehydroabietic acid methyl ester, condensing with 2, 2-bipyridyl diketone to generate a quinoxaline intermediate, and continuously reacting the intermediate with 4-dimethylamino phenylboronic acid to generate a target compound. Experiments prove that the compound can be selectively complexed with mercury ions and leads to quenching of orange fluorescence within 10s of reaction time, the effect of detecting the mercury ions in real time is achieved, the lowest detection limit reaches 10.3nM, and meanwhile, the compound is applied to detecting the mercury ions in an environmental water sample and seafood food, so that the compound can be used as a specific fluorescent probe to quickly detect the mercury ions and has a good application prospect.
It should be noted that the above-mentioned embodiments are only for illustrating the technical solutions of the present invention and not for limiting, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions may be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention, which should be covered by the claims of the present invention.
Claims (10)
1. A dehydroabietic acid based quinoxaline mercury ion fluorescent probe is characterized in that: the name of the fluorescent probe is: 12- (4- (dimethylamino) phenyl) -7,10 a-dimethyl-2, 3-di (pyridin-2-yl) -5,6,6a,7,8,9,10,10 a-octahydronaphthalene [2,1-f ] quinoxaline-7-methyl ester having the formula:
2. the method for preparing a dehydroabietic acid based quinoxaline mercury ion fluorescent probe according to claim 1, which is characterized in that: comprises the steps of (a) preparing a mixture of a plurality of raw materials,
carrying out methyl esterification, bromination and double nitration on the dehydroabietic acid to obtain 12-bromo-13, 14-dinitrodehydroabietic acid methyl ester;
reducing the 12-bromo-13, 14-dinitrodehydroabietic acid methyl ester by Fe/HCl to prepare 12-bromo-13, 14-diamino isopropyl dehydroabietic acid methyl ester;
12-bromo-13, 14-diamino-deisopropyldehydroabietic acid methyl ester reacts with 2, 2' -pyridone to generate 12-bromo-7, 10 a-dimethyl-2, 3-di (pyridin-2-yl) -5,6,6a,7,8,9,10,10 a-octahydronaphthalene [2,1-f ] quinoxaline-7-methyl ester;
reacting 12-bromo-7, 10 a-dimethyl-2, 3-di (pyridine-2-yl) -5,6,6a,7,8,9,10,10 a-octahydronaphthalene [2,1-f ] quinoxaline-7-methyl ester with 4-dimethylaminobenzeneboronic acid to generate 12- (4- (dimethylamino) phenyl) -7,10 a-dimethyl-2, 3-di (pyridine-2-yl) -5,6,6a,7,8,9,10,10 a-octahydronaphthalene [2,1-f ] quinoxaline-7-methyl ester, and obtaining the mercury ion fluorescent probe.
3. The method for preparing a dehydroabietic acid based quinoxaline mercury ion fluorescent probe according to claim 2, which is characterized in that: the preparation method of the 12-bromo-13, 14-dinitrodehydroabietic acid methyl ester comprises the following steps,
dissolving dehydroabietic acid in toluene, adding excessive thionyl chloride for reaction, performing vacuum drying after the reaction is finished, adding excessive methanol for methyl esterification, performing vacuum drying after the reaction is finished, adding ethanol for dissolution, and standing for crystallization to obtain a dehydroabietic acid methyl ester solid; the method comprises the following steps of preparing dehydroabietic acid and methyl benzene, wherein the dosage ratio of the dehydroabietic acid to the methyl benzene is 1g: 1.5-3 mL, the dosage ratio of the dehydroabietic acid to the thionyl chloride is 1g: 0.3-0.4 mL, the dosage ratio of the dehydroabietic acid to the methyl alcohol is 1g: 1-3 mL, the reaction temperature of the dehydroabietic acid to the thionyl chloride is 75-80 ℃, the reaction time is 3-5 hours, the methyl esterification reaction temperature is 75-80 ℃, and the reaction time is 3-5 hours;
dissolving the dehydroabietic acid methyl ester solid in acetonitrile, adding N-bromosuccinimide, reacting at normal temperature in a dark place, after the reaction is finished, carrying out vacuum spin-drying, washing twice with dichloromethane, spin-drying, adding methanol, heating for dissolving, standing, cooling and crystallizing to obtain a 12-bromodehydroabietic acid methyl ester solid; the method comprises the following steps of (1) mixing dehydroabietic acid methyl ester and acetonitrile in a ratio of 1g to 5-8 mL, reacting for 22-25 hours, heating methanol at the temperature of 60-65 ℃, wherein the mass ratio of dehydroabietic acid methyl ester to N-bromosuccinimide is 1.0-1.5: 1;
adding 12-bromo-dehydroabietic acid methyl ester into a mixed acid of fuming nitric acid and concentrated sulfuric acid, carrying out double nitration reaction under an ice bath condition, pouring into a proper amount of ice-water mixture after the reaction is finished, extracting with ethyl acetate for three times, washing with water for three times, washing with a saturated sodium bicarbonate aqueous solution and a saturated saline solution for one time respectively, drying with anhydrous sodium sulfate, spin-drying, and recrystallizing with a proper amount of methanol to obtain a light yellow needle-shaped solid of 12-bromo-13, 14-dinitrodehydroabietic acid methyl ester; wherein the dosage ratio of the 12-bromo dehydroabietic acid methyl ester to fuming nitric acid is 1g: 6-7 mL, the dosage ratio of the 12-bromo dehydroabietic acid methyl ester to concentrated sulfuric acid is 1-3 g:1mL, and the reaction time of the nitration reaction under the ice bath condition is 0.5-1.5 h.
4. The method for preparing a dehydroabietic acid based quinoxaline mercury ion fluorescent probe according to claim 2, which is characterized in that: the preparation method of the 12-bromo-13, 14-diamino dehydroabietic acid methyl ester comprises the following steps,
dissolving 12-bromo-13, 14-dinitrodehydroabietic acid methyl ester in ethanol, adding excessive iron powder, adding distilled water and concentrated hydrochloric acid, and carrying out reduction reaction under a heating condition, wherein petroleum ether: TLC monitoring is carried out on acetone 2:1, after the reaction is finished, ethyl acetate is used for extraction three times, water washing is carried out for three times, saturated sodium bicarbonate water solution and saturated salt water are respectively washed once, anhydrous sodium sulfate is dried, and vacuum spin drying is carried out to obtain oily crude 12-bromo-13, 14-diamino dehydroabietic acid methyl ester; wherein,
the dosage ratio of the 12-bromo-13, 14-dinitrodehydroabietic acid methyl ester to HFIP is 1g: 4-5 mL, the mass ratio of the 12-bromo-13, 14-dinitrodehydroabietic acid methyl ester to iron powder is 1: 1.2-1.3, and the dosage ratio of the 12-bromo-13, 14-dinitrodehydroabietic acid methyl ester to hydrochloric acid is 0.1-0.12 g:1 mL;
the dosage ratio of the 12-bromo-13, 14-dinitrodehydroabietic acid methyl ester to the distilled water is 1g: 44-46 mL;
the reduction temperature of the Fe/HCl is 40-50 ℃, and the reaction time is 2-3 h.
5. The method for preparing a dehydroabietic acid based quinoxaline mercury ion fluorescent probe according to claim 2, which is characterized in that: the 12-bromo-7, 10 a-dimethyl-2, 3-di (pyridin-2-yl) -5,6,6a,7,8,9,10,10 a-octahydronaphthalene [2,1-f ] quinoxalin-7-methyl ester is prepared by a process comprising,
dissolving 2, 2' -pyridone in ethanol, dissolving 12-bromo-13, 14-diamino dehydroabietic acid methyl ester in acetic acid, mixing an acetic acid-ethanol reaction system, performing reflux reaction at 85-95 ℃ for 12 hours under the protection of nitrogen, and performing petroleum ether: TLC monitoring was performed at 2:1, and after the reaction was completed, vacuum spin-drying, extraction three times with ethyl acetate, washing three times with water, extraction once each of saturated sodium carbonate solution and saturated brine, drying over anhydrous sodium sulfate, extraction with petroleum ether: purifying the ethyl acetate by a column at a ratio of 100:1-20:1 to obtain off-white solid 12-bromo-7, 10 a-dimethyl-2, 3-di (pyridin-2-yl) -5,6,6a,7,8,9,10,10 a-octahydronaphthalene [2,1-f ] quinoxaline-7-methyl ester; wherein,
the molar ratio of the 12-bromo-13, 14-diamino dehydroabietic acid methyl ester to the 2, 2' -pyridone is 1.1-1.2: 1.
6. The method for preparing a dehydroabietic acid based quinoxaline mercury ion fluorescent probe according to claim 2, which comprises the following steps: the preparation method of the 12- (4- (dimethylamino) phenyl) -7,10 a-dimethyl-2, 3-di (pyridine-2-yl) -5,6,6a,7,8,9,10,10 a-octahydronaphthalene [2,1-f ] quinoxaline-7-methyl ester comprises the following steps,
the 12-bromo-7, 10 a-dimethyl-2, 3-di (pyridine-2-yl) -5,6,6a,7,8,9,10,10 a-octahydronaphthalene [2,1-f ]]Dissolving quinoxaline-7-methyl ester in toluene and ethanol, and adding 4-dimethylamino phenylboronic acid and K2CO3Solution, pd (pph)3)4Carrying out reflux reaction for 12h at 80-100 ℃ under the protection of nitrogen, and carrying out TLC monitoring on petroleum ether and acetone in a ratio of 2: 1;
after the reaction is finished, the reaction product is dried in vacuum, extracted three times by ethyl acetate and washed three times by water, saturated sodium carbonate solution is extracted and extracted once by saturated saline water respectively, dried by anhydrous sodium sulfate and purified by petroleum ether and ethyl acetate which are 50:1-10:1 through a column, and pure orange-red solid 12- (4- (dimethylamino) phenyl) -7,10 a-dimethyl-2, 3-di (pyridine-2-yl) -5,6,6a,7,8,9,10,10 a-octahydronaphthalene [2,1-f ] quinoxaline-7-methyl ester is obtained.
7. The use of 12- (4- (dimethylamino) phenyl) -7,10 a-dimethyl-2, 3-di (pyridin-2-yl) -5,6,6a,7,8,9,10,10 a-octahydronaphthalene [2,1-f ] quinoxaline-7-methyl ester according to claim 1 as a fluorescent probe for the detection of mercury ions.
8. The use of claim 7, wherein: the 12- (4- (dimethylamino) phenyl) -7,10 a-dimethyl-2, 3-di (pyridine-2-yl) -5,6,6a,7,8,9,10,10 a-octahydronaphthalene [2,1-f ] quinoxaline-7-methyl ester is used as a fluorescent probe to carry out spectral reaction on the detected mercury ions, the fluorescent probe reduces the fluorescence intensity to quenching under the action of the mercury ions, the minimum detection limit on the mercury ions is as low as nM level, and the maximum detection limit reaches 10.3 nM.
9. The use of claim 7, wherein: the detection of the 12- (4- (dimethylamino) phenyl) -7,10 a-dimethyl-2, 3-di (pyridine-2-yl) -5,6,6a,7,8,9,10,10 a-octahydronaphthalene [2,1-f ] quinoxaline-7-methyl ester as a fluorescent probe to mercury ions is not interfered by other coexisting ions.
10. The use of claim 7, wherein: the application of the 12- (4- (dimethylamino) phenyl) -7,10 a-dimethyl-2, 3-di (pyridine-2-yl) -5,6,6a,7,8,9,10,10 a-octahydronaphthalene [2,1-f ] quinoxaline-7-methyl ester as a fluorescent probe in detecting mercury ions in environmental water samples and seafood is provided.
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