CN111533760B - Fluorescent probe for content of fluorine ions in acetate esterification reaction system, preparation method and detection method thereof - Google Patents
Fluorescent probe for content of fluorine ions in acetate esterification reaction system, preparation method and detection method thereof Download PDFInfo
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- 239000007850 fluorescent dye Substances 0.000 title claims abstract description 71
- 238000001514 detection method Methods 0.000 title claims abstract description 17
- 238000005886 esterification reaction Methods 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 title claims abstract description 14
- -1 fluorine ions Chemical class 0.000 title claims description 29
- 229910052731 fluorine Inorganic materials 0.000 title claims description 24
- 239000011737 fluorine Substances 0.000 title claims description 24
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims abstract description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 43
- 238000006243 chemical reaction Methods 0.000 claims description 29
- 239000000523 sample Substances 0.000 claims description 28
- 238000000034 method Methods 0.000 claims description 23
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- 238000010992 reflux Methods 0.000 claims description 16
- 239000002904 solvent Substances 0.000 claims description 15
- 150000001875 compounds Chemical class 0.000 claims description 14
- 239000013067 intermediate product Substances 0.000 claims description 13
- 239000007788 liquid Substances 0.000 claims description 13
- 238000012937 correction Methods 0.000 claims description 12
- 238000001914 filtration Methods 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 7
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-Diisopropylethylamine (DIPEA) Chemical compound CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 claims description 7
- 239000002994 raw material Substances 0.000 claims description 6
- MKKSTJKBKNCMRV-UHFFFAOYSA-N 5-bromo-2-hydroxybenzaldehyde Chemical compound OC1=CC=C(Br)C=C1C=O MKKSTJKBKNCMRV-UHFFFAOYSA-N 0.000 claims description 5
- OXEUETBFKVCRNP-UHFFFAOYSA-N 9-ethyl-3-carbazolamine Chemical compound NC1=CC=C2N(CC)C3=CC=CC=C3C2=C1 OXEUETBFKVCRNP-UHFFFAOYSA-N 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 4
- 238000005259 measurement Methods 0.000 claims description 4
- 238000000746 purification Methods 0.000 claims description 4
- 238000009776 industrial production Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 239000002808 molecular sieve Substances 0.000 claims description 3
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 238000000605 extraction Methods 0.000 claims 1
- 238000006386 neutralization reaction Methods 0.000 claims 1
- 230000015572 biosynthetic process Effects 0.000 abstract description 9
- 238000003786 synthesis reaction Methods 0.000 abstract description 9
- 230000004044 response Effects 0.000 abstract description 7
- 239000000243 solution Substances 0.000 description 36
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 18
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- 238000011088 calibration curve Methods 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 230000032050 esterification Effects 0.000 description 5
- 238000002189 fluorescence spectrum Methods 0.000 description 5
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Natural products OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 150000001450 anions Chemical class 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 235000019439 ethyl acetate Nutrition 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 230000003472 neutralizing effect Effects 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 230000035945 sensitivity Effects 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000006356 dehydrogenation reaction Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical group [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 238000007323 disproportionation reaction Methods 0.000 description 1
- 150000002168 ethanoic acid esters Chemical class 0.000 description 1
- 238000001506 fluorescence spectroscopy Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 230000004043 responsiveness Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 238000007039 two-step reaction Methods 0.000 description 1
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- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/02—Boron compounds
- C07F5/022—Boron compounds without C-boron linkages
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- 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 discloses a fluorescent probe for fluorine ion content in an acetate esterification reaction system, a preparation method thereof and a detection method using the fluorescent probe. The invention has the characteristics of low detection limit, double signal response, simple synthesis and convenient use.
Description
Technical Field
The invention relates to the technical field of fluorescent probes, in particular to a fluorescent probe for fluorine content in an acetate esterification reaction kettle, a preparation method thereof and a detection method using the fluorescent probe.
Background
The current industrialized acetic acid esterification method mainly comprises an alkyd esterification method, an acetaldehyde condensation method, an ethanol dehydrogenation disproportionation method, an ethylene addition method and the like, but in China, the esterification method and the ethanol dehydrogenation method are basically the only methods, the price of acetic acid is greatly reduced due to the large production of a domestic methanol carbonyl synthesis device, the esterification method has obvious advantages, the raw materials of the esterification method comprise acetic acid and low-carbon alcohol, such as methanol, ethanol, propanol, butanol and the like, the used catalysts comprise sulfuric acid, methanesulfonic acid, p-toluenesulfonic acid and the like, reaction equipment is often seriously corroded due to the large amount of corrosive acid in a reaction system, equipment damage is easy to find safety accidents, and the equipment investment is increased for preventing risks of enterprises. It is known that metals are corroded by a strong acid catalyst, raw material acetic acid, and corrosion of equipment is greatly accelerated if halogen ions are present in a reaction system, wherein equipment lining tetrafluoride is an important means for preventing corrosion, but on the other hand, precipitation of fluorine ions in fluororesin causes corrosion of equipment not lined with fluororesin in the reaction system. Therefore, it is necessary to periodically detect the content of fluorine ions in a reaction apparatus for industrially producing acetic acid esters, to improve the maintenance level of equipment, and to guide the correct type selection of equipment.
Disclosure of Invention
The invention mainly aims to provide a fluorescent probe for the content of fluorine ions in an acetate esterification reaction system, a preparation method thereof and a detection method using the fluorescent probe, and the fluorescent probe has the characteristics of low detection limit, simple synthesis and convenient use.
The invention can be realized by the following technical scheme:
the invention discloses a molecular structure of the fluorescent probe, which is as follows:
when the compound of the structural formula is used as a fluorescent probe, when fluorine ions are added, boron atoms on the compound can react with the fluorine ions to a certain degree to unlock the effect on B-N, and a-C-N-part can rotate again, so that conjugation of probe molecules is reduced, planarity is reduced, fluorescent emission moves to a short wavelength, yellow light is weakened, and blue-green fluorescence is enhanced.
Another aspect of the present invention is to provide a method for preparing the above fluorescent probe, comprising the steps of:
s1, preparation of intermediate product: taking 3-amino-9-ethylcarbazole and 2-hydroxy-5-bromobenzaldehyde as raw materials, adding a dry ethanol solvent under the protection of nitrogen, and carrying out heating reflux reaction to obtain an intermediate product; during the operation, the reflux reaction conditions are as follows: the oil bath is heated to reflux at 85 ℃.
Preparation of fluorescent probe compound: after the intermediate product is purified, dry dichloroethane solvent is added under the protection of nitrogen for heating reflux, and BF is slowly dropped3OEt2After the system is discolored or insoluble, dropwise adding N, N-diisopropylethylamine, and heating and refluxing for reaction to obtain the fluorescent materialA photo probe compound. In the actual operation process, the generation of insoluble substances is specifically that a large amount of insoluble substances are separated out from the system; the reflux reaction conditions were: the oil bath is heated to reflux at 85 ℃.
The preparation method comprises the following specific reaction processes:
further, the preparation method further comprises the following step S3 of purification treatment: and (4) recrystallizing and purifying the fluorescent probe compound obtained in the step S2.
Further, the dry ethanol solvent and the dry dichloroethane solvent are prepared by adding the solvent of AR grade to the dry 4A molecular sieve and drying. In practice, to ensure the effect. Drying is generally carried out for more than 8 h.
Further, the intermediate product of step S2 is purified by direct filtration and ethanol washing.
In addition, another aspect of the present invention is directed to a detection method using the above fluorescent probe, comprising the steps of:
A. pretreatment of a sample to be detected: extracting kettle liquid in a reaction kettle, and pretreating the kettle liquid of the acetate esterification reaction kettle to obtain a sample to be detected;
B. drawing a correction curve: calibrating the prepared standard fluorine ion solution to obtain a correction curve of the fluorescence intensity and the fluorine ion content;
C. preparing a fluorescent probe solution: fluorescent probes were formulated as 10-5mol/L of a fluorescent probe solution to be detected;
D. measuring the content of fluorine ions in the reaction system: and D, uniformly mixing the sample to be detected obtained in the step A with the fluorescent probe solution obtained in the step C, then carrying out fluorescence intensity measurement, and comparing the correction curve obtained in the step B to obtain the content of the fluorine ions in the kettle liquid.
Further, the pretreatment of the sample to be detected in the step A comprises one or more of filtering, extracting and neutralizing the kettle liquid. Filtering to remove insoluble substances to prevent influence on fluorescence intensity, extracting with acetate and water, collecting water phase, and neutralizing with sodium bicarbonate or sodium carbonate or sodium hydroxide solution.
The fluorescent probe for the content of fluorine ions in the acetate esterification reaction kettle, the preparation method thereof and the detection method using the fluorescent probe have the following beneficial technical effects:
the fluorescent probe has strong information contrast and selective response to fluorine ions, on one hand, the fluorescent probe molecule has the characteristic of aggregation induced luminescence, so that the fluorescent probe has good fluorescence emission in the prepared probe aqueous solution, on the other hand, the fluorine ions have selectivity and high responsiveness, and the lower detection limit reaches 0.01 ppm;
second, and the fluorescence information has a two-information response, affecting the data more accurately, with the increase in the fluorine ion content in the assay, the fluorescence of the probe at 540nm decreases, while the fluorescence signal at short wavelength (about 450 nm) increases, forming a fluorine-responsive fluorescence ratiometer.
Thirdly, the synthesis is simple, the fluorescent probe can be obtained by taking 3-amino-9-ethylcarbazole and 2-hydroxy-5-bromobenzaldehyde as raw materials through two-step reaction, the whole synthesis operation process is simple, and strict reaction synthesis and separation conditions are not needed;
fourthly, the fluorescent probe is convenient to use, is suitable for detecting the content of fluoride ions in a reaction kettle for industrial production of acetate, is operated conventionally in the whole operation process, effectively reduces the application cost and expands the application prospect.
Fifthly, the detection result can guide the production of acetate, indicate the condition of the base material in the period, improve the quality of finished products and prolong the service life of equipment.
Drawings
FIG. 1 is a graph showing the sensitivity of fluorescent response of the fluorescent probe of the present invention to different anions;
FIG. 2 is a graph showing the fluorescence response spectrum of the fluorescent probe of the present invention to a standard fluoride ion prepared.
Detailed Description
In order to make the technical solution of the present invention better understood by those skilled in the art, the following detailed description is provided for the product of the present invention with reference to the examples.
The invention discloses a structure of a molecule of the fluorescent probe, which is as follows:
to verify the response sensitivity of the fluorescent probe of the present invention, FIG. 1 provides a graph showing the fluorescence response sensitivity of the fluorescent probe of the present invention to different anions, and in the graph 1, the ordinate is the ratio of the fluorescence intensity at 450 nm to 540nm, and the anion concentration is 0.2 ppm. In this case, in the detection process, the phenomenon occurring when fluorine ions are detected is discoloration (fluorescence is turned on), and the detection process is a double signal, so that a ratio meter can be formed to improve the detection resolution.
Another aspect of the present invention is to provide a method for preparing the above fluorescent probe, comprising the steps of:
s1, preparation of intermediate product: taking 3-amino-9-ethylcarbazole and 2-hydroxy-5-bromobenzaldehyde as raw materials, adding a dry ethanol solvent under the protection of nitrogen, and carrying out heating reflux reaction to obtain an intermediate product;
preparation of fluorescent probe compound: after the intermediate product is purified, dry dichloroethane solvent is added under the protection of nitrogen for heating reflux, and BF is slowly dropped3OEt2And after the system is discolored or insoluble, dropwise adding N, N-diisopropylethylamine, and then heating and refluxing to react to obtain the fluorescent probe compound.
Further, the preparation method further comprises the following step S3 of purification treatment: and (4) recrystallizing and purifying the fluorescent probe compound obtained in the step S2.
Further, the dry ethanol solvent and the dry dichloroethane solvent are prepared by adding the solvent of AR grade to the dry 4A molecular sieve and drying.
Further, the intermediate product of step S2 is purified by direct filtration and ethanol washing.
In addition, another aspect of the present invention is directed to a detection method using the above fluorescent probe, comprising the steps of:
A. pretreatment of a sample to be detected: extracting kettle liquid in a reaction kettle, and pretreating the kettle liquid of the acetate esterification reaction kettle to obtain a sample to be detected;
B. drawing a correction curve: calibrating the prepared standard fluorine ion solution to obtain a calibration curve of the fluorescence intensity and the fluorine ion content, wherein the fluorescence spectra of different concentrations can be shown in the attached figure 2;
C. preparing a fluorescent probe solution: fluorescent probes were formulated as 10-5mol/L of a fluorescent probe solution to be detected;
D. measuring the content of fluorine ions in the reaction system: and D, uniformly mixing the sample to be detected obtained in the step A with the fluorescent probe solution obtained in the step C, then carrying out fluorescence intensity measurement, and comparing the correction curve obtained in the step B to obtain the content of the fluorine ions in the reaction system.
Further, the pretreatment of the sample to be detected in the step A comprises filtering, extracting and neutralizing the kettle liquid.
Application example 1
The invention discloses a fluorescent probe for detecting the content of fluorine ions in an esterification reaction kettle for industrial production of acetate, which is applied to the following specific application processes in practice:
synthesis of fluorescent Probe Compound: a50 mL reactor was charged with 3-amino-9-ethylcarbazole (4.92g) and 2-hydroxy-5-bromobenzaldehyde (3g), and under nitrogen, dry ethanol (50 mL) was added and the reaction was heated at 85 ℃ under reflux for 8 h. After cooling and standing, filtration and rinsing with ethanol, an intermediate product (3g) was obtained. The intermediate (1.5g) was charged into a 40mL reactor under nitrogen, dry dichloroethane (5.5mL) was added and heated at 85 deg.C under reflux, and BF was slowly added dropwise to the reactor3OEt2(1.50mL), DIEA (1.8mL) was added dropwise after a period of time for the reaction to change the color or to render the system insoluble. The reaction was heated at 85 ℃ under reflux for 8 h. Cooling to room temperature, dripping the reaction solution into 50mL of dry ethanol for crystallization, and filtering to obtain a dark orange solid productYield, yield: 42 percent.
Pretreatment of a sample to be detected: taking the bottom liquid of a reboiler or a reaction kettle, filtering to remove insoluble salt and other solids, adding water and acetic ester to extract the filtrate, and distilling and concentrating the water phase to obtain a sample.
Drawing a correction curve: and preparing solutions containing different concentrations of fluoride ions to form a calibration curve so as to measure the content of the fluoride ions by fluorescence spectroscopy of the prepared fluorescent probe solution.
Preparing a fluorescent probe solution, namely preparing 10-3Taking out acetonitrile solution of mol/L probe molecules, taking out the acetonitrile solution from 0.1mL to 10mL volumetric flask, adding deionized water to prepare 10mL solution, and uniformly oscillating to obtain 10-5mol/L fluorescent probe solution. Transferring 3mL of the fluorescent probe solution into a cuvette, adding 30 mu L of a sample aqueous solution to be tested with a certain concentration ratio of 1/1, stirring uniformly, carrying out fluorescence spectrum test, and comparing with a calibration curve to obtain the content of fluorine ions.
Application example 2
The synthesis of the fluorescent probe compounds is carried out with reference to application example 1 and will not be described again.
Pretreatment of a sample to be detected: taking the bottom liquid of a reboiler or a reaction kettle, filtering to remove insoluble salt and other solids, adding water and acetic ester to extract the filtrate, and distilling and concentrating the water phase to obtain a sample.
Drawing a correction curve: and preparing solutions containing fluoride ions with different concentrations to form a calibration curve so as to be used for the prepared fluorescent probe solution to carry out fluorescent spectrum quantitative determination.
Preparing a fluorescent probe solution, namely preparing 10-3Taking out acetonitrile solution of mol/L probe molecules, taking out the acetonitrile solution from 0.1mL to 10mL volumetric flask, adding deionized water to prepare 10mL solution, and uniformly oscillating to obtain 10-5mol/L fluorescent probe solution. Transferring 3mL of the fluorescent probe solution into a cuvette, adding 30 mu L of a sample aqueous solution to be tested with a certain concentration ratio of 10/1, stirring uniformly, carrying out fluorescence spectrum test, and comparing with a calibration curve to obtain the content of fluorine ions.
Application example 3
The synthesis of the fluorescent probe compounds is carried out with reference to application example 1 and will not be described again.
Pretreatment of a sample to be detected: taking the bottom liquid of a reboiler or a reaction kettle, filtering to remove insoluble salt and other solids, adding water and acetic ester to extract the filtrate, and distilling and concentrating the water phase to obtain a sample.
Drawing a correction curve: and preparing a solution shape correction curve containing different concentrations of fluoride ions so as to determine the content of the fluoride ions by performing fluorescence spectrum measurement on the prepared fluorescent probe solution.
Preparing a fluorescent probe solution, namely preparing 10-3Taking out acetonitrile solution of mol/L probe molecules, taking out the acetonitrile solution from a 0.1mL volumetric flask to a 10mL volumetric flask, adding deionized water to prepare 10mL solution, and uniformly oscillating to obtain 10-5mol/L fluorescent probe solution. Transferring 3mL of the fluorescent probe solution into a cuvette, adding 30 mu L of a sample aqueous solution to be tested with a certain concentration ratio of 100/1, stirring uniformly, carrying out fluorescence spectrum test, and comparing with a calibration curve to obtain the content of fluorine ions.
The foregoing is merely a preferred embodiment of the invention and is not intended to limit the invention in any manner; as will be apparent to those skilled in the art from this disclosure, the present invention may be practiced without these specific details; however, those skilled in the art should appreciate that they can readily use the disclosed conception and specific embodiments as a basis for designing or modifying other structures for carrying out the same purposes of the present invention; meanwhile, any changes, modifications, and evolutions of the equivalent changes of the above embodiments according to the actual techniques of the present invention are still within the protection scope of the technical solution of the present invention.
Claims (7)
1. A fluorescent probe for detecting the content of fluorine ions in an esterification reaction kettle for industrial production of acetate is characterized in that: the structure of the molecule of the fluorescent probe is as follows:
2. a method for preparing the fluorescent probe of claim 1, characterized by comprising the steps of:
s1, preparation of intermediate product: taking 3-amino-9-ethylcarbazole and 2-hydroxy-5 bromobenzaldehyde as raw materials, adding a dry ethanol solvent under the protection of nitrogen, and carrying out heating reflux reaction to obtain an intermediate product;
s2, preparation of fluorescent probe compound: after the intermediate product is purified, dry dichloroethane solvent is added under the protection of nitrogen for heating reflux, and BF is slowly dropped3OEt2And after the system is discolored or insoluble, dropwise adding N, N-diisopropylethylamine, and then heating and refluxing to react to obtain the fluorescent probe compound.
3. The method for preparing a fluorescent probe according to claim 2, characterized in that: further comprising the following step S3 of purification: and (4) recrystallizing and purifying the fluorescent probe compound obtained in the step S2.
4. The method for preparing a fluorescent probe according to claim 3, characterized in that: the dry ethanol solvent and dry dichloroethane solvent are prepared by adding the AR grade solvent to a dry 4A molecular sieve and drying.
5. The method for preparing a fluorescent probe according to claim 4, characterized in that: the purification mode of the intermediate product in the step S2 is direct filtration and ethanol washing.
6. A detection method using the fluorescent probe according to claim 1, characterized by comprising the steps of:
A. pretreatment of a sample to be detected: extracting kettle liquid in a reaction kettle, and pretreating the kettle liquid of the acetate esterification reaction kettle to obtain a sample to be detected;
B. drawing a correction curve: calibrating the prepared standard fluorine ion solution to obtain a correction curve of the fluorescence intensity and the fluorine ion content;
C. fluorescent probePreparing a solution: fluorescent probes were formulated as 10-5 mol/L of a fluorescent probe solution to be detected;
D. measuring the content of fluorine ions in the reaction system: and D, uniformly mixing the sample to be detected obtained in the step A and the fluorescent probe solution obtained in the step C, then carrying out fluorescence intensity measurement, and comparing the correction curve obtained in the step B to obtain the content of the fluorine ions in the reaction system.
7. The detection method using a fluorescent probe according to claim 6, characterized in that: the pretreatment of the sample to be detected in the step A comprises one or more of filtration, extraction and neutralization of the kettle liquid.
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Non-Patent Citations (2)
| Title |
|---|
| "A simplecomplex: ‘on–off–on’ colorimetric and ratiometric fluorescence response towards fluoride ions and its solid stateoptical properties";Shengying Wu等;《Tetrahedron Letters》;20160221;第57卷;第1390-1395页 * |
| "Carbazole-based salicylaldimine difluoroboron complex with crystallization-induced emission enhancement and reversible piezofluorochromism characteristics";Yong Zhan等;《Tetrahedron Letters》;20161024;第57卷;第5385-8389页 * |
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