CN111410664A - Probe for detecting fluorine ions in water-containing system and preparation method thereof - Google Patents
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- 239000000523 sample Substances 0.000 title claims abstract description 49
- -1 fluorine ions Chemical class 0.000 title claims abstract description 30
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 29
- 239000011737 fluorine Substances 0.000 title claims abstract description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000000243 solution Substances 0.000 claims description 20
- 238000005406 washing Methods 0.000 claims description 16
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 13
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 10
- SMQUZDBALVYZAC-UHFFFAOYSA-N salicylaldehyde Chemical compound OC1=CC=CC=C1C=O SMQUZDBALVYZAC-UHFFFAOYSA-N 0.000 claims description 10
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- 238000000926 separation method Methods 0.000 claims description 7
- 230000015572 biosynthetic process Effects 0.000 claims description 6
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 6
- 238000003786 synthesis reaction Methods 0.000 claims description 6
- VRVRGVPWCUEOGV-UHFFFAOYSA-N 2-aminothiophenol Chemical compound NC1=CC=CC=C1S VRVRGVPWCUEOGV-UHFFFAOYSA-N 0.000 claims description 5
- MHYGQXWCZAYSLJ-UHFFFAOYSA-N tert-butyl-chloro-diphenylsilane Chemical compound C=1C=CC=CC=1[Si](Cl)(C(C)(C)C)C1=CC=CC=C1 MHYGQXWCZAYSLJ-UHFFFAOYSA-N 0.000 claims description 5
- 239000012043 crude product Substances 0.000 claims description 4
- 238000000967 suction filtration Methods 0.000 claims description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 3
- 238000000605 extraction Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical class [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 2
- 238000001953 recrystallisation Methods 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 238000012856 packing Methods 0.000 claims 1
- 238000001514 detection method Methods 0.000 abstract description 13
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 6
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 5
- 231100000167 toxic agent Toxicity 0.000 description 5
- 239000003440 toxic substance Substances 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 230000035622 drinking Effects 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 238000001917 fluorescence detection Methods 0.000 description 2
- 238000002189 fluorescence spectrum Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000003068 molecular probe Substances 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- FPGGTKZVZWFYPV-UHFFFAOYSA-M tetrabutylammonium fluoride Chemical compound [F-].CCCC[N+](CCCC)(CCCC)CCCC FPGGTKZVZWFYPV-UHFFFAOYSA-M 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 1
- DYAHQFWOVKZOOW-UHFFFAOYSA-N Sarin Chemical compound CC(C)OP(C)(F)=O DYAHQFWOVKZOOW-UHFFFAOYSA-N 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical class [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- GRXKLBBBQUKJJZ-UHFFFAOYSA-N Soman Chemical compound CC(C)(C)C(C)OP(C)(F)=O GRXKLBBBQUKJJZ-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000006757 chemical reactions by type Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 208000002925 dental caries Diseases 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000003673 groundwater Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 239000008239 natural water Substances 0.000 description 1
- 210000005036 nerve Anatomy 0.000 description 1
- 150000003961 organosilicon compounds Chemical class 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000010898 silica gel chromatography Methods 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Images
Classifications
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- 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 System
- 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 System
- 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
- C07F7/188—Preparation; Treatments not provided for in C07F7/20 by reactions involving the formation of Si-O linkages
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
- G01N21/643—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes" non-biological material
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
- G01N33/18—Water
- G01N33/182—Water specific anions in water
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
- G01N33/18—Water
- G01N33/1886—Water using probes, e.g. submersible probes, buoys
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
- C09K2211/1037—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom with sulfur
Abstract
The invention discloses a probe for detecting fluorine ions and a preparation method thereof. The molecular structure of the probe is shown as the formula (I):
the probe provided by the invention can realize detection of fluorine ions in a water-containing system, and has the advantages of high detection speed and high selectivity.
Description
Technical Field
The invention belongs to the technical field of fluoride ion detection, and particularly relates to a probe for detecting fluoride ions in a water-containing system and a preparation method thereof.
Background
G-type toxicants such as sarin, soman and the like in nerve toxicants contain phosphorus-fluorine bonds in the molecular structure, and under hydrolysis conditions (especially alkaline), the phosphorus-fluorine bonds of the toxicants are broken, and fluorine is released as fluorine ions. Therefore, for the identification and quantitative detection of the fluorine ions, the existence of G-type toxic agents can be judged, and a basis is provided for the protection and treatment of the G-type toxic agents.
In addition, fluorine ions widely exist in natural water bodies, the content of surface water such as rivers, lakes and the like is usually several percent to several ten milligrams per liter, while the content of fluorine in groundwater is about 1 milligram per liter, drinking is not suitable when the content of fluorine in water exceeds 1 milligram per liter, plaque and odontopathy can be caused after long-term drinking, but if the content of fluorine ions in drinking water is too low, caries can be caused.
Compared with the two molecular probes for detecting the fluorine ions, the organosilicon compound reaction type molecular probe has higher selectivity and can also realize the detection of the fluorine ions in a water system.
Disclosure of Invention
The invention aims to make up the defects of the prior art and provides a probe for detecting fluorine ions in an aqueous system and a preparation method thereof. The probe provided by the invention can realize detection of fluorine ions in a water-containing system, and has the advantages of high detection speed and high selectivity.
In order to achieve the purpose, the invention adopts the following technical scheme:
a probe for detecting fluorine ions in an aqueous system, the molecular structure of the probe is represented by formula (I):
a preparation method of a probe for detecting fluorine ions in an aqueous system comprises the following steps:
(1) synthesis of intermediate of probe molecule
Dissolving salicylaldehyde and 2-aminothiophenol in an ethanol solution, dripping a mixed solution of hydrogen peroxide and hydrochloric acid at room temperature, and reacting at room temperature for 12-20 hours to obtain a probe molecular intermediate;
(2) synthesis of Probe molecules
Dropwise adding the pyridine solution of tert-butyldiphenylchlorosilane into the pyridine solution of the probe molecule intermediate, heating and stirring, controlling the temperature at 65-70 ℃, and reacting for 12-24h to obtain the probe molecule.
Preferably, the molar ratio of the salicylaldehyde to the 2-aminothiophenol to the hydrogen peroxide to the hydrochloric acid in the step (1) is 1:1:6: 1.5.
Preferably, the mass concentration of the hydrogen peroxide solution in the step (1) is 30%, and the mass concentration of the hydrochloric acid solution is 37%.
Preferably, the method further comprises the steps of suction filtration, washing and recrystallization after the reaction in the step (1) is finished.
Preferably, the solvent for washing in the step (1) is absolute ethanol.
Preferably, the molar ratio of the probe molecule intermediate to the tert-butyldiphenylchlorosilane in the step (2) is 5: 6.
Preferably, the step (2) further comprises a post-treatment step after the reaction is finished, wherein the post-treatment step comprises extraction, washing and column separation steps.
Preferably, the washing step comprises washing with water, 10% citric acid solution, saturated sodium bicarbonate solution, saturated saline solution, and water in sequence twice or more.
Preferably, the column separation is performed by filling an alkaline alumina column with ethyl acetate to perform column separation on the crude product.
The invention has the following technical characteristics:
1) when the probe provided by the invention meets fluorine ions, probe molecules generate silicon removal reaction, strong fluorescence is generated under the irradiation of exciting light, and the whole detection system has good OFF-ON or the wavelength of a fluorescence spectrum is remarkably changed, so that the detection of the fluorine ions is completed.
2) The probe has a diphenyl tert-butyl structure, has larger steric hindrance and molecular rigidity, and is favorable for the reaction of fluorine ions and silicon.
3) According to the probe provided by the invention, under the action of fluorine ions, an organic silicon compound is subjected to desilication (fluorine addition of silicon), a reaction product is subjected to intramolecular proton transfer under the action of exciting light, the molecular structure is remarkably changed, and the reaction has specificity, so that the probe has high selectivity on the fluorine ions.
4) The probe provided by the invention can rapidly realize the detection of the fluorine ions in a water-containing system, and the fluorescence detected in a few minutes can reach the maximum value.
Drawings
FIG. 1 shows fluorescence detection of different concentrations of fluoride ions by probe molecules.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions of the embodiments of the present invention will be clearly and completely described below. It is to be understood that the embodiments described are only a few embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the described embodiments of the invention without any inventive step, are within the scope of protection of the invention.
Unless defined otherwise, technical or scientific terms used herein shall have the ordinary meaning as understood by one of ordinary skill in the art to which this invention belongs.
Example 1: preparation method of probe for detecting fluorine ions in water-containing system
The method comprises the following steps:
(1) synthesis of intermediate of probe molecule
2.44g (20mmol) of salicylaldehyde and 2.50g (20mmol) of 2-aminothiophenol are weighed out and dissolved in 20ml of ethanol, and 10ml (120mmol) of 30% H is added dropwise at room temperature2O2And 2ml (30mmol) of 37% HCl mixed solution, reacting at room temperature for 12 hours, performing suction filtration by using a Buchner funnel and a water pump, filtering out precipitates, washing the precipitates by using absolute ethyl alcohol for a plurality of times, and then performing dry weight crystallization on the precipitates by a rotary evaporator to obtain 2.77g of probe intermediate, wherein the product yield is 61.0%.
(2) Synthesis of Probe molecules
Weighing 1.135g (5mmol) of probe molecule intermediate A, adding 35ml of pyridine, weighing 1.65g (6mmol) of tert-butyldiphenylchlorosilane, dissolving in 20ml of pyridine, dropwise adding into the probe molecule P3 intermediate, heating and stirring, controlling the temperature at 65-70 ℃, monitoring the reaction process by T L C, after 12h of reaction, spin-drying on a rotary evaporator, adding 50ml of ethyl acetate and 50ml of water for extraction, filtering out a water layer, washing twice with 20ml of water, washing twice with 10% citric acid, washing twice with 20ml of saturated sodium bicarbonate, washing twice with 20ml of saturated saline solution, washing twice with 20ml of water, adding anhydrous magnesium sulfate, drying overnight, performing reduced pressure spin-drying on a rotary evaporator the next day to obtain light yellow viscous liquid, performing suction filtration for two hours by an oil pump, and weighing to obtain 0.935g of crude product.
The analysis was carried out by thin layer silica gel chromatography. Filling an alkaline alumina column with ethyl acetate to carry out column separation on the crude product, firstly using petroleum ether as a mobile phase, filtering out by-products or reactants, and then using the petroleum ether: taking ethyl acetate 1:1 as a mobile phase, and filtering to obtain the product. After passing through the column, spin-dried on a rotary evaporator and suction-filtered with an oil pump, light yellow silicon-etherified probe molecule P3 was obtained in an amount of 0.827g with a yield of 31.4% each.
Example 2 determination of fluorescence detection wavelength
(1) Determination of detection wavelength
325mg of the probe molecule prepared in example 1 was weighed and dissolved in 5m L acetonitrile to prepare a probe molecule solution with a concentration of 1 mmol/L for use.
A1 mol/L solution of tetrabutylammonium fluoride in tetrahydrofuran was diluted to a1 mmol/L solution of fluoride ions.
The fluorescence spectrum is characterized in that 2.0m L target solution is added into a quartz fluorescence pool with the width of 10mm, the sum of the volumes of fluorine ion solutions introduced in the measurement process is not more than 100u L, so that the influence of volume change on the fluorescence property is reduced as much as possible.
(2) Detection of different concentrations of fluoride ion
To explore the probe molecules under 1% aqueous conditions (1% H)2O/DMF), the influence on the fluorescence intensity under the condition of different concentrations of fluoride ions, preparing fluoride ion solutions with the fluoride ion concentrations of 0 uM/L, 20 uM/L, 40 uM/L, 60 uM/L, 80 uM/L and 100 uM/L respectively, detecting the fluorescence intensity of probe molecules at different concentrations of fluoride ions, drawing a relation curve (shown in figure 1) between the fluorescence intensity and the fluoride ion concentration, and detecting whether the detection range of the probe molecules can reach the highest concentration of the fluorine content of water for domestic application in China.
The test conditions are that the room temperature, the sample cell is a quartz cuvette with the width of 5nm and the excitation wavelength of probe molecules is 398nm, the sample cell is 1cm × 1cm × 4cm, and the fluorescence intensity is detected in the emission wavelength range of 420-600 nm.
As can be seen from FIG. 1, the lowest concentration of fluorine ions detected by the probe molecule under the condition of water content of 1% is 20 uM/L (0.38 mg/L).
The above description of the embodiments is only intended to facilitate the understanding of the method of the invention and its core ideas. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention.
Claims (10)
1. A probe for detecting fluorine ions in an aqueous system, wherein the molecular structure of the probe is as shown in formula (I):
2. a preparation method of a probe for detecting fluorine ions in an aqueous system is characterized by comprising the following steps:
(1) synthesis of intermediate of probe molecule
Dissolving salicylaldehyde and 2-aminothiophenol in an ethanol solution, dripping a mixed solution of hydrogen peroxide and hydrochloric acid at room temperature, and reacting at room temperature for 12-20 hours to obtain a probe molecular intermediate;
(2) synthesis of Probe molecules
Dropwise adding the pyridine solution of tert-butyldiphenylchlorosilane into the pyridine solution of the probe molecule intermediate, heating and stirring, controlling the temperature at 65-70 ℃, and reacting for 12-24h to obtain the probe molecule.
3. The preparation method according to claim 2, wherein the molar ratio of the salicylaldehyde to the 2-aminothiophenol to the hydrogen peroxide to the hydrochloric acid in the step (1) is 1:1:6: 1.5.
4. The preparation method according to claim 2, wherein the mass concentration of the hydrogen peroxide solution in the step (1) is 30%, and the mass concentration of the hydrochloric acid solution is 37%.
5. The preparation method according to claim 2, characterized in that the reaction in step (1) further comprises the steps of suction filtration, washing and recrystallization after the reaction is finished.
6. The method according to claim 2, wherein the solvent for washing in the step (1) is absolute ethanol.
7. The method according to claim 2, wherein the molar ratio of the probe molecule intermediate to tert-butyldiphenylchlorosilane in step (2) is 5: 6.
8. The method according to claim 2, wherein the step (2) further comprises a post-treatment step after the reaction is completed, wherein the post-treatment step comprises extraction, washing and column separation steps.
9. The method according to claim 2, wherein the washing step comprises washing with water, a 10% citric acid solution, a saturated sodium bicarbonate solution, a saturated saline solution, and water in this order twice or more.
10. The method according to claim 2, wherein the column separation is performed by packing an alkaline alumina column with ethyl acetate to perform column separation on the crude product.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2022104414A1 (en) * | 2020-11-17 | 2022-05-27 | The University Of Queensland | Detection method |
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|---|---|---|---|---|
| CN102250134A (en) * | 2010-05-21 | 2011-11-23 | 中国科学院化学研究所 | Fluorescent probe for identifying fluorine ions and preparation method and use thereof |
| CN104449677A (en) * | 2014-12-29 | 2015-03-25 | 大连理工常熟研究院有限公司 | Specific fluorescent probe for recognizing fluorine ions and application of specific fluorescent probe |
| CN104610955A (en) * | 2014-05-16 | 2015-05-13 | 中南大学 | Synthesis method and application of ratiometric fluorescent molecular probe for simultaneously detecting fluorine ion and sulfite radical |
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2020
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102250134A (en) * | 2010-05-21 | 2011-11-23 | 中国科学院化学研究所 | Fluorescent probe for identifying fluorine ions and preparation method and use thereof |
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