CN111518128A - 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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- CN111518128A CN111518128A CN202010250045.XA CN202010250045A CN111518128A CN 111518128 A CN111518128 A CN 111518128A CN 202010250045 A CN202010250045 A CN 202010250045A CN 111518128 A CN111518128 A CN 111518128A
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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 71
- 239000011737 fluorine Substances 0.000 title claims abstract description 32
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title abstract description 8
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 18
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 18
- 229910001882 dioxygen Inorganic materials 0.000 claims abstract description 13
- 239000007864 aqueous solution Substances 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 10
- 239000000126 substance Substances 0.000 claims abstract description 3
- 239000002904 solvent Substances 0.000 claims description 66
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 59
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 37
- 239000000243 solution Substances 0.000 claims description 26
- 239000007787 solid Substances 0.000 claims description 23
- 238000010992 reflux Methods 0.000 claims description 22
- SUSQOBVLVYHIEX-UHFFFAOYSA-N phenylacetonitrile Chemical compound N#CCC1=CC=CC=C1 SUSQOBVLVYHIEX-UHFFFAOYSA-N 0.000 claims description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 19
- 238000006243 chemical reaction Methods 0.000 claims description 18
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 18
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 claims description 15
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- YKVOXTVWPRNYFP-UHFFFAOYSA-N [4-(bromomethyl)phenoxy]-tert-butyl-diphenylsilane Chemical compound C=1C=CC=CC=1[Si](C=1C=CC=CC=1)(C(C)(C)C)OC1=CC=C(CBr)C=C1 YKVOXTVWPRNYFP-UHFFFAOYSA-N 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 11
- 229910052757 nitrogen Inorganic materials 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 11
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- 230000035484 reaction time Effects 0.000 claims description 6
- 101001018064 Homo sapiens Lysosomal-trafficking regulator Proteins 0.000 claims description 5
- 102100033472 Lysosomal-trafficking regulator Human genes 0.000 claims description 5
- 235000010703 Modiola caroliniana Nutrition 0.000 claims description 5
- 244000038561 Modiola caroliniana Species 0.000 claims description 5
- 239000013078 crystal Substances 0.000 claims description 5
- 239000007795 chemical reaction product Substances 0.000 claims description 3
- 150000001450 anions Chemical class 0.000 abstract description 22
- 230000035945 sensitivity Effects 0.000 abstract description 5
- 229910000104 sodium hydride Inorganic materials 0.000 description 24
- 239000000047 product Substances 0.000 description 12
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 10
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 10
- 238000000862 absorption spectrum Methods 0.000 description 10
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- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 7
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 6
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- 238000002474 experimental method Methods 0.000 description 4
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- 150000002500 ions Chemical class 0.000 description 4
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- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
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- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 3
- 239000012312 sodium hydride Substances 0.000 description 3
- 239000012265 solid product Substances 0.000 description 3
- 238000004448 titration Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 2
- 206010016818 Fluorosis Diseases 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
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- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
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- 239000011550 stock solution Substances 0.000 description 2
- SWGJCIMEBVHMTA-UHFFFAOYSA-K trisodium;6-oxido-4-sulfo-5-[(4-sulfonatonaphthalen-1-yl)diazenyl]naphthalene-2-sulfonate Chemical compound [Na+].[Na+].[Na+].C1=CC=C2C(N=NC3=C4C(=CC(=CC4=CC=C3O)S([O-])(=O)=O)S([O-])(=O)=O)=CC=C(S([O-])(=O)=O)C2=C1 SWGJCIMEBVHMTA-UHFFFAOYSA-K 0.000 description 2
- 229910018557 Si O Inorganic materials 0.000 description 1
- 230000009435 amidation Effects 0.000 description 1
- 238000007112 amidation reaction Methods 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- XJHABGPPCLHLLV-UHFFFAOYSA-N benzo[de]isoquinoline-1,3-dione Chemical compound C1=CC(C(=O)NC2=O)=C3C2=CC=CC3=C1 XJHABGPPCLHLLV-UHFFFAOYSA-N 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
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- 238000004445 quantitative analysis Methods 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
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- C07—ORGANIC CHEMISTRY
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- 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
- C07F7/1892—Preparation; Treatments not provided for in C07F7/20 by reactions not provided for in C07F7/1876 - C07F7/1888
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
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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 fluoride ions, a preparation method and application thereof, wherein the chemical name of the fluorescent probe is 2- (2-butyl-1, 3-dioxygen carbonyl-2, 3-dihydro-1H-benzo [ de ] isoquinoline-6-yl) -3- (4- ((tert-butyl diphenyl silyl) oxy) phenyl) -2-phenylpropanenitrile, and the fluorescent probe is synthesized by (1) N-butyl-4-bromine-1, 8-naphthalimide; (2) synthesis of 2- (2-butyl-1, 3-dioxocarbonyl-2, 3-dihydro-1H-benzo [ des ] isoquinolin-6-yl) -2-phenylacetonitrile; (3) synthesis of 2- (2-butyl-1, 3-dioxocarbonyl-2, 3-dihydro-1H-benzo [ des ] isoquinolin-6-yl) -3- (4- ((tert-butyldiphenylsilyl) oxy) phenyl) -2-phenylpropanenitrile: finally, the fluorescent probe is applied to detecting the fluorine ions in the aqueous solution. Compared with the prior art, the method has the advantages of high sensitivity, capability of circularly identifying anions, capability of detecting fluorine ions in aqueous solution and the like.
Description
Technical Field
The invention relates to the 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. The wide existence of anions in the environment and organisms plays a great role in the metabolism and mechanism regulation in the organisms. In the biomedical field, a small amount of fluorine ions can enhance the stability of a tooth structure and protect the health of bones and teeth; and the excessive storage of human body causes fluorosis, light people cause dental fluorosis, serious people cause fluorosis, and even the self-care ability of labor and life is completely lost.
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 the fluorescent probe is that by means of a fluorescence spectrum instrument, the structure of the fluorescent molecule is changed by observing the specific reaction between the anions and the fluorescent probe molecules, and finally, the quantitative and qualitative analysis of the anions is realized by the change of the fluorescent signal. At present, people have designed and synthesized many anion fluorescent probes with potential application value, but most of the probes are complex to synthesize, high in cost and incapable of being identified repeatedly, and the anions can not be identified in aqueous solution easily. Therefore, the development of a fluorescent probe which has high sensitivity, can circularly identify anions and can detect fluorine ions in an aqueous solution is of great significance.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a fluorescent probe which has high sensitivity, can circularly identify anions and can detect fluoride ions in an aqueous solution, and a preparation method and application thereof.
The purpose of the invention can be realized by the following technical scheme:
first, the inventors have known that 1, 8-naphthalimide is an excellent fluorophore with stable structure, easy synthesis, excellent optical properties, such as absorption and emission wavelength in the visible region, larger stokes red shift, higher light stability, etc., and has the advantages of typical ICT photoelectric properties in the molecular structure, extremely high sensitivity under micro-environmental conditions, etc. Therefore, the fluorescent chromophore can be used as a potential fluorescent chromophore to be applied to the design of probes for recognizing anions, and also can be applied to the industrial fields of medicine, fluorescence, dyes, pigments and the like, so that the following scheme is obtained:
a fluorescent probe for detecting fluoride ions, which has a chemical name of 2- (2-butyl-1, 3-dioxycarbonyl-2, 3-dihydro-1H-benzo [ de ] isoquinolin-6-yl) -3- (4- ((tert-butyl diphenyl silyl) oxy) phenyl) -2-phenylpropanenitrile and has a structural formula as follows:
a method for preparing a fluorescent probe for detecting fluoride ions, which comprises the following steps:
(1) synthesis of N-butyl-4-bromo-1, 8-naphthalimide:
dissolving 4-bromo-1, 8-naphthalic anhydride in a first solvent, gradually dripping N-butylamine, heating to a reflux state, reacting, crystallizing, filtering and washing after the reaction is finished to obtain a gray yellow needle crystal N-N-butyl-4-bromo-1, 8-naphthalimide;
(2) synthesis of 2- (2-butyl-1, 3-dioxocarbonyl-2, 3-dihydro-1H-benzo [ des ] isoquinolin-6-yl) -2-phenylacetonitrile:
in the dry nitrogen atmosphere, firstly stirring and dissolving phenylacetonitrile and NaH in a second solvent, replacing the solvent with nitrogen, then dissolving N-N-butyl-4-bromo-1, 8-naphthalimide in the second solvent, and injecting the solution into the second solvent to heat to a reflux state; after the reaction is completed, the reaction product is recovered to room temperature, acidified, washed, dried, distilled under reduced pressure, and collected after column chromatography to obtain mauve solid 2- (2-butyl-1, 3-dioxygen carbonyl-2, 3-dihydro-1H-benzo [ de ] isoquinoline-6-yl) -2-phenyl acetonitrile;
(3) synthesis of 2- (2-butyl-1, 3-dioxocarbonyl-2, 3-dihydro-1H-benzo [ des ] isoquinolin-6-yl) -3- (4- ((tert-butyldiphenylsilyl) oxy) phenyl) -2-phenylpropanenitrile:
adding NaH and 2- (2-butyl-1, 3-dioxycarbonyl-2, 3-dihydro-1H-benzo [ de ] isoquinolin-6-yl) -2-phenyl acetonitrile into a third solvent in a dry nitrogen atmosphere, stirring and dissolving the mixture in the third solvent, replacing the third solvent with nitrogen, adding (4- (bromomethyl) -phenoxy) (tert-butyl) diphenylsilane, and heating to reflux; and after the reaction is completed, returning to room temperature, acidifying, extracting, washing, drying, distilling under reduced pressure, and collecting a white solid 2- (2-butyl-1, 3-dioxygen carbonyl-2, 3-dihydro-1H-benzo [ de ] isoquinoline-6-yl) -3- (4- ((tert-butyl diphenyl silyl) oxy) phenyl) -2-phenylpropanenitrile after column chromatography, namely the fluorescent probe for detecting the fluorine ions.
Since NaH is a flammable solid and is highly pyrophoric when the purity is too high, commercial NaH is typically around 60% pure and dispersed in mineral oil, so when metered, the moles shown are the moles of NaH in the product and the mass is the mass of the entire solid product. The reflux temperature in the present invention is the boiling point of the mixed liquid in each step, and therefore the reaction temperature in each step is not particularly specified.
Further, the molar volume ratio of the 4-bromo-1, 8-naphthalic anhydride, the n-butylamine and the first solvent in the step (1) is (10-15) mmol, (80-90) mmol:50 ml; the mol volume ratio of the N-N-butyl-4-bromo-1, 8-naphthalimide, the phenylacetonitrile, the NaH and the second solvent in the step (2) is (2-4) mmol, (2-5) mmol, (15-20) mmol, 40 ml; the molar volume ratio of the 2- (2-butyl-1, 3-dioxycarbonyl-2, 3-dihydro-1H-benzo [ de ] isoquinolin-6-yl) -2-phenylacetonitrile, (4- (bromomethyl) -phenoxy) (tert-butyl) diphenylsilane, NaH and the third solvent in the step (3) is (1-2) mmol, (15-20) mmol and 25 ml.
Further, the first solvent comprises acetic acid or ethanol; the second solvent comprises anhydrous tetrahydrofuran; the third solvent comprises anhydrous tetrahydrofuran.
And (3) water removal treatment of tetrahydrofuran: adding appropriate amount of sodium filament into tetrahydrofuran, heating and refluxing for about 10h, cooling to room temperature for storage, and adding activated 4A molecular sieve for sealing and storing.
Further, the reaction time in the step (1) is 1-2h, the reaction time in the step (2) is 3-6h, and the reaction time in the step (3) is 3-6 h.
The application of the fluorescent probe for detecting the fluorine ions is to detect the fluorine ions in the aqueous solution.
Further, in the detection, the fluorescent probe was dissolved in acetonitrile, and the fluoride ion was tested.
The fluorescent probe of the invention takes 4-bromine-1, 8-naphthalimide as a fluorophore and takes-Si-O group as a recognition site, ultraviolet absorption peaks exist at 331nm and 348nm under the condition that acetonitrile is taken as a solvent, and F is added-Then, absorption peaks at 331nm and 348nm were reduced, and two new peaks at 385nm and 631nm were observed. And when other anions are added, the ultraviolet absorption spectrum of the fluorescent probe is not obviously changed. In the fluorescence spectrum, 333nm is taken as an excitation wavelength, the maximum emission wavelength of the fluorescent probe is 378nm, weak blue fluorescence is realized, and F is added-After that, the fluorescence intensity at 378nm was significantly reduced. Under the irradiation of 365nm ultraviolet lamp, the addition of F is observed-Fluorescence quenching occurs later, while the other anions are unchanged. Adding F under the interference of other ions-After that, a new absorption peak still appears at 631nm, and is hardly interfered by other ions.
Compared with the prior art, the invention has the following advantages:
(1) compared with the traditional series release reaction, the fluorescence signal containing carbanion is released by cutting off the silicon-oxygen bond by the aid of the fluorinion in series, and other ions cannot cut off the silicon-oxygen bond, so that the optical signal is changed, and the fluorescence signal shows good specificity;
(2) in other ions, e.g. CN-，Cl-，Br-，I-，HSO4 -，H2PO4 -，AcO-，BF4 -，NO3 -，ClO4 -In the presence of interference, F is added-Then, the fluorescent probe still has a new absorption peak at 631nm, is hardly interfered by other ions, and shows good anti-interference performance;
(3) whether tested at high concentrations of F-And a low concentration of F-The invention can show effectiveness, and the fluorescent probe can still be combined with F at extremely high and extremely low concentration-The specific fluorescence reaction occurs, and the strong concentration adaptability is shown.
Drawings
FIG. 1 is a diagram showing the UV absorption spectra of the fluorescent probe of example 1 when different anions are added to the acetonitrile solution;
FIG. 2 is a photograph under visible light irradiation of different anions added to an acetonitrile solution of the fluorescent probe in example 1;
FIG. 3 shows different F in acetonitrile solutions of the fluorescent probes of example 1-Ultraviolet absorption spectrum at concentration;
FIG. 4 shows A-631nm and F-A concentration relation curve;
FIG. 5 shows different F in acetonitrile solutions of the fluorescent probes of example 1-Fluorescence emission spectra at concentration;
FIG. 6 shows I-530nm and F-A concentration relation curve;
FIG. 7 shows the fluorescent probes in example 1 for F in the presence of other anions-Response is a histogram of the change in UV absorption at 631 nm.
Detailed Description
The invention is described in detail below with reference to the figures and specific embodiments.
The names, specifications and manufacturer information of the various raw materials used in the examples of the present invention are shown in Table 1.
TABLE 1
| Name of raw material | Manufacturer information |
| 4-bromo-1, 8-naphthalic anhydride | SHANGHAI TITAN TECHNOLOGY Co.,Ltd. |
| N-butylamine | SHANGHAI TITAN TECHNOLOGY Co.,Ltd. |
| Benzyl cyanide | SHANGHAI TITAN TECHNOLOGY Co.,Ltd. |
| (4- (bromomethyl) -phenoxy) (tert-butyl) diphenylsilane | SHANGHAI TITAN TECHNOLOGY Co.,Ltd. |
| Acetic acid | SHANGHAI TITAN TECHNOLOGY Co.,Ltd. |
| Tetrahydrofuran (THF) | SHANGHAI TITAN TECHNOLOGY Co.,Ltd. |
| Sodium hydride | SHANGHAI TITAN TECHNOLOGY Co.,Ltd. |
The silica gel column used in each example of the present invention was a silica gel column having a length of 45cm and a diameter of 45mm, which was manufactured by Beijing Bihua glass instruments Co., Ltd.
Example 1
The invention relates to a synthesis method of fluorescent probe molecules for detecting fluoride ions, which is prepared from 4-bromo-1, 8-naphthalic anhydride, phenylacetonitrile and (4- (bromomethyl) -phenoxy) (tert-butyl) diphenylsilane through amidation, arylethanonincyanization and nucleophilic substitution, and comprises the following steps
(1) Synthesis of N-butyl-4-bromo-1, 8-naphthalimide:
4-bromo-1, 8-naphthalic anhydride (4.12g,14.90mmol) and acetic acid solvent (50ml) were added to a 100ml single-neck flask, stirred at room temperature for 10min, then n-butylamine (6.50g,85.00mmol) was gradually added dropwise, slowly heated to reflux, and the reaction was stirred at reflux for 1.5 h. After the reaction is completed, the oil bath is removed, the reaction solution is gradually cooled to room temperature, a large amount of needle crystals are separated out, the filtration is carried out, the filter cake is washed twice by 100ml of absolute ethyl alcohol and dried, and a gray yellow solid (3.76g, 76%) is obtained.
The product obtained as a pale yellow solid in the above is measured by means of a nuclear magnetic resonance instrument (Bruker AVANCE III500MHz) and the data are as follows:
1H NMR(500MHz,CDCl3),8.58(d,J＝7.2Hz,1H),8.49(d,J＝8.5Hz,1H),8.34(d,J＝7.8Hz,1H),7.97(d,J＝7.9Hz,1H),7.77(t,J＝7.5Hz,1H),4.10(t,J＝7.5Hz,2H),1.68-1.61(m,3H),1.42-1.34(m,2H),0.91(t,J＝7.4Hz,3H).
the result of the nuclear magnetic resonance spectrum data analysis of the obtained gray yellow solid powder product shows that the obtained gray yellow solid powder product is N-N-butyl-4-bromo-1, 8-naphthalimide.
(2) Synthesis of 2- (2-butyl-1, 3-dioxocarbonyl-2, 3-dihydro-1H-benzo [ des ] isoquinolin-6-yl) -2-phenylacetonitrile:
phenylacetonitrile (0.50g,4.20mmol), 60 w% sodium hydride (0.65g,16.30mmol) and anhydrous tetrahydrofuran (25ml) were rapidly charged into a 100ml three-necked flask, and replaced with nitrogen three times, and after stirring at room temperature for 1 hour, N-butyl-4-bromo-1, 8-naphthalimide (1.00g,3.00mmol) was dissolved in a tetrahydrofuran solvent (15ml) and injected into the solvent, and the temperature was slowly raised to a reflux state from the completion of the addition. After the raw materials are reacted, removing the oil bath, gradually cooling the reaction liquid to room temperature, adding 15% hydrochloric acid to adjust the reaction liquid to acidity, separating liquid, washing an aqueous phase with 60ml of toluene for 2 times, combining organic phases, washing the organic phases with 300ml of saturated saline solution for 3 times, separating liquid, drying and filtering the organic phases with anhydrous sodium sulfate, removing the solvent by spinning, and separating and purifying by silica gel column chromatography (the volume ratio of petroleum ether to ethyl acetate is 15:1) to obtain a mauve solid (0.45g, 66%), a melting point: 140.7-140.8 ℃.
The magenta solid powder product obtained above was measured by means of a nuclear magnetic resonance instrument (Bruker AVANCE III500MHz) and the data are as follows:
1H NMR(500MHz,CDCl3),8.59(d,J＝7.5Hz,1H),8.54(d,J＝6.5Hz,2H),8.39(d,J＝8.5Hz,1H),7.98(d,J＝7.5Hz,1H),7.70(t,J＝7.5Hz,1H),7.62(td,J＝7.5,1.5Hz,1H),7.30(d,J＝8.0Hz,1H),7.20(dd,J＝7.5,5.5Hz,1H),6.01(s,1H),4.10(t,J＝7.5Hz,2H),1.66-1.60(m,2H),1.39-1.33(m,2H),0.90(t,J＝7.0Hz,1H)；
13C-NMR(125MHz,CDCl3),163.81,163.50,154.25,150.15,137.80,136.99,131.38,130.86,129.62,129.01,128.90,127.81,127.52,123.72,123.62,123.58,122.30,118.13,43.43,40.36,30.17,20.35,13.79.
the result of the nuclear magnetic resonance spectrum data analysis of the purple red solid powder product shows that the purple red solid powder product is 2- (2-butyl-1, 3-dioxygen carbonyl-2, 3-dihydro-1H-benzo [ de ] isoquinoline-6-yl) -2-phenyl acetonitrile.
(3) Synthesis of 2- (2-butyl-1, 3-dioxocarbonyl-2, 3-dihydro-1H-benzo [ des ] isoquinolin-6-yl) -3- (4- ((tert-butyldiphenylsilyl) oxy) phenyl) -2-phenylpropanenitrile:
2- (2-butyl-1, 3-dioxocarbonyl-2, 3-dihydro-1H-benzo [ des ] isoquinolin-6-yl) -2-phenylacetonitrile (0.50g,1.36mmol), 60 w% sodium hydride (0.65g,16.30mmol) and anhydrous tetrahydrofuran (25ml) were quickly added to a 100ml three-necked flask and replaced with nitrogen three times, and after stirring at room temperature for 1 hour, 4- (t-butyldiphenylsiloxy) benzyl bromide (0.56g,1.36mmol) was replaced with nitrogen three times and stirred at reflux for 3 hours. After cooling at room temperature, 15% hydrochloric acid was added to adjust the mixture to acidity, the mixture was extracted three times with 60ml of ethyl acetate, the combined organic phases were washed 3 times with 300ml of saturated saline solution, the mixture was separated, the organic phase was dried over anhydrous sodium sulfate and filtered, the solvent was removed by rotation, and the mixture was separated and purified by silica gel column chromatography (volume ratio: petroleum ether: ethyl acetate: 15:1) to obtain a white solid (0.64g, 66%).
The white solid powder product obtained above was measured by means of a nuclear magnetic resonance instrument (Bruker AVANCE III500MHz) and the data are as follows:
1H NMR(500MHz,CDCl3),8.64(d,J＝7.5Hz,1H),8.49(d,J＝7.5Hz,1H),8.14-8.09(m,2H),7.72-7.70(m,4H),7.49-7.36(m,7H),7.32-7.71(m,3H),6.94(d,J＝7.5Hz,2H),6.58(d,J＝8.5Hz,2H),6.47(d,J＝8.5Hz,2H),4.18(t,J＝7.5Hz,2H),3.87(d,J＝12.5Hz,1H),3.56(d,J＝12.5Hz,1H)1.75-1.69(m,2H),1.48-1.41(m,2H),1.10(s,9H),0.97(t,J＝7.0Hz,3H)；
13C-NMR(125MHz,CDCl3)163.87,163.56,155.28,141.47,139.53,135.57,135.51,132.87,132.83,11.69,131.61,130.90,130.14,129.93,129.89,129.47,129.06,128.84,128.15,127.73,127.70,126.95,126.77,125.81,125.76,123.79,123.53,120.85,119.43,51.64,45.56,4.33,30.18,26.53,20.38,19.47,13.83.
as a result of nuclear magnetic resonance spectrum data analysis of the white solid powder product obtained above, it was found that the white solid powder product obtained above was 2- (2-butyl-1, 3-dioxocarbonyl-2, 3-dihydro-1H-benzo [ des ] isoquinolin-6-yl) -3- (4- ((tert-butyldiphenylsilyl) oxy) phenyl) -2-phenylpropanenitrile.
Identification performance of fluorescent probe for detecting fluorine ions on anions
1. Selective study of fluorescent probes for fluoride ions
(1) Fluorescent probes were prepared to 20. mu. mol. L-1The acetonitrile solution of (1); separately prepare CN-，F-，Cl-，Br-，I-，HSO4 -，H2PO4 -，AcO-，BF4 -，NO3 -，ClO4 -5000. mu. mol. L of-1The solution was measured in an amount of 0.4mL of 5000. mu. mol. L-1The fluorescent probe solution is prepared into 20 mu mol.L by using acetonitrile to fix the volume to 100mL-1The probe solutions of (1) were divided into 12 groups (5 mL each), the first group was a blank experiment,to each of the other components was added 180 equivalents (180.0. mu.L, 5000. mu. mol. L)-1) The response of the fluorescent probe to various anions is observed through ultraviolet absorption spectrum.
As shown in FIG. 1, the fluorescent probe has UV absorption peaks at 331nm and 348nm in acetonitrile as solvent, and F is added-Then, absorption peaks at 331nm and 348nm were reduced, and two new peaks at 385nm and 631nm were observed. And when other anions are added, the ultraviolet absorption spectrum of the fluorescent probe is not obviously changed. The fluorescent probe can specifically detect the fluorine ions.
2. Interference test study on fluoride ions in the Presence of other anions
The prepared CN-，Cl-，Br-，I-，HSO4 -，H2PO4 -，AcO-，BF4 -，NO3 -，ClO4 -The ten groups of solutions are observed by ultraviolet absorption spectrum, and then 180 equivalent (180.0 mu L,5000 mu mol. L) are respectively added-1) The response of the fluorescent probe to the fluorine ions under the interference of various anions is observed through ultraviolet absorption spectrum.
The results show that, as shown in FIG. 7, the light color bars of the fluorescent probe in acetonitrile as a solvent respectively indicate the presence of CN only-，Cl-，Br-，I-，HSO4 -，H2PO4 -，AcO-，BF4 -，NO3 -，ClO4 -Emission at 631nm for anions. The dark bars indicate the change that occurs when 180 equivalents of fluoride ion are subsequently added. Result in at CN-，Cl-，Br-，I-，HSO4 -，H2PO4 -，AcO-，BF4 -，NO3 -，ClO4 -In the presence of anions, the interference on the detection of fluorine ions by the fluorescent probe in an acetonitrile solution is small, and the influence is almost avoided.
3. Fluorescent probe titration experiment of fluoride ion
Dissolving the fluorescent probe in acetonitrile to prepare 5000 mu mol.L-1Stock solution of (1), preparation F-Stock solution with a concentration of 50000. mu. mol. L-1. 100. mu.L of 5000. mu. mol. L was measured-1The fluorescent probe solution is put into a 25mL volumetric flask, and the volume is adjusted to 25mL by acetonitrile solution to prepare 25mL,20 mu mol.L-1Acetonitrile solvent (b) of the fluorescent probe solution of (a).
(1) High concentration titration experiment: 25mL of the solution was added in an amount of 20. mu. mol. L-1The probe solution of acetonitrile solvent (2) was poured into a 250mL wide-mouth flask, and 10.0. mu.L, 5000. mu. mol. L, was added dropwise thereto-1(10.0 equiv.) of F-The solution is shaken uniformly and then the ultraviolet absorption spectrum is detected, the operation is repeated until 180.0 equivalent of the fluorine ion solution is added, and the result shows that, as shown in the figure 3-4, the ultraviolet absorption spectrum of the fluorescent probe is influenced by the concentration of the fluorine ions, the absorption peaks of the fluorescent probe at 385nm and 631nm are gradually increased along with the gradual addition of the fluorine ions until 3600 mu mol. L is added-1F of (A)-Equilibrium is reached.
(2) Low concentration titration experiment: 25mL of the solution was added in an amount of 20. mu. mol. L-1The probe solution of acetonitrile solvent (2) was poured into a 100mL wide-necked flask, and 1.0. mu.L, 50000. mu. mol. L, was added dropwise thereto-1(0.1 equiv.) of F-The solution was shaken well and the UV absorption spectrum was measured and the procedure was repeated until 2.5 equivalents of fluoride ion solution were added. Then measuring fluorescence emission spectrum, as shown in FIGS. 5-6, the fluorescence intensity of the fluorescent probe is very strong at 378nm, and gradually decreases with the addition of fluoride ion until 50. mu. mol. L is added-1F of (A)-Equilibrium is reached.
The fluorescent probe for detecting the fluorine ions is applied to detecting the fluorine ions in the aqueous solution, and during detection, the fluorescent probe is dissolved in acetonitrile to test the fluorine ions.
Example 2
A preparation method of a fluorescent probe for detecting fluorine ions comprises the following steps:
(1) synthesis of N-butyl-4-bromo-1, 8-naphthalimide: dissolving 4-bromo-1, 8-naphthalic anhydride in a first solvent, gradually dripping N-butylamine, heating to a reflux state, reacting for 1h, and after the reaction is finished, crystallizing, filtering and washing to obtain a gray yellow needle crystal N-N-butyl-4-bromo-1, 8-naphthalimide; wherein the molar volume ratio of the 4-bromo-1, 8-naphthalic anhydride to the n-butylamine to the first solvent is 10mmol:90mmol:50 ml; the first solvent is ethanol.
(2) Synthesis of 2- (2-butyl-1, 3-dioxocarbonyl-2, 3-dihydro-1H-benzo [ des ] isoquinolin-6-yl) -2-phenylacetonitrile: in the dry nitrogen atmosphere, firstly stirring and dissolving phenylacetonitrile and NaH in a second solvent, replacing the solvent with nitrogen, then dissolving N-N-butyl-4-bromo-1, 8-naphthalimide in the second solvent, and injecting the solution into the second solvent to heat to a reflux state; after reacting for 3 hours, recovering to room temperature, acidifying, washing, drying, distilling under reduced pressure, and collecting to obtain mauve solid 2- (2-butyl-1, 3-dioxygen carbonyl-2, 3-dihydro-1H-benzo [ de ] isoquinoline-6-yl) -2-phenyl acetonitrile after column chromatography; wherein the molar volume ratio of the N-N-butyl-4-bromo-1, 8-naphthalimide to the phenylacetonitrile to the NaH to the second solvent is 2mmol:2mmol:20mmol:40 ml; the second solvent is anhydrous tetrahydrofuran;
(3) synthesis of 2- (2-butyl-1, 3-dioxocarbonyl-2, 3-dihydro-1H-benzo [ des ] isoquinolin-6-yl) -3- (4- ((tert-butyldiphenylsilyl) oxy) phenyl) -2-phenylpropanenitrile: adding NaH and 2- (2-butyl-1, 3-dioxycarbonyl-2, 3-dihydro-1H-benzo [ de ] isoquinolin-6-yl) -2-phenyl acetonitrile into a third solvent in a dry nitrogen atmosphere, stirring and dissolving the mixture in the third solvent, replacing the third solvent with nitrogen, adding (4- (bromomethyl) -phenoxy) (tert-butyl) diphenylsilane, and heating to reflux; after reacting for 3 hours, returning to room temperature, acidifying, extracting, washing, drying, distilling under reduced pressure, and collecting a white solid 2- (2-butyl-1, 3-dioxygen carbonyl-2, 3-dihydro-1H-benzo [ de ] isoquinoline-6-yl) -3- (4- ((tert-butyl diphenyl silyl) oxy) phenyl) -2-phenylpropyl nitrile after column chromatography, namely a fluorescent probe for detecting fluorine ions, wherein the fluorescent probe for detecting fluorine ions comprises 2- (2-butyl-1, 3-dioxygen carbonyl-2, 3-dihydro-1H-benzo [ de ] isoquinoline-6-yl) -2-phenyl acetonitrile, (4- (bromomethyl) -phenoxy) (tert-butyl) diphenylsilane, N-methyl-ethyl-phenyl-N-ethyl-methyl-phenyl-N-propyl-phenyl-2-phenyl-propionitrile, The molar volume ratio of NaH to the third solvent is 1mmol:1mmol:20mmol:25 ml; the third solvent is anhydrous tetrahydrofuran.
In particular, since NaH is a flammable solid and is highly pyrophoric when the purity is too high, commercial NaH is generally about 60% pure and dispersed in mineral oil, so that the moles shown are the moles of NaH in the product when metered and the mass is the mass of the entire solid product. The reflux temperature in the present invention is the boiling point of the mixed liquid in each step, and therefore the reaction temperature in each step is not particularly specified.
And (3) water removal treatment of tetrahydrofuran: adding appropriate amount of sodium filament into tetrahydrofuran, heating and refluxing for about 10h, cooling to room temperature for storage, and adding activated 4A molecular sieve for sealing and storing.
The fluorescent probe for detecting the fluorine ions is applied to detecting the fluorine ions in the aqueous solution, and during detection, the fluorescent probe is dissolved in acetonitrile to test the fluorine ions.
Example 3
A preparation method of a fluorescent probe for detecting fluorine ions comprises the following steps:
(1) synthesis of N-butyl-4-bromo-1, 8-naphthalimide: dissolving 4-bromo-1, 8-naphthalic anhydride in a first solvent, gradually dripping N-butylamine, heating to a reflux state, reacting for 2 hours, and after the reaction is finished, crystallizing, filtering and washing to obtain a gray yellow needle crystal N-N-butyl-4-bromo-1, 8-naphthalimide; wherein the molar volume ratio of the 4-bromo-1, 8-naphthalic anhydride to the n-butylamine to the first solvent is 15mmol:80mmol:50 ml; the first solvent is ethanol.
(2) Synthesis of 2- (2-butyl-1, 3-dioxocarbonyl-2, 3-dihydro-1H-benzo [ des ] isoquinolin-6-yl) -2-phenylacetonitrile: in the dry nitrogen atmosphere, firstly stirring and dissolving phenylacetonitrile and NaH in a second solvent, replacing the solvent with nitrogen, then dissolving N-N-butyl-4-bromo-1, 8-naphthalimide in the second solvent, and injecting the solution into the second solvent to heat to a reflux state; after reacting for 6 hours, recovering to room temperature, acidifying, washing, drying, distilling under reduced pressure, and collecting to obtain mauve solid 2- (2-butyl-1, 3-dioxygen carbonyl-2, 3-dihydro-1H-benzo [ de ] isoquinoline-6-yl) -2-phenyl acetonitrile after column chromatography; wherein the molar volume ratio of the N-N-butyl-4-bromo-1, 8-naphthalimide to the phenylacetonitrile to the NaH to the second solvent is 4mmol:5mmol:15mmol:40 ml; the second solvent is anhydrous tetrahydrofuran;
(3) synthesis of 2- (2-butyl-1, 3-dioxocarbonyl-2, 3-dihydro-1H-benzo [ des ] isoquinolin-6-yl) -3- (4- ((tert-butyldiphenylsilyl) oxy) phenyl) -2-phenylpropanenitrile: adding NaH and 2- (2-butyl-1, 3-dioxycarbonyl-2, 3-dihydro-1H-benzo [ de ] isoquinolin-6-yl) -2-phenyl acetonitrile into a third solvent in a dry nitrogen atmosphere, stirring and dissolving the mixture in the third solvent, replacing the third solvent with nitrogen, adding (4- (bromomethyl) -phenoxy) (tert-butyl) diphenylsilane, and heating to reflux; after 6 hours of reaction, the reaction product is recovered to room temperature, acidified, extracted, washed and dried, and distilled under reduced pressure, and white solid 2- (2-butyl-1, 3-dioxygen carbonyl-2, 3-dihydro-1H-benzo [ de ] isoquinoline-6-yl) -3- (4- ((tert-butyl diphenyl silyl) oxy) phenyl) -2-phenylpropyl nitrile is collected after column chromatography, namely the fluorescent probe for detecting fluorine ions, wherein the fluorescent probe for detecting fluorine ions comprises 2- (2-butyl-1, 3-dioxygen carbonyl-2, 3-dihydro-1H-benzo [ de ] isoquinoline-6-yl) -2-phenyl acetonitrile, (4- (bromomethyl) -phenoxy) (tert-butyl) diphenylsilane, N-methyl-ethyl acetate, N-butyl-, The molar volume ratio of NaH to the third solvent is 2mmol:2mmol:15mmol:25 ml; the third solvent is anhydrous tetrahydrofuran.
In particular, since NaH is a flammable solid and is highly pyrophoric when the purity is too high, commercial NaH is generally about 60% pure and dispersed in mineral oil, so that the moles shown are the moles of NaH in the product when metered and the mass is the mass of the entire solid product. The reflux temperature in the present invention is the boiling point of the mixed liquid in each step, and therefore the reaction temperature in each step is not particularly specified.
And (3) water removal treatment of tetrahydrofuran: adding appropriate amount of sodium filament into tetrahydrofuran, heating and refluxing for about 10h, cooling to room temperature for storage, and adding activated 4A molecular sieve for sealing and storing.
The fluorescent probe for detecting the fluorine ions is applied to detecting the fluorine ions in the aqueous solution, and during detection, the fluorescent probe is dissolved in acetonitrile to test the fluorine ions.
The embodiments described above are described to facilitate an understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.
Claims (9)
1. A fluorescent probe for detecting fluoride ions is characterized in that the chemical name of the fluorescent probe is 2- (2-butyl-1, 3-dioxygen carbonyl-2, 3-dihydro-1H-benzo [ de ] isoquinoline-6-yl) -3- (4- ((tert-butyl diphenyl silyl) oxy) phenyl) -2-phenylpropanenitrile, and the structural formula of the fluorescent probe is as follows:
2. a method for preparing a fluorescent probe for detecting fluoride ions according to claim 1, comprising the steps of:
(1) synthesis of N-butyl-4-bromo-1, 8-naphthalimide:
dissolving 4-bromo-1, 8-naphthalic anhydride in a first solvent, gradually dripping N-butylamine, heating to a reflux state, reacting, crystallizing, filtering and washing after the reaction is finished to obtain a gray yellow needle crystal N-N-butyl-4-bromo-1, 8-naphthalimide;
(2) synthesis of 2- (2-butyl-1, 3-dioxocarbonyl-2, 3-dihydro-1H-benzo [ des ] isoquinolin-6-yl) -2-phenylacetonitrile:
in the dry nitrogen atmosphere, firstly stirring and dissolving phenylacetonitrile and NaH in a second solvent, replacing the solvent with nitrogen, then dissolving N-N-butyl-4-bromo-1, 8-naphthalimide in the second solvent, and injecting the solution into the second solvent to heat to a reflux state; after the reaction is completed, the reaction product is recovered to room temperature, acidified, washed, dried, distilled under reduced pressure, and collected after column chromatography to obtain mauve solid 2- (2-butyl-1, 3-dioxygen carbonyl-2, 3-dihydro-1H-benzo [ de ] isoquinoline-6-yl) -2-phenyl acetonitrile;
(3) synthesis of 2- (2-butyl-1, 3-dioxocarbonyl-2, 3-dihydro-1H-benzo [ des ] isoquinolin-6-yl) -3- (4- ((tert-butyldiphenylsilyl) oxy) phenyl) -2-phenylpropanenitrile:
adding NaH and 2- (2-butyl-1, 3-dioxycarbonyl-2, 3-dihydro-1H-benzo [ de ] isoquinolin-6-yl) -2-phenyl acetonitrile into a third solvent in a dry nitrogen atmosphere, stirring and dissolving the mixture in the third solvent, replacing the third solvent with nitrogen, adding (4- (bromomethyl) -phenoxy) (tert-butyl) diphenylsilane, and heating to reflux; and after the reaction is completed, returning to room temperature, acidifying, extracting, washing, drying, distilling under reduced pressure, and collecting a white solid 2- (2-butyl-1, 3-dioxygen carbonyl-2, 3-dihydro-1H-benzo [ de ] isoquinoline-6-yl) -3- (4- ((tert-butyl diphenyl silyl) oxy) phenyl) -2-phenylpropanenitrile after column chromatography, namely the fluorescent probe for detecting the fluorine ions.
3. The method for preparing a fluorescent probe for detecting fluoride ions according to claim 2, wherein the molar volume ratio of the 4-bromo-1, 8-naphthalic anhydride, n-butylamine and first solvent in step (1) is (10-15) mmol, (80-90) mmol:50 ml.
4. The method for preparing the fluorescent probe for detecting the fluoride ions according to claim 2, wherein the molar volume ratio of the N-N-butyl-4-bromo-1, 8-naphthalimide, the phenylacetonitrile, the NaH and the second solvent in the step (2) is (2-4) mmol, (2-5) mmol:40 ml.
5. The method for preparing a fluorescent probe for detecting fluoride ions according to claim 2, wherein the molar volume ratio of the 2- (2-butyl-1, 3-dioxycarbonyl-2, 3-dihydro-1H-benzo [ de ] isoquinolin-6-yl) -2-phenylacetonitrile, (4- (bromomethyl) -phenoxy) (tert-butyl) diphenylsilane, NaH and the third solvent in the step (3) is (1-2) mmol, (15-20) mmol:25 ml.
6. The method of claim 2, wherein the first solvent comprises acetic acid or ethanol; the second solvent comprises anhydrous tetrahydrofuran, and the third solvent comprises anhydrous tetrahydrofuran.
7. The method of claim 2, wherein the reaction time in step (1) is 1-2h, the reaction time in step (2) is 3-6h, and the reaction time in step (3) is 3-6 h.
8. Use of a fluorescent probe for detecting fluoride ions according to claim 1 for detecting fluoride ions in an aqueous solution.
9. The use of a fluorescent probe for detecting fluoride ions according to claim 8, wherein the fluoride ions are detected by dissolving the fluorescent probe in acetonitrile.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104003935A (en) * | 2014-05-16 | 2014-08-27 | 上海应用技术学院 | 4-aroyl-1,8-naphthalimide compound and preparation method and use thereof |
| CN107118155A (en) * | 2017-05-22 | 2017-09-01 | 上海应用技术大学 | Fragrant naphthoyl imide compounds of ethanol base 1,8 of one kind 4 and its preparation method and application |
-
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104003935A (en) * | 2014-05-16 | 2014-08-27 | 上海应用技术学院 | 4-aroyl-1,8-naphthalimide compound and preparation method and use thereof |
| CN107118155A (en) * | 2017-05-22 | 2017-09-01 | 上海应用技术大学 | Fragrant naphthoyl imide compounds of ethanol base 1,8 of one kind 4 and its preparation method and application |
Non-Patent Citations (2)
| Title |
|---|
| BAIYUN LI等: "Chemodosimeter for fluoride ions based on F--triggered Si-O cleavage followed by the deprotonation/autoxidation of secondary nitrile C-H group", 《RSC ADV.》 * |
| ZENGWEI LUO等: "A dual-channel probe for selective fluoride determination and application in live cell imaging", 《DYES AND PIGMENTS》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111848664A (en) * | 2020-07-15 | 2020-10-30 | 河西学院 | Receptor compound for colorimetric detection of fluoride ions, and preparation method and application thereof |
| CN112961180A (en) * | 2021-03-03 | 2021-06-15 | 安徽农业大学 | Fluorine ion fluorescent colorimetric probe and preparation method and application thereof |
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| CN111518128B (en) | 2022-08-23 |
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