CN108864162B - BODIPY-based fluorescent probe containing 2, 2' -dipyridine amine and synthetic method and application thereof - Google Patents
BODIPY-based fluorescent probe containing 2, 2' -dipyridine amine and synthetic method and application thereof Download PDFInfo
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- 239000007850 fluorescent dye Substances 0.000 title claims abstract description 22
- 238000010189 synthetic method Methods 0.000 title description 4
- -1 2, 2' -dipyridine amine Chemical class 0.000 title description 2
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 18
- HMMPCBAWTWYFLR-UHFFFAOYSA-N n-pyridin-2-ylpyridin-2-amine Chemical compound C=1C=CC=NC=1NC1=CC=CC=N1 HMMPCBAWTWYFLR-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000001514 detection method Methods 0.000 claims abstract description 10
- 150000001875 compounds Chemical class 0.000 claims description 53
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical group CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 30
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 24
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 24
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 24
- 239000012043 crude product Substances 0.000 claims description 20
- 239000002904 solvent Substances 0.000 claims description 20
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 12
- 239000003480 eluent Substances 0.000 claims description 12
- 238000001704 evaporation Methods 0.000 claims description 12
- 238000001914 filtration Methods 0.000 claims description 11
- 239000003054 catalyst Substances 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- 238000004440 column chromatography Methods 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- 239000000706 filtrate Substances 0.000 claims description 8
- 239000003208 petroleum Substances 0.000 claims description 8
- 239000000741 silica gel Substances 0.000 claims description 8
- 229910002027 silica gel Inorganic materials 0.000 claims description 8
- 239000012295 chemical reaction liquid Substances 0.000 claims description 7
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 7
- CSNNHWWHGAXBCP-UHFFFAOYSA-L magnesium sulphate Substances [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- 238000001308 synthesis method Methods 0.000 claims description 5
- 239000000945 filler Substances 0.000 claims description 4
- 238000000746 purification Methods 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 4
- 229910021595 Copper(I) iodide Inorganic materials 0.000 claims description 3
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 claims description 3
- YNHIGQDRGKUECZ-UHFFFAOYSA-N dichloropalladium;triphenylphosphanium Chemical compound Cl[Pd]Cl.C1=CC=CC=C1[PH+](C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1[PH+](C=1C=CC=CC=1)C1=CC=CC=C1 YNHIGQDRGKUECZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 239000012046 mixed solvent Substances 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 230000002194 synthesizing effect Effects 0.000 claims 1
- 239000000523 sample Substances 0.000 abstract description 4
- 230000035945 sensitivity Effects 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 2
- 238000010791 quenching Methods 0.000 abstract description 2
- 230000000171 quenching effect Effects 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 13
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 10
- 239000012074 organic phase Substances 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 229910052786 argon Inorganic materials 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 238000002189 fluorescence spectrum Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical class OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- ICSNLGPSRYBMBD-UHFFFAOYSA-N 2-aminopyridine Chemical compound NC1=CC=CC=N1 ICSNLGPSRYBMBD-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 150000007960 acetonitrile Chemical class 0.000 description 1
- 238000000559 atomic spectroscopy Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000012496 blank sample Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 238000006862 quantum yield reaction Methods 0.000 description 1
- 238000010223 real-time analysis Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000002798 spectrophotometry method Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
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Abstract
The invention designs and synthesizes the BODIPY-based fluorescent probe containing 2, 2' -dipyridyl amine shown in the formula (N1), and the BODIPY-based fluorescent probe is applied to the detection of metal ions, and compared with a plurality of quenching fluorescent probes, the fluorescent probe belongs to an enhanced fluorescent probe and has higher sensitivity in terms of detection effect, in addition, the effective detection of a plurality of metal ions is realized, and the efficiency and the utilization rate of the probe are improved;
Description
(I) technical field
The invention relates to a BODIPY-based fluorescent probe containing 2, 2' -dipyridyl amine, a synthetic method thereof and application thereof in metal ion detection.
(II) background of the invention
The excessive heavy metal ions can cause great harm to the environment and human bodies, so that it is necessary to research how to detect the ions efficiently and reliably.
Compared with traditional methods such as coordination titration, spectrophotometry, atomic spectrometry and the like, the fluorescence probe method is gradually becoming one of the most important methods for detecting ions due to its fast response to analytes, high sensitivity, simplicity, real-time analysis, low cost and simple detection process [ chem.Soc.Rev.2012,41,4511-4535 ], [ chem.Rev.2015,115,11718-11940 ], [ J.Am.chem.Soc.2017,139,5067-5074 ].
The 4, 4-difluoro-4-boron-3 a,4 a-diaza-s-indacene (BODIPY) derivatives have a great deal of unique advantages, such as high absorption coefficient and fluorescence quantum yield, narrow absorption and emission bands, multiple modification sites, etc. [ J.Org.Chem.2006,71,2881- & 2884 ], [ Sens.Actuator B: Chem.2017,253,1194-1198 ] ], [ J.Mater.Chem.B 2016,4,7549- & 7559 ] ], [ J.Am.Chem.Soc.2006,128,10-11 ] ], [ Angew.Chem.int.Ed.2008,47,8025- & 8029 ] ], [ J.Am.Chem.Soc.130, 130,16160-16161 ], and thus have a great prospect for the research on the synthesis and construction of BODIPY derivatives and fluorescent probes.
Disclosure of the invention
The invention aims to provide a novel BODIPY-based fluorescent probe containing 2, 2' -dipyridyl amine, a synthetic method thereof and application thereof in metal ion detection.
The technical scheme of the invention is as follows:
a BODIPY-based fluorescent probe containing 2, 2' -dipyridyl amine represented by formula (N1):
the synthesis method of the BODIPY-based fluorescent probe containing 2, 2' -dipyridyl amine shown in the formula (N1) comprises the following steps:
(1) mixing a compound shown as a formula (I), a compound shown as a formula (II), a catalyst and a solvent under anhydrous and anaerobic conditions, reacting for 12-24 h at 30-60 ℃, and then carrying out post-treatment on a reaction solution to obtain a compound shown as a formula (III);
the mass ratio of the compound represented by the formula (I) to the compound represented by the formula (II) is 1: 1-2, preferably 1: 1.5;
the amount of the catalyst substance is 5-20%, preferably 16% of the amount of the compound represented by the formula (I);
the volume dosage of the solvent is 100-250 mL/g based on the mass of the compound shown in the formula (I);
the solvent is anhydrous tetrahydrofuran and triethylamine in a volume ratio of 200-300: 1 (preferably 250: 1);
the catalyst is prepared by mixing bis (triphenylphosphine) palladium dichloride and cuprous iodide according to the mass ratio of 1-5: 1 (preferably 1: 1);
the anhydrous and anaerobic condition can be, for example, freezing and pumping the reaction liquid by using liquid nitrogen, then unfreezing and filling nitrogen, and repeating for three times;
the post-treatment method comprises the following steps: after the reaction is finished, cooling the reaction liquid to room temperature (20-30 ℃), filtering to remove the catalyst, extracting with dichloromethane, and extracting the extract with anhydrous MgSO4Drying, filtering, evaporating the filtrate to remove the solvent to obtain a crude product, and performing column chromatography separation and purification on the crude product, wherein 200-mesh and 300-mesh silica gel is used as a filler, and the volume ratio of petroleum ether to ethyl acetate is 4:1 as eluent, collecting eluent containing a target compound, evaporating the solvent and drying to obtain a compound shown as a formula (III);
(2) under the protection of inert gas (such as argon), dissolving the compound shown in the formula (III) obtained in the step (1) and the compound shown in the formula (IV) in an organic solvent, reacting for 6-24 h at 20-90 ℃, and then carrying out post-treatment on a reaction solution to obtain a compound shown in the formula (N1);
the mass ratio of the compound shown in the formula (III) to the compound shown in the formula (IV) is 1: 1-3, preferably 1: 2;
the volume dosage of the organic solvent is 100-200 mL/g based on the mass of the compound shown in the formula (III);
the organic solvent is acetonitrile and triethylamine in a volume ratio of 20-50: 1 (preferably 25: 1);
the post-treatment method comprises the following steps: after the reaction is finished, cooling the reaction liquid to room temperature (20-30 ℃), extracting the reaction liquid by dichloromethane, and extracting the extract by anhydrous MgSO4Drying, filtering, evaporating the filtrate to remove the solvent to obtain a crude product, and performing column chromatography separation and purification on the crude product, wherein 200-mesh and 300-mesh silica gel is used as a filler, and the volume ratio of petroleum ether to ethyl acetate is 4:1 as an eluent, collecting the eluent containing the target compound, evaporating the solvent and drying to obtain the compound shown as the formula (N1).
The compound shown in the formula (N1) prepared by the invention can be used as a fluorescent probe for detecting metal ions.
The invention has the beneficial effects that: a novel BODIPY-based fluorescent probe containing pyridylamine is designed and synthesized, and is applied to detection of metal ions, and compared with a plurality of quenching fluorescent probes, the fluorescent probe belongs to an enhanced fluorescent probe and has higher sensitivity in terms of detection effect, effective detection of various metal ions is realized, and the efficiency and the utilization rate of the probe are improved.
(IV) description of the drawings
FIG. 1 is a nuclear magnetic resonance hydrogen spectrum of compound N1 (deuterated acetonitrile is used as solvent);
FIG. 2 is a NMR carbon spectrum of compound N1 (deuterated chloroform as solvent);
FIG. 3 is a high resolution mass spectrum of compound N1;
FIG. 4 is a graph showing the UV absorption spectrum of compound N1 in example 4 mixed with different metal ions;
FIG. 5 shows fluorescence emission spectra of compound N1 mixed with different metal ions in example 5.
(V) detailed description of the preferred embodiments
The invention will be further described with reference to specific examples, but the scope of the invention is not limited thereto.
Example 1
(1) Preparation of the compound of formula (III):
a50 mL two-necked round bottom flask, plus spherical condenser, was charged with compound of formula (I) (130mg,0.37mmol) and compound of formula (II) (64mg,0.4mmol), bis (triphenylphosphine) palladium dichloride (21.1mg,0.03mmol) and cuprous iodide (5.7mg,0.03mmol), evacuated on two rows of tubes and air replaced with argon, and cycled three times for anhydrous oxygen-free treatment. A mixed solvent of 25mL of ultra-dry tetrahydrofuran and 100. mu.L of triethylamine was injected into a reaction flask using a steel needle, and the mixture was heated to 60 ℃ to react for 24 hours.
And (3) post-treatment: stopping heating, cooling the reaction system, filtering to remove catalyst, extracting with dichloromethane, collecting lower organic phase and water phaseExtracting for several times, combining organic phases, washing the organic phase with water, and then using anhydrous MgSO4Drying, filtering, evaporating to remove the solvent of the filtrate to obtain a crude product, separating and purifying the crude product by column chromatography, wherein the crude product is 200-300-mesh silica gel, and the eluent is a mixed solution of petroleum ether and ethyl acetate in a volume ratio of 4: 1. 45.6mg of a violet-black solid compound of the formula (III) was obtained, which showed substantially no hetero-peaks in the hydrogen spectrum and a yield of 26%.
(2) Preparation of a compound of formula N1:
a50 mL round-bottom flask was purged of air with argon, to which was added a compound of formula (III) (131mg,0.28mmol) and 2, 2' -dipyridylamine (71.82mg,0.42mmol), 20mL of acetonitrile to triethylamine in a volume ratio of 20: 1 for 6 hours at room temperature.
And (3) post-treatment: stopping heating, cooling the reaction system, extracting with dichloromethane, collecting lower organic phase, extracting water phase for several times, mixing organic phases, washing with water, and adding anhydrous MgSO4Drying, filtering, evaporating to remove the solvent of the filtrate to obtain a crude product, separating and purifying the crude product by column chromatography, wherein the crude product is 200-300-mesh silica gel, and the eluent is a mixed solution of petroleum ether and ethyl acetate in a volume ratio of 4: 1. 26.4mg of N1 solid compound was obtained in red color, and the hydrogen spectrum was substantially free of hetero peaks at a yield of 15%.
Example 2
Step (1) As in step (1) of example 1
(2) A50 mL round-bottom flask was purged of air with argon, to which was added a compound of formula (III) (131mg,0.28mmol) and 2, 2' -dipyridylamine (71.82mg,0.42mmol), 20mL acetonitrile to triethylamine in a volume ratio of 50: 1, heating to 90 ℃ and reacting for 6 hours.
And (3) post-treatment: stopping heating, cooling the reaction system, extracting with dichloromethane, collecting lower organic phase, extracting water phase for several times, mixing organic phases, washing with water, and adding anhydrous MgSO4Drying, filtering, evaporating to remove the solvent of the filtrate to obtain a crude product, separating and purifying the crude product by column chromatography, wherein the crude product is 200-300-mesh silica gel, and the eluent is a mixed solution of petroleum ether and ethyl acetate in a volume ratio of 4: 1. Red N1 solidification was obtained42.3mg of compound, substantially free of hetero-peaks in the hydrogen spectrum, in 24% yield.
Example 3
Step (1) As in step (1) of example 1
(2) A50 mL round-bottom flask was purged of air with argon, to which was added a compound of formula (III) (131mg,0.28mmol) and 2, 2' -dipyridylamine (71.82mg,0.42mmol), 20mL acetonitrile to triethylamine in a volume ratio of 25: 1, heating to 90 ℃ and reacting for 24 hours.
And (3) post-treatment: stopping heating, cooling the reaction system, extracting with dichloromethane, collecting lower organic phase, extracting water phase for several times, mixing organic phases, washing with water, and adding anhydrous MgSO4Drying, filtering, evaporating to remove the solvent of the filtrate to obtain a crude product, separating and purifying the crude product by column chromatography, wherein the crude product is 200-300-mesh silica gel, and the eluent is a mixed solution of petroleum ether and ethyl acetate in a volume ratio of 4: 1. 47.6mg of N1 solid was obtained in a red color, and the hydrogen spectrum was substantially free from hetero peaks at a yield of 27%.
The characterization data for the compounds of formula (III), compounds of formula (N1) prepared in the examples of the present invention are shown in table 1:
TABLE 1 Nuclear magnetic data of Compound (III), (N1)
Example 4
(1) N1 molecule was formulated to a concentration of 2. mu. mol. L-1The acetonitrile solution of the silver is selected to obtain Ag+,Ba2+,Ca2+,Cd2+,Co2 +,Cu2+,Fe2+,Hg2+,K+,Mg2+,Na+,Ni2+,Pb2+,Zn2+The perchlorates of the 14 metal ions are respectively prepared into perchlorates with the concentration of 30 mmol.L-1The acetonitrile solution of (1); for preparing solutionsThe acetonitrile is spectrum-grade acetonitrile;
(2) transferring 5 mu L of the 14 metal ion solutions by using a 0.5-10 mu L liquid transfer gun, and adding the metal ion solutions into 3mL of fluorescent probe molecule solution to ensure that the concentration of the metal ions in the solution is 50 mu mol per L-1. Preparing 15 samples to be tested including blank samples, and standing for 10 minutes at room temperature;
(3) respectively scanning solution ultraviolet absorption spectra of the 15 samples to be detected between 250 nm and 750nm by using Perkin Elmer Lambda 750 and spectral acetonitrile as a blank background sample;
(4) the experimental results are as follows: when Hg is added to the solution2+,Pb2+And Cu2+After the three metal ions are generated, the ultraviolet absorption peak positions are respectively blue-shifted from the original 595nm to 572nm (Hg)2+And Pb2+) At 512nm (Cu)2+) Under natural illumination, the color of the solution is changed from original blue to purple and purple respectively, and the addition of other metal ions does not cause the absorption peak and the solution color to be obviously changed
Example 5
Steps (1) and (2) were the same as those of (1) and (2) in example 4
(3) Fluorescence emission spectra of 15 samples to be tested were determined using a Perkin Elmer LS 55. Setting parameters with excitation wavelength of 510nm, slit widths of 0.5nm and 0.5nm, scanning voltage of 600V, and scanning speed of 1200 nm-min-1The scanning wavelength range is 500-750 nm;
(4) the experimental results are as follows: when Hg is added to the solution2+,Pb2+And Cu2+After these three metal ions, the fluorescence intensity is significantly enhanced and blue-shifted. Accompanied by Hg2+And Pb2+When the fluorescent dye is added, a new emission peak appears at 587nm, and the fluorescent color is changed from original dark red to bright orange; while adding Cu2+Thereafter, a new emission peak appeared at 545nm, and the fluorescence color changed to green. Under the same conditions, the fluorescence spectrum and the fluorescence color are not obviously changed after other 11 metal ions are added.
Claims (7)
1. A BODIPY-based fluorescent probe containing 2, 2' -dipyridyl amine represented by formula (N1):
2. the method for synthesizing the 2, 2' -dipyridyl amine-containing BODIPY-based fluorescent probe of claim 1, represented by formula (N1), comprising:
(1) mixing a compound shown as a formula (I), a compound shown as a formula (II), a catalyst and a solvent under anhydrous and anaerobic conditions, reacting for 12-24 h at 30-60 ℃, and then carrying out post-treatment on a reaction solution to obtain a compound shown as a formula (III);
the mass ratio of the compound represented by the formula (I) to the compound represented by the formula (II) is 1: 1-2;
the amount of the catalyst substance is 5-20% of that of the compound shown in the formula (I);
the solvent is anhydrous tetrahydrofuran and triethylamine in a volume ratio of 200-300: 1, a mixed solvent;
the catalyst is prepared by mixing bis (triphenylphosphine) palladium dichloride and cuprous iodide according to the mass ratio of 1-5: 1;
(2) under the protection of inert gas, dissolving the compound shown in the formula (III) obtained in the step (1) and the compound shown in the formula (IV) in an organic solvent, reacting for 6-24 h at 20-90 ℃, and then carrying out post-treatment on a reaction liquid to obtain a compound shown in the formula (N1);
the mass ratio of the compound shown in the formula (III) to the compound shown in the formula (IV) is 1: 1-3;
the organic solvent is acetonitrile and triethylamine in a volume ratio of 20-50: 1, a mixed solvent;
3. the synthesis method according to claim 2, wherein in the step (1), the volume usage amount of the solvent is 100-250 mL/g based on the mass of the compound represented by the formula (I).
4. The synthesis method according to claim 2, wherein in the step (1), the post-treatment method comprises the following steps: after the reaction, cooling the reaction solution to room temperature, filtering to remove the catalyst, extracting with dichloromethane, and extracting the extract with anhydrous MgSO4Drying, filtering, evaporating the filtrate to remove the solvent to obtain a crude product, and performing column chromatography separation and purification on the crude product, wherein 200-mesh and 300-mesh silica gel is used as a filler, and the volume ratio of petroleum ether to ethyl acetate is 4:1 as eluent, collecting the eluent containing the target compound, evaporating the solvent and drying to obtain the compound shown in the formula (III).
5. The synthesis method according to claim 2, wherein in the step (2), the volume usage amount of the organic solvent is 100 to 200mL/g based on the mass of the compound represented by the formula (III).
6. The synthesis method according to claim 2, wherein in the step (2), the post-treatment method comprises the following steps: after the reaction is finished, cooling the reaction liquid to room temperature, extracting the reaction liquid by dichloromethane, and using anhydrous MgSO (MgSO) as an extract liquid4Drying, filtering, evaporating the filtrate to remove the solvent to obtain a crude product, and performing column chromatography separation and purification on the crude product, wherein 200-mesh and 300-mesh silica gel is used as a filler, and the volume ratio of petroleum ether to ethyl acetate is 4:1 as an eluent, collecting the eluent containing the target compound, evaporating the solvent and drying to obtain the compound shown as the formula (N1).
7. Use of the BODIPY-based fluorescent probe comprising 2, 2' -dipyridyl amine of formula (N1) according to claim 1 for the detection of metal ions.
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| CN101205416A (en) * | 2007-12-06 | 2008-06-25 | 山东师范大学 | Pyrrole dimethine fluorescent dyes as well as synthetic method and use thereof |
| CN103013495A (en) * | 2012-12-14 | 2013-04-03 | 江苏大学 | Copper ion fluorescence probe and synthetic method thereof |
| CN106749362A (en) * | 2016-12-14 | 2017-05-31 | 江苏大学 | A kind of manganese and the fluorescence probe of copper double ion response and preparation method thereof |
| CN108148575A (en) * | 2018-02-27 | 2018-06-12 | 江汉大学 | A kind of bivalent cupric ion fluorescence probe and its preparation method and application |
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|---|---|---|---|---|
| CN101205416A (en) * | 2007-12-06 | 2008-06-25 | 山东师范大学 | Pyrrole dimethine fluorescent dyes as well as synthetic method and use thereof |
| CN103013495A (en) * | 2012-12-14 | 2013-04-03 | 江苏大学 | Copper ion fluorescence probe and synthetic method thereof |
| CN106749362A (en) * | 2016-12-14 | 2017-05-31 | 江苏大学 | A kind of manganese and the fluorescence probe of copper double ion response and preparation method thereof |
| CN108148575A (en) * | 2018-02-27 | 2018-06-12 | 江汉大学 | A kind of bivalent cupric ion fluorescence probe and its preparation method and application |
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