CN115611939A - Fluorescent probe for detecting fluorine ions and preparation method and application thereof - Google Patents
Fluorescent probe for detecting fluorine ions and preparation method and application thereof Download PDFInfo
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- -1 fluorine ions Chemical class 0.000 title claims abstract description 84
- 239000007850 fluorescent dye Substances 0.000 title claims abstract description 59
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 28
- 239000011737 fluorine Substances 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 42
- SMUQFGGVLNAIOZ-UHFFFAOYSA-N quinaldine Chemical compound C1=CC=CC2=NC(C)=CC=C21 SMUQFGGVLNAIOZ-UHFFFAOYSA-N 0.000 claims abstract description 28
- RGHHSNMVTDWUBI-UHFFFAOYSA-N 4-hydroxybenzaldehyde Chemical compound OC1=CC=C(C=O)C=C1 RGHHSNMVTDWUBI-UHFFFAOYSA-N 0.000 claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 90
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 claims description 45
- 125000005504 styryl group Chemical group 0.000 claims description 30
- 230000015572 biosynthetic process Effects 0.000 claims description 29
- 238000003786 synthesis reaction Methods 0.000 claims description 29
- 238000000034 method Methods 0.000 claims description 24
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 22
- 239000007787 solid Substances 0.000 claims description 18
- 239000002904 solvent Substances 0.000 claims description 17
- 238000001035 drying Methods 0.000 claims description 14
- 238000010521 absorption reaction Methods 0.000 claims description 13
- ZIZCWUNKNLIXMX-UHFFFAOYSA-N 4-(2-quinolin-2-ylethenyl)phenol Chemical compound C1=CC(O)=CC=C1C=CC1=CC=C(C=CC=C2)C2=N1 ZIZCWUNKNLIXMX-UHFFFAOYSA-N 0.000 claims description 12
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 12
- ZJVXXEFZKXBKPU-UHFFFAOYSA-N (4-bromophenoxy)-tert-butyl-diphenylsilane Chemical compound C=1C=CC=CC=1[Si](C=1C=CC=CC=1)(C(C)(C)C)OC1=CC=C(Br)C=C1 ZJVXXEFZKXBKPU-UHFFFAOYSA-N 0.000 claims description 10
- 239000013078 crystal Substances 0.000 claims description 10
- 238000001514 detection method Methods 0.000 claims description 10
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- 230000002194 synthesizing effect Effects 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 7
- 238000000967 suction filtration Methods 0.000 claims description 7
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 6
- 238000010992 reflux Methods 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- 238000004440 column chromatography Methods 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 238000012360 testing method Methods 0.000 claims description 4
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- 238000002425 crystallisation Methods 0.000 claims description 3
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- 239000000523 sample Substances 0.000 abstract description 19
- 230000035945 sensitivity Effects 0.000 abstract description 8
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 abstract description 7
- 239000002994 raw material Substances 0.000 abstract description 7
- 230000029936 alkylation Effects 0.000 abstract description 5
- 238000005804 alkylation reaction Methods 0.000 abstract description 5
- 238000002474 experimental method Methods 0.000 abstract description 5
- 238000006482 condensation reaction Methods 0.000 abstract description 4
- 238000010534 nucleophilic substitution reaction Methods 0.000 abstract description 4
- 229910018557 Si O Inorganic materials 0.000 abstract description 3
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 abstract description 3
- 238000001308 synthesis method Methods 0.000 abstract description 3
- 238000011160 research Methods 0.000 abstract description 2
- 238000006073 displacement reaction Methods 0.000 abstract 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract 1
- 238000000033 nuclear magnetic resonance titration Methods 0.000 abstract 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 abstract 1
- KTQKOGBTMNDCFG-UHFFFAOYSA-N tert-butyl(diphenyl)silicon Chemical compound C=1C=CC=CC=1[Si](C(C)(C)C)C1=CC=CC=C1 KTQKOGBTMNDCFG-UHFFFAOYSA-N 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 28
- 150000001450 anions Chemical class 0.000 description 20
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 18
- NZCHHEFOTMKOJX-UHFFFAOYSA-K [6-[[3-carboxy-4-(3-oxido-6-oxoxanthen-9-yl)phenyl]carbamothioylamino]hexoxy-oxidophosphoryl] [5-(2,4-dioxopyrimidin-1-yl)-3,4-dihydroxyoxolan-2-yl]methyl phosphate Chemical compound O1C(COP([O-])(=O)OP([O-])(=O)OCCCCCCNC(=S)NC=2C=C(C(=CC=2)C2=C3C=CC(=O)C=C3OC3=CC([O-])=CC=C32)C(O)=O)C(O)C(O)C1N1C=CC(=O)NC1=O NZCHHEFOTMKOJX-UHFFFAOYSA-K 0.000 description 10
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 8
- 238000002189 fluorescence spectrum Methods 0.000 description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 239000012265 solid product Substances 0.000 description 6
- 238000000862 absorption spectrum Methods 0.000 description 5
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 4
- 230000003247 decreasing effect Effects 0.000 description 4
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- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000007405 data analysis Methods 0.000 description 3
- 208000004042 dental fluorosis Diseases 0.000 description 3
- 230000005284 excitation Effects 0.000 description 3
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000000741 silica gel Substances 0.000 description 3
- 229910002027 silica gel Inorganic materials 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- VTORJPDWMOIOIQ-UHFFFAOYSA-N tert-butyl(diphenyl)silane Chemical compound C=1C=CC=CC=1[SiH](C(C)(C)C)C1=CC=CC=C1 VTORJPDWMOIOIQ-UHFFFAOYSA-N 0.000 description 3
- 238000002211 ultraviolet spectrum Methods 0.000 description 3
- 229910020366 ClO 4 Inorganic materials 0.000 description 2
- 206010016818 Fluorosis Diseases 0.000 description 2
- 239000007810 chemical reaction solvent Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 238000001917 fluorescence detection Methods 0.000 description 2
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- 238000010898 silica gel chromatography Methods 0.000 description 2
- 239000011550 stock solution Substances 0.000 description 2
- 238000004448 titration Methods 0.000 description 2
- KZMAWJRXKGLWGS-UHFFFAOYSA-N 2-chloro-n-[4-(4-methoxyphenyl)-1,3-thiazol-2-yl]-n-(3-methoxypropyl)acetamide Chemical compound S1C(N(C(=O)CCl)CCCOC)=NC(C=2C=CC(OC)=CC=2)=C1 KZMAWJRXKGLWGS-UHFFFAOYSA-N 0.000 description 1
- 208000001132 Osteoporosis Diseases 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000012491 analyte Substances 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
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- 229940079593 drug Drugs 0.000 description 1
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- 239000003480 eluent Substances 0.000 description 1
- 238000000295 emission spectrum Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001506 fluorescence spectroscopy Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000002156 mixing Methods 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
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 238000004451 qualitative analysis Methods 0.000 description 1
- 238000004445 quantitative analysis Methods 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
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 1
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- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
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- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
- C07F7/1872—Preparation; Treatments not provided for in C07F7/20
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- 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 relates to a fluorescent probe for detecting fluorine ions, a preparation method and application thereof, wherein the fluorescent probe is a fluorine ion fluorescent probe taking 2-methylquinoline as a fluorophore framework and-Si-O group as an action site. 2-methylquinoline is used as a fluorophore framework, p-hydroxybenzaldehyde is introduced through a condensation reaction to increase a conjugated surface, tert-butyl diphenyl silicon base (TBDPS) is introduced through nucleophilic substitution to protect active hydroxyl, water solubility and sensitivity are further improved through N alkylation, and a quaternary ammonium salt fluorescent probe based on a serial release reaction initiated by cutting a siloxane bond through fluorine ions is successfully designed. The technical researches such as ultraviolet, fluorescence and NMR titration experiments show that the probe can identify fluorine ions. The fluorescent probe of the invention has the advantages of simple and convenient synthesis method, simple and easily obtained raw materials, good selectivity to fluorine ions, higher sensitivity, large Stokes displacement and better prospect for detecting the fluorine ions.
Description
Technical Field
The invention relates to the technical field of fluorescent probes, in particular to a fluorescent probe for detecting fluorine ions and a preparation method and application thereof.
Background
The design and development of artificial anion receptors in supramolecular chemistry has attracted considerable attention. Anion recognition is an important branch of supramolecular chemistry and has important significance in the research fields of life science, medicine, environmental science and the like. Fluoride, as a minimum-volume and extremely electronegative anion, has a high charge density and unique chemical properties, and is widely found in living organisms and nature and occupies an irreplaceable position. Fluoride has important application in modern science and technology, and in the field of biomedicine, a small amount of fluoride ions can enhance the stability of the structure of teeth, protect the health of bones and teeth, and treat osteoporosis; and the excessive storage of the human body causes fluorosis, the light causes dental fluorosis, the serious causes fluorosis, and even completely loses the labor and the self-care ability of life.
In recent years, the anion fluorescent probe is widely applied due to good selective identification, high detection sensitivity, strong anti-interference capability and simple operation of the method. The main principle of detecting anions by using the fluorescent probe is that through special interaction between molecules, a receptor is specifically combined with a specific anion, so that the structure of the fluorescent molecule is changed, and finally, the quantitative and qualitative analysis of the anions is realized through the change of a fluorescent signal. At present, people have designed and synthesized many anionic fluorescent probes with potential application values, but most of the probes are complex to synthesize, high in cost and poor in selectivity. Therefore, the development of a fluorescent probe with high sensitivity and good selectivity for detecting fluorine ions is of great significance.
Quinoline fluorophores are often used in the fields of drug synthesis, optical materials and the like because the molecules have semi-rigid structures, contain nitrogen heterocycles, and have good water solubility. However, the quinoline fluorophore has the disadvantages of small conjugate plane, short excitation wavelength and the like, and the identification performance of detecting the analyte by using the quinoline fluorophore as the fluorescent probe is poor, so that the quinoline fluorophore cannot be directly used in the actual life.
Disclosure of Invention
The invention mainly aims to provide a fluorescent probe for detecting fluorine ions, a preparation method and application thereof, which can effectively solve the problems in the background technology.
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 surface, increase ultraviolet absorption wavelength and improve probe water solubility and sensitivity through further N alkylation.
In order to realize the purpose, the invention adopts the technical scheme that:
a fluorescent probe for detecting fluoride ions has a chemical name of 2- (4- ((4- ((tert-butyl diphenyl silyl) oxy) benzyl) oxy) styryl) -1-methylquinoline-1-iodonium; the structural formula is shown in figure 1.
Preferably, the preparation method of the fluorescent probe for detecting the fluoride ions is obtained by taking 2-methylquinoline, p-hydroxybenzaldehyde, 4-bromophenyloxy) (tert-butyl) diphenylsilane and methyl iodide as raw materials through condensation reaction, nucleophilic substitution and N alkylation, and the reaction flow is shown in FIG. 2;
the preparation method comprises the following steps:
(S1) synthesizing 4- (2- (2-quinolyl) ethenyl) phenol;
(S2) synthesizing 2- (4- (4- (tert-butyldiphenylsiloxy) benzyl) styryl) quinoline by using the 4- (2- (2-quinolyl) ethenyl) prepared in the step (S1) and a solvent;
(S3) synthesizing 2- (4- ((4- ((tert-butyldiphenylsilyl) oxy) benzyl) oxy) styryl) -1-methylquinoline-1-iodonium by using the 2- (4- (4- (tert-butyldiphenylsiloxy) benzyl) styryl) quinoline prepared in the step (S2) and a solvent.
Preferably, in the synthesis step of step (S1), p-hydroxybenzaldehyde is slowly added to 2-methylquinoline, the temperature is raised, the reaction time is 10 hours, and when a yellow solid appears, the heating is stopped and the reaction solution is cooled. After the reaction is finished, crystallization, filtration, washing and drying are carried out, and yellow powdery solid 4- (2- (2-quinolyl) vinyl) phenol is obtained.
Preferably, in the synthesis step of step (S1), the ratio of the amounts of 2-methylquinoline and p-hydroxybenzaldehyde added is 34.92mmol:41.90mmol.
Preferably, in the synthesis step of step (S1): and (3) carrying out reflux reaction for 10 hours, cooling after complete reaction, adding absolute ethyl alcohol into the reaction solution, carrying out suction filtration, and drying.
Preferably, in the synthesis step of step (S2), the 4- (2- (2-quinolyl) vinyl group prepared in step (S1) is dissolved in N, N-dimethylformamide as a solvent by stirring, potassium carbonate is added, reaction is carried out for 30min, then (4-bromophenoxy) (tert-butyl) diphenylsilane is added, reaction time is 3h, after the reaction is completed, acidification, washing, drying, reduced pressure distillation are carried out, and after column chromatography, white silk-like solid 2- (4- (4- (tert-butyldiphenylsiloxy) benzyl) styryl) quinoline is collected.
Preferably, in the synthesis step of step (S2), the ratio of the amounts of 4- (2- (2-quinolyl) vinyl) phenol, potassium carbonate, (4-bromophenoxy) (tert-butyl) diphenylsilane, and N, N-dimethylformamide added is 4.04mmol:6.07mmol:6.07mmol:25ml.
Preferably, in the synthesis step of step (S2), after completion of the reaction, the reaction mixture is washed with a saturated aqueous citric acid solution. Extracting with ethyl acetate, combining organic phases, drying an organic layer with anhydrous sodium sulfate, collecting a filtrate, concentrating, purifying by silica gel column chromatography, and purifying by petroleum ether: ethyl acetate = 30.
Preferably, in the synthesis step of step (S3), the 2- (4- (4- (tert-butyldiphenylsilyl) benzyl) styryl) quinoline prepared in step (S2) is dissolved in acetonitrile as a solvent, methyl iodide is added, after 30min of reaction, (4-bromophenyloxy) (tert-butyl) diphenylsilane is added, the temperature is slowly raised to a reflux state, and after the reaction is completed, the brown-red filamentous crystal 2- (4- ((4- ((tert-butyldiphenylsilyl) oxy) benzyl) oxy) styryl) -1-methylquinoline-1-iodonium is cooled, filtered, washed and dried.
Preferably, in the synthesis step of step (S3), the ratio of the amounts of methyl iodide, 2- (4- (4- (tert-butyldiphenylsiloxy) benzyl) styryl) quinoline, and acetonitrile to be added is 0.84mmol:0.17mmol:2mL.
Preferably, in the synthesis step of step (S3), after overnight reaction, a solid is precipitated, heating is stopped to naturally cool the reaction solution to room temperature, crystals are precipitated, a buchner funnel is used for suction filtration, the filter cake is washed with acetonitrile for 3 times, and the solid is dried.
Preferably, the fluorescent probe is used for detecting fluorine ions in an aqueous solution.
Preferably, when the ultraviolet absorption and fluorescence emission spectrometry is adopted for detection, the fluorescent probe is dissolved in a mixed solution of acetonitrile and water 9:1 to test the fluorine ions.
In summary, the invention includes at least one of the following beneficial technical effects:
1. the fluorescent probe prepared by the method takes 2-methylquinoline as a fluorophore, -Si-O group as an identification site, has ultraviolet absorption peaks at 405nm and 555nm in an ultraviolet spectrum under the condition that acetonitrile is used as a solvent, and is added with F - Thereafter, the absorption peak at 405nm decreased and the absorption peak at 555nm gradually increased. And when other anions are added, the ultraviolet absorption spectrum of the fluorescent probe is not obviously changed. In the fluorescence spectrum, 475nm is taken as an excitation wavelength, the maximum emission wavelength of the fluorescent probe is 530nm, and F is added - After that, the 563nm fluorescence emission peak was reduced and the fluorescence was quenched. Under the irradiation of 365nm ultraviolet lamp, the addition of F is observed - The fluorescence of the probe solution is quenched, the yellow-green fluorescence is changed into no fluorescence, and other anions are not changed;
2. the fluorescent probe provided by the invention has the advantages of simple and convenient synthesis method, simple and easily obtained raw materials, good selectivity to fluorine ions, higher sensitivity, large Stokes shift and good application prospect in the detection of the fluorine ions.
Drawings
FIG. 1 is a structural diagram of a fluorescent probe for detecting fluorine ions, a preparation method and an application thereof;
FIG. 2 is a reaction flow chart of a fluorescent probe for detecting fluorine ions, a preparation method and an application thereof according to the present invention;
FIG. 3 shows fluorescence emission spectra of the optical probe of the present invention (20 μ M) when different anions (500 mM) are added to acetonitrile and water (V/V = 9/1) solutions;
FIG. 4 is a photograph under UV irradiation of a fluorescent probe of the present invention (20. Mu.M) in acetonitrile and water (V/V = 9/1) with different anions (500 mM);
FIG. 5 shows fluorescence probes of the invention (20. Mu.M) in acetonitrile and water (V/V = 9/1) solutions at different F - UV absorption spectrum at concentration (0-18 mM);
FIG. 6 shows fluorescence probes of the invention (20. Mu.M) in acetonitrile and water (V/V = 9/1) solutions at different F - Fluorescence emission spectrum (. Lamda.) at a concentration of 0-18mM ex ＝457nm)；
FIG. 7 is a graph showing calculation of fluorescence detection limits of the fluorescent probe of the present invention in a solution of acetonitrile and water (V/V = 9/1);
FIG. 8 shows the fluorescent probe (20. Mu.M) of the present invention in the presence of other anions (500 mM) for F - (18 mM) histogram of change in fluorescence emission at 530nm in response.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention. In addition, for the convenience of description, the terms "upper", "lower", "left" and "right" are used to refer to the same direction as the upper, lower, left, right, etc. of the drawings, and the terms "first", "second", etc. are used for descriptive distinction and have no special meaning.
The names, specifications, and manufacturer information of the raw materials used in the examples of the present invention are shown in table 1.
Table 1 raw material information table
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, manufactured by Beijing Union glass instruments Ltd.
Example 1
Referring to fig. 1-8, a fluorescent probe for detecting fluoride ions, a preparation method and an application thereof are disclosed, wherein the chemical name of the fluorescent probe is 2- (4- ((4- ((tert-butyl diphenyl silyl) oxy) benzyl) oxy) styryl) -1-methylquinoline-1-iodonium.
A method for preparing a fluorescent probe for detecting fluoride ions is prepared by taking 2-methylquinoline, p-hydroxybenzaldehyde, 4-bromophenyloxy) (tert-butyl) diphenylsilane and methyl iodide as raw materials through condensation reaction, nucleophilic substitution and N alkylation, wherein the reaction flow is shown in figure 2;
the preparation method comprises the following steps:
(S1) synthesizing 4- (2- (2-quinolyl) ethenyl) phenol;
(S2) synthesizing 2- (4- (4- (tert-butyldiphenylsiloxy) benzyl) styryl) quinoline by using the 4- (2- (2-quinolyl) ethenyl) prepared in the step (S1) and a solvent;
(S3) synthesizing 2- (4- ((4- ((tert-butyldiphenylsilyl) oxy) benzyl) oxy) styryl) -1-methylquinoline-1-iodonium by using the 2- (4- (4- (tert-butyldiphenylsiloxy) benzyl) styryl) quinoline prepared in the step (S2) and a solvent.
In the synthesis procedure of the step (S1), p-hydroxybenzaldehyde is slowly added into 2-methylquinoline, the temperature is raised, the reaction time is 10 hours, and when yellow solid appears, the heating is stopped to cool the reaction liquid. After the reaction is finished, crystallization, filtration, washing and drying are carried out, and yellow powdery solid 4- (2- (2-quinolyl) vinyl) phenol is obtained.
In the synthesis step of step (S1), the ratio of the added amounts of 2-methylquinoline and p-hydroxybenzaldehyde is 34.92mmol:41.90mmol.
In the synthesis step of step (S1): and (3) carrying out reflux reaction for 10 hours, cooling after complete reaction, adding absolute ethyl alcohol into the reaction solution, carrying out suction filtration, and drying.
And (S2) in the synthesis procedure of the step (S2), stirring and dissolving the 4- (2- (2-quinolyl) vinyl group prepared in the step (S1) in a solvent N, N-dimethylformamide, adding potassium carbonate, reacting for 30min, adding (4-bromophenyloxy) (tert-butyl) diphenylsilane, reacting for 3h, after the reaction is completed, acidifying, washing, drying, distilling under reduced pressure, and carrying out column chromatography to collect white silk-like solid 2- (4- (4- (tert-butyldiphenylsiloxy) benzyl) styryl) quinoline.
In the synthesis step of step (S2), the ratio of the amounts of 4- (2- (2-quinolyl) vinyl) phenol, potassium carbonate, (4-bromophenyloxy) (tert-butyl) diphenylsilane, and N, N-dimethylformamide added was 4.04mmol:6.07mmol:6.07mmol:25ml.
In the synthesis step of step (S2), after completion of the reaction, the reaction mixture is washed with a saturated citric acid aqueous solution. Extracting with ethyl acetate, combining organic phases, drying an organic layer with anhydrous sodium sulfate, collecting a filtrate, concentrating, purifying by silica gel column chromatography, and purifying by petroleum ether: ethyl acetate = 30.
In the synthesis procedure of the step (S3), the 2- (4- (4- (tert-butyldiphenylsilyl) benzyl) styryl) quinoline prepared in the step (S2) is dissolved in acetonitrile serving as a solvent, methyl iodide is added, after the reaction is carried out for 30min, (4-bromophenoxy) (tert-butyl) diphenylsilane is added, the temperature is slowly raised to a reflux state, after the reaction is completed, the mixture is cooled, filtered, washed and dried, and the brownish red filamentous crystal 2- (4- ((4- ((tert-butyldiphenylsilyl) oxy) benzyl) oxy) styryl) -1-methylquinoline-1-iodonium is obtained.
In the synthesis step of step (S3), the ratio of the amounts of methyl iodide, 2- (4- (4- (tert-butyldiphenylsiloxy) benzyl) styryl) quinoline, and acetonitrile added was 0.84mmol:0.17mmol:2mL.
And (S3) in the synthesis procedure, after overnight reaction, precipitating a solid, stopping heating to naturally cool the reaction solution to room temperature, precipitating crystals, performing suction filtration by using a Buchner funnel, washing a filter cake for 3 times by using acetonitrile, and drying the solid.
The fluorescent probe is applied to detecting fluorine ions in an aqueous solution.
When the detection is carried out by adopting an ultraviolet absorption and fluorescence emission spectrometry, the fluorescent probe is dissolved in a mixed solution of acetonitrile and water 9:1 to test fluorine ions.
The fluorescent probe prepared by the method takes 2-methylquinoline as a fluorophore and takes a-Si-O group as a recognition site, under the condition that acetonitrile is taken as a solvent, the fluorescent probe has ultraviolet absorption peaks at 405nm and 555nm in an ultraviolet spectrum, after F-is added, the absorption peak at 405nm is reduced, and the absorption peak at 555nm is gradually increased. And when other anions are added, the ultraviolet absorption spectrum of the fluorescent probe is not obviously changed. In a fluorescence spectrum, 475nm is taken as an excitation wavelength, the maximum emission wavelength of the fluorescent probe is 530nm, and after F-is added, 563nm fluorescence emission peak is reduced and fluorescence is quenched. Under the irradiation of an ultraviolet lamp at 365nm, the fluorescence quenching of the probe solution after the F-is added is observed, the yellow-green fluorescence is changed into non-fluorescence, and other anions are not changed.
The fluorescent probe provided by the invention has the advantages of simple and convenient synthesis method, simple and easily obtained raw materials, good selectivity to fluorine ions, higher sensitivity, large Stokes shift and good application prospect in the detection of the fluorine ions.
Example 2
As shown in fig. 1 to 8, a fluorescent probe for detecting fluoride ions according to an embodiment of the present invention, a method for preparing the same, and applications thereof:
1. synthesis of fluorescent probe molecule 1 for detecting fluorine ions
The invention relates to synthesis of a fluorescent probe molecule for detecting fluoride ions, which is prepared from 2-methylquinoline, p-hydroxybenzaldehyde, 4-bromophenyloxy) (tert-butyl) diphenylsilane and methyl iodide through condensation reaction, nucleophilic substitution and N alkylation.
(1) Synthesis of 4- (2- (2-quinolyl) vinyl) phenol:
in a 50mL single neck round bottom flask, 2-methylquinoline (5.00g, 34.92mmol) was added, parahydroxybenzaldehyde (5.12g, 41.90mmol) was slowly added, the temperature was raised to 120 ℃, and TCL followed the progress of the reaction. After the reaction is finished after 10 hours, when yellow solid appears, stopping heating and cooling the reaction liquid. Adding absolute ethyl alcohol into the reaction solution, carrying out suction filtration by using a Buchner funnel, washing a filter cake for 3 times by using 15mL of absolute ethyl alcohol, and drying to obtain a yellow powdery solid (7.52g, 87%);
the yellow powdery solid product obtained above was measured by means of a nuclear magnetic resonance instrument (Bruker AVANCE III500 MHz) and the data are as follows:
1H-NMR(400MHz,DMSO-d6),δ[ppm]:8.30(d,J＝8.4Hz,1H),7.95(d,J＝8.4Hz,1H),7.91(d,J＝7.6Hz,1H),7.81(d,J＝8.4Hz,1H),7.76-7.70(m,2H),7.57(d,J＝8.4Hz,2H),7.52(t,J＝7.4Hz,1H),7.25(d,J＝8.2Hz,1H),6.82(d,J＝8.8Hz,2H)；13C-NMR(101MHz,DMSO-d6),δ[ppm]:158.81,156.62,148.17,136.78,134.76,130.21,129.38,128.97,128.25,127.78,127.30,126.32,125.85,120.18,116.23.
the result of nuclear magnetic resonance spectrum data analysis of the yellow powdery solid product obtained above shows that the yellow powdery solid product obtained above is 4- (2- (2-quinolyl) ethenyl) phenol.
(2) Synthesis of 2- (4- (4- (tert-butyldiphenylsiloxy) benzyl) styryl) quinoline:
to a 50mL single neck round bottom flask was added 25mL of N, N-Dimethylformamide (DMF) as a reaction solvent, 4- (2- (2-quinolyl) vinyl) phenol (1.00g, 4.04mmol) was added, and after stirring at room temperature for 5min, K was added 2 CO 3 (0.84g, 6.07mmol), and after 30min of reaction, (4-bromophenoxy) (tert-butyl) diphenylsilane (2.58g, 6.07mmol) was slowly added to the single-necked flask, the reaction was stirred at room temperature, and TCL followed the progress of the reaction. After the reaction is finished after 3h, adding a saturated citric acid aqueous solution into the reaction solution, adjusting the pH value to be acidic, extracting with ethyl acetate, extracting the aqueous phase for multiple times, combining the organic phases, washing with a large amount of saturated saline solution for 3 times, drying the organic phase with anhydrous sodium sulfate, concentrating by reduced pressure distillation, mixing with silica gel, and purifying by column chromatography (eluent is petroleum ether: ethyl acetate =30: 1) to obtain a white silk-like solid (0.25g, 10%).
The white silk-like solid product obtained above was measured by a nuclear magnetic resonance apparatus (Bruker AVANCE III500 MHz), and the data are as follows:
1H-NMR(400MHz,CDCl3),δ[ppm]:8.09(t,J＝10.0Hz,2H),7.78-7.62(m,8H),7.57(d,J＝8.0Hz,2H),7.50-7.36(m,8H),7.18(d,J＝8.0Hz,2H),6.97(d,J＝8.0Hz,2H),6.80(d,J＝7.6Hz,2H),4.95(s,2H),1.12(s,9H)；13C-NMR(101MHz,CDCl3),δ[ppm]:159.46,156.39,155.58,148.33,136.27,135.56,134.12,132.86,129.97,129.71,129.14,128.99,128.65,127.84,127.51,125.98,119.85,119.21,115.21,69.97,26.56,19.50.HRMS-ESI:m/z Calcd for C40H38NO2Si+[M+H]+:592.2666；Found:592.2663.
the result of the nuclear magnetic resonance spectrum data analysis of the white silk-like solid product obtained in the above way shows that the white silk-like solid product obtained in the above way is 2- (4- (4- (tert-butyl diphenyl siloxy) benzyl) styryl) quinoline.
(3) Synthesis of 2- (4- ((4- ((tert-butyldiphenylsilyl) oxy) benzyl) oxy) styryl) -1-methylquinolin-1-ium iodide:
2mL of acetonitrile was added as a reaction solvent to a 10mL sealed tube, 2- (4- (4- (tert-butyldiphenylsiloxy) benzyl) styryl) quinoline (0.10g, 0.17mmol) was added, the mixture was stirred at room temperature for 10min to dissolve, methyl iodide (0.12g, 0.84mmol) was added, the temperature was slowly raised to reflux, and TCL followed the progress of the reaction. After overnight reaction, a brownish red solid is precipitated, heating is stopped, the reaction solution is naturally cooled to room temperature, a large amount of brownish red filamentous crystals are precipitated, a Buchner funnel is used for suction filtration, a filter cake is washed for 3 times by 5mL of acetonitrile, and the solid is dried to obtain the brownish red filamentous crystals, namely 2- (4- ((4- ((tert-butyldiphenylsilyl) oxy) benzyl) oxy) styryl) -1-methylquinoline-1-iodonium (0.07g, 68%).
The red brown filamentous crystal product obtained above was measured by a nuclear magnetic resonance instrument (Bruker AVANCE III MHz) and the data are as follows:
1H-NMR(400MHz,DMSO-d6),δ[ppm]:8.99(d,J＝9.2Hz,1H),8.54-8.51(m,2H),8.32(d,J＝7.6Hz,1H),8.20-8.14(m,2H),7.95-7.91(m,3H),7.77(d,J＝16.0Hz,1H),7.68(d,J＝6.8Hz,4H),7.51-7.42(m,6H),7.26(d,J＝8.4Hz,2H),7.14(d,J＝8.8Hz,2H),6.77(d,J＝8.4Hz,2H),5.05(s,2H),4.53(s,3H),1.05(s,9H)；13C-NMR(101MHz,DMSO-d6),δ[ppm]:161.80,156.85,155.37,147.56,144.17,139.68,135.52,135.26,132.51,131.82,130.77,130.52,130.12,129.70,129.30,128.57,128.05,121.31,119.80,119.69,117.10,115.94,115.14,69.80,40.20,26.80,19.43.HRMS-ESI:m/z Calcd for C41H40NO2Si+[M-I]+:606.2823；Found:606.2831.
the result of the nuclear magnetic resonance spectrum data analysis of the obtained brownish red filamentous crystal product shows that the obtained brownish red filamentous crystal product is 2- (4- ((4- ((tert-butyl diphenyl silyl) oxy) benzyl) oxy) styryl) -1-methylquinoline-1-iodonium.
2. Fluorescent probe 1 for detecting fluorine ions and identification performance of anions
1. Selective study of fluorescent probes for fluoride ions
The results showed that probe 1 had only F under acetonitrile/water (v: v = 9:1) as the solvent - The added probe solution showed yellow-green fluorescence quenching and the fluorescence emission peak at 530nm decreased, while the fluorescence emission spectrum and the solution fluorescence color did not change with the addition of other anions (FIGS. 3-4). The fluorescent probe can specifically detect the fluorine ions.
2. Fluorescent probe titration experiment of fluoride ion
The results show that the ultraviolet absorption spectrum of the fluorescent probe 1 is influenced by the concentration of the fluorine ions (figure 5), the fluorescent probe has ultraviolet absorption peaks at 405nm and 555nm in the ultraviolet spectrum along with the gradual addition of the fluorine ions, and F is added - Thereafter, the absorption peak at 405nm decreased and the absorption peak at 555nm increased gradually until 18mM F was added - Equilibrium is reached. Then, the fluorescence emission spectrum was measured (FIG. 6), and the fluorescence emission peak of the fluorescent probe 1 at 530nm was decreased until 18mM F was added - Equilibrium is reached.
3. Determination of fluorine ion minimum detection limit by fluorescent probe 1
For fluorescence emission intensity at 530nm and F - The concentration has good linear relation (R) 2 Up to 0.96676). The probe 1 in CH was calculated by the formula LOD =3 × δ/S 3 CN/H 2 The fluorescence detection limit for fluoride ions in the O (v: v = 9:1) mixed solvent was 2.37. Mu.M (FIG. 7). Where δ and S in the formula represent the standard deviation and slope, respectively, of the fitted curve. This indicates that probe fluorescent probe 1 is paired with F in acetonitrile - Has better sensitivity.
4. Detection of interference rejection
25mL of 20. Mu.M CH 3 CN/H 2 The probe solution of O (v: v = 9:1) was poured into 11 tubes of 15mL each of 5mL, and 500mM of a different anion (F) was added to each tube - ,CN - ,OH - ,AcO - ,H 2 PO 4 - ,Cl - ,Br - ,I - ,HSO 4 - ,NO 3 - ,BF 4 - ,ClO 4 - ) Shaking thoroughly, detecting fluorescence emission spectrum, adding 18mM fluoride ion into each test tube, shaking, and detecting againFluorescence emission spectrum.
Experiments have shown that F in the coexistence with other anions - The fluorescence intensity of the fluorescent probe 1 at 530nm can still be obviously reduced (FIG. 8), so that the fluorescent probe 1 is opposite to F - The detection has good anti-interference capability, and other anions can not bring any interference to the detection result.
The foregoing shows and describes the general principles and broad features of the present invention and advantages thereof. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (10)
1. A fluorescent probe for detecting fluorine ions is characterized in that the chemical name of the fluorescent probe is as follows: 2- (4- ((4- ((tert-butyldiphenylsilyl) oxy) benzyl) oxy) styryl) -1-methylquinolin-1-ium iodide.
2. The method for preparing the fluorescent probe for detecting the fluoride ions according to claim 1, which comprises the following steps:
(S1) synthesizing 4- (2- (2-quinolyl) ethenyl) phenol;
(S2) synthesizing 2- (4- (4- (tert-butyldiphenylsiloxy) benzyl) styryl) quinoline by using the 4- (2- (2-quinolyl) ethenyl) prepared in the step (S1) and a solvent;
(S3) synthesizing 2- (4- ((4- ((tert-butyldiphenylsilyl) oxy) benzyl) oxy) styryl) -1-methylquinoline-1-iodonium by using the 2- (4- (4- (tert-butyldiphenylsiloxy) benzyl) styryl) quinoline prepared in the step (S2) and a solvent.
3. The method for preparing a fluorescent probe for detecting fluoride ions according to claim 2, wherein the method comprises the following steps: in the synthesis process of the step (S1), p-hydroxybenzaldehyde is slowly added into 2-methylquinoline, the temperature is raised, the reaction time is 10 hours, and when yellow solid appears, the heating is stopped to cool the reaction liquid. After the reaction is finished, crystallization, filtration, washing and drying are carried out, and yellow powdery solid 4- (2- (2-quinolyl) vinyl) phenol is obtained.
4. The method for preparing a fluorescent probe for detecting fluoride ions according to claim 2, wherein the method comprises the following steps: in the synthesis step of the step (S1), the ratio of the addition amounts of 2-methylquinoline and p-hydroxybenzaldehyde is 34.92mmol:41.90mmol.
5. The method for preparing a fluorescent probe for detecting fluoride ions according to claim 2, wherein the method comprises the following steps: in the synthesis procedure of the step (S2), 4- (2- (2-quinolyl) vinyl) prepared in the step (S1) is stirred and dissolved in a solvent N, N-dimethylformamide, potassium carbonate is added, reaction is carried out for 30min, then (4-bromophenoxy) (tert-butyl) diphenylsilane is added, reaction time is 3h, after complete reaction, acidification, washing, drying and reduced pressure distillation are carried out, and white silk-like solid 2- (4- (4- (tert-butyldiphenylsiloxy) benzyl) styryl) quinoline is obtained after column chromatography is carried out.
6. The method for preparing a fluorescent probe for detecting fluoride ions according to claim 2, wherein the method comprises the following steps: in the synthesis step of step (S2), the ratio of the amounts of 4- (2- (2-quinolyl) vinyl) phenol, potassium carbonate, (4-bromophenoxy) (tert-butyl) diphenylsilane, and N, N-dimethylformamide added is 4.04mmol:6.07mmol:6.07mmol:25ml.
7. The method for preparing a fluorescent probe for detecting fluoride ions according to claim 2, wherein the method comprises the following steps: in the step (S3), the 2- (4- (4- (tert-butyldiphenylsiloxy) benzyl) styryl) quinoline prepared in the step (S2) is dissolved in acetonitrile as a solvent, methyl iodide is added, reaction is carried out for 30min, then (4-bromophenoxy) (tert-butyl) diphenylsilane is added, the temperature is slowly raised to a reflux state, after the reaction is completed, cooling, suction filtration, washing and drying are carried out, and the brownish red filamentous crystal 2- (4- ((4- ((tert-butyldiphenylsilyl) oxy) benzyl) oxy) styryl) -1-methylquinoline-1-iodonium is obtained.
8. The method for preparing a fluorescent probe for detecting fluoride ions according to claim 2, wherein the method comprises the following steps: in the synthesis step of step (S3), the ratio of the amounts of methyl iodide, 2- (4- (4- (tert-butyldiphenylsiloxy) benzyl) styryl) quinoline, and acetonitrile added is 0.84mmol:0.17mmol:2mL.
9. The use of a fluorescent probe for detecting fluoride ions according to claim 1, wherein: the fluorescent probe is applied to detecting fluorine ions in an aqueous solution.
10. The use of a fluorescent probe for detecting fluoride ions according to claim 9, wherein: when the detection is carried out by adopting an ultraviolet absorption and fluorescence emission spectrometry, the fluorescent probe is dissolved in a mixed solution of acetonitrile and water 9:1 to test fluorine ions.
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