CN115096862B - Ratio type fluorescence detection method for rapidly detecting trace water in organic solvent - Google Patents
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 113
- 238000000034 method Methods 0.000 title claims abstract description 33
- 239000003960 organic solvent Substances 0.000 title claims abstract description 27
- 238000001917 fluorescence detection Methods 0.000 title claims abstract description 15
- 150000003220 pyrenes Chemical class 0.000 claims abstract description 33
- 239000012086 standard solution Substances 0.000 claims abstract description 12
- 238000002360 preparation method Methods 0.000 claims abstract description 8
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 103
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 51
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 51
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 49
- 239000000243 solution Substances 0.000 claims description 31
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 30
- 238000002189 fluorescence spectrum Methods 0.000 claims description 18
- 238000001514 detection method Methods 0.000 claims description 17
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 16
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 15
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 12
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 10
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 10
- 238000004364 calculation method Methods 0.000 claims description 10
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 10
- -1 pyrene formaldehyde hydrazone Chemical compound 0.000 claims description 10
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 8
- SMQUZDBALVYZAC-UHFFFAOYSA-N salicylaldehyde Chemical compound OC1=CC=CC=C1C=O SMQUZDBALVYZAC-UHFFFAOYSA-N 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- 238000004440 column chromatography Methods 0.000 claims description 6
- 239000003480 eluent Substances 0.000 claims description 6
- 238000012417 linear regression Methods 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- 238000001228 spectrum Methods 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- 238000010521 absorption reaction Methods 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 229960000583 acetic acid Drugs 0.000 claims description 3
- 239000000706 filtrate Substances 0.000 claims description 3
- 238000001506 fluorescence spectroscopy Methods 0.000 claims description 3
- 239000012362 glacial acetic acid Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 239000003208 petroleum Substances 0.000 claims description 3
- 239000011550 stock solution Substances 0.000 claims description 3
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 3
- 239000012498 ultrapure water Substances 0.000 claims description 3
- 150000007960 acetonitrile Chemical class 0.000 claims description 2
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- 238000010790 dilution Methods 0.000 claims description 2
- 239000012895 dilution Substances 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 238000004140 cleaning Methods 0.000 claims 1
- 239000007788 liquid Substances 0.000 abstract description 3
- 230000035945 sensitivity Effects 0.000 abstract description 3
- 125000005581 pyrene group Chemical group 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000010586 diagram Methods 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 238000001819 mass spectrum Methods 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 230000005284 excitation Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000000835 electrochemical detection Methods 0.000 description 1
- 238000002795 fluorescence method Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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- 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
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Abstract
The invention discloses a ratio type fluorescence detection method for rapidly detecting trace water in an organic solvent, which comprises the following steps: (1) preparation of pyrene derivative fluorescence sensor storage liquid; (2) preparing a standard solution; and (3) drawing a standard curve to obtain various linear equations. The fluorescence sensor for detecting the trace water in the organic solvent is a pyrene derivative, the preparation process is simple, and the process for detecting the trace water in the organic solvent has the advantages of simplicity in operation, extremely fast response, high sensitivity, good selectivity and low cost.
Description
Technical Field
The invention belongs to the technical field of electrochemical detection methods, and particularly relates to a ratio type fluorescence detection method for rapidly detecting trace water in an organic solvent.
Background
Among many organic solvents, water is a common impurity. The small amount of water in the organic solvent has a great influence on the products of the chemical reaction, the yield and the selectivity of the reaction, and even generates serious accident risks. Therefore, detection of minute amounts of water is of great importance in a variety of fields of chemistry and industry. Therefore, the establishment of the method for measuring the water content in the organic solvent, which is simple and convenient to operate, low in cost, sensitive and rapid, becomes a target.
The traditional method for detecting the water content has the defects of low reaction rate, easiness in interference, low sensitivity, poor precision, complex reagent preparation, complex detection operation and the like.
Disclosure of Invention
Aiming at the technical problems that the prior art has high use cost, needs professional technicians, has complex detection process, almost needs complicated pretreatment process, is time-consuming to operate and has no advantage in quick detection of samples, the invention provides a fluorescence detection method for quickly detecting the micro water in the organic solvent, and aims to obtain a method for quickly detecting the micro water in the organic solvent, which is simple to operate by using a fluorescence method, has low cost and is sensitive.
In order to achieve the above purpose, the technical scheme provided by the invention is as follows:
a fluorescence detection method for rapidly detecting the ratio of trace water in an organic solvent comprises the following operation steps:
(1) Preparation of pyrene derivative fluorescence sensor stock solution: dissolving 1-pyrene formaldehyde in tetrahydrofuran solution, stirring at room temperature to dissolve completely, adding hydrazine hydrate, stirring at room temperature, vacuum filtering the reaction product, washing with diethyl ether, and drying to obtain pyrene formaldehyde hydrazone; dissolving the obtained pyrene formaldehyde hydrazone and 4-tertiary butyl-2, 6-formylphenol in tetrahydrofuran, dropwise adding glacial acetic acid, reacting for 24 hours at normal temperature, filtering, concentrating the filtrate, separating and purifying by using a column chromatography, and standing to volatilize a solvent to finally obtain a pyrene derivative solid; dissolving pyrene derivative solid in dimethyl sulfoxide to prepare a storage solution of a pyrene derivative fluorescence sensor;
(2) Preparing a standard solution: adding a certain amount of ultrapure water into acetonitrile to prepare acetonitrile storage solution with the mass concentration of 20%; taking acetonitrile storage liquid (aqueous acetonitrile storage liquid), and adding acetonitrile for respective dilution to obtain a series of acetonitrile standard solutions with water content; preparing standard solutions of N, N-dimethylformamide, ethanol and methanol with corresponding water contents according to the same method;
(3) Drawing a standard curve: mixing the storage solution of the pyrene derivative fluorescence sensor obtained in the step (1) with the acetonitrile solution obtained in the step (2), performing fluorescence emission spectrum scanning within the absorption wavelength range of 375-700 nm, recording the spectrum, drawing a standard curve by using the measured fluorescence intensity and water content value, and calculating to obtain a linear regression equation; in the process of actually detecting the water content in the organic solvent, replacing the standard solution with a sample to be detected, performing fluorescence spectrum scanning, recording a spectrum, substituting the measured related fluorescence data into the corresponding linear equation, and calculating to obtain the water content in the sample to be detected;
the linear equation is:
Standard curve for water in acetonitrile: the fluorescence intensity ratio at 440nm and 390nm is in good linear relation with the water content in the ranges of 0.2-4.0% and 4.0-10.0%, a standard curve and a linear equation are calculated, the obtained linear equation is F 440nm/390nm＝0.4138+0.1618C1 (0-4.0% and a correlation coefficient R 2＝0.9960),F440nm/390nm＝0.4638+0.3883C1 (4.0-10.0% and a correlation coefficient R 2 = 0.9966) respectively, wherein F 440nm/390nm is the fluorescence intensity ratio at 440nm and 390nm, C 1 is the water content in acetonitrile, and the detection limit is 0.0034% according to LOD=3SD/K;
The same procedure was used to plot the standard curves for water content in N, N-dimethylformamide, ethanol and methanol, and the standard curves for water in N, N-dimethylformamide: the fluorescence intensity at 389nm and the water content at 0-2.5% are in good linear relation, the fluorescence intensity at 437nm and the water content at 3.0-6.0% are in good linear relation, a standard curve and a linear equation are obtained through calculation, the obtained linear equation is F 389nm＝671.00-135.39C2 (0-2.5%, correlation coefficient R 2＝0.9955),F437nm＝201.25+204.08C2 (3.0-6.0% and correlation coefficient R 2 =0.9975), wherein F 389nm is the fluorescence intensity at 389nm, F 437nm is the fluorescence intensity at 437nm, C 2 is the water content in N, N-dimethylformamide, and the detection limit is 0.046%;
standard curve for water in ethanol: the fluorescence intensity at 450nm and the water content at 0-10.0% are in good linear relation, a standard curve and a linear equation are obtained through calculation, and the obtained linear equation is F 450nm＝799.51+100.64C3 (0-10.0% and a correlation coefficient R 2 =0.9967) respectively; wherein F 450nm is fluorescence intensity at 450nm, C 3 is water content in ethanol, and the detection limit is: 0.082%;
standard curve for water in methanol: the fluorescence intensity at 456nm and the water content at 0-8.0% are in good linear relation, a standard curve and a linear equation are obtained through calculation, the obtained linear equation is F 456nm＝1158.57+104.09C4 (0-8.0% and correlation coefficient R 2 = 0.9923), wherein F 456nm is the fluorescence intensity at 456nm, C 4 is the water content in methanol, and the detection limit is: 0.066%.
Preferably, the amount of 1-pyrene formaldehyde in the step (1) is 0.5756g (2.5 mmol) and the amount of tetrahydrofuran is 10mL.
Preferably, the volume percentage of the hydrazine hydrate in the step (1) is 25%, the dosage is 4.85mL (25 mmol), and the mass ratio of the 1-pyrene formaldehyde to the hydrazine hydrate is 1:10; the reaction time of 1-pyrene formaldehyde and hydrazine hydrate was 12 hours.
Preferably, the mass ratio relationship of pyrene formaldehyde hydrazone and 4-tertiary butyl-2, 6-formylphenol in the step (1) is 1:1.1; the reaction time of pyrene formaldehyde hydrazone and 4-tert-butyl-2, 6-formylphenol was 24 hours.
Preferably, the eluent in the column chromatography in the step (1) is petroleum ether and ethyl acetate, and the volume ratio of the eluent to the ethyl acetate is 16:1, 12:1, 10:1,8:1,6:1 and 4:1 in sequence.
Preferably, in the step (1), a reservoir solution of a pyrene derivative fluorescence sensor having a concentration of 40. Mu. Mol/L is prepared.
Compared with the prior art, the invention has the following beneficial effects:
The fluorescence sensor for detecting the trace water in the organic solvent is a pyrene derivative, the preparation process is simple, and the process for detecting the trace water in the organic solvent has the advantages of simplicity in operation, extremely fast response, high sensitivity, good selectivity and low cost.
Drawings
FIG. 1 is a mass spectrum of a pyrene derivative biosolids prepared by the invention (1).
FIG. 2 is a fluorescence spectrum and standard curve of the water content in acetonitrile according to the method of the invention; wherein a is a fluorescence spectrum diagram of acetonitrile with different water contents in pyrene derivative fluorescence sensor solution; b is a standard curve of the ratio of fluorescence intensities at 440nm and 390nm and the water content corresponding thereto.
FIG. 3 is a fluorescence spectrum and standard chart of the water content in N, N-dimethylformamide; wherein a is a fluorescence spectrum diagram of N, N-dimethylformamide with different water contents in pyrene derivative fluorescence sensor solution; b is a standard curve of fluorescence intensity at 389 and 437nm and corresponding water content.
FIG. 4 is a fluorescence spectrum and standard graph of water content in ethanol; wherein a is a fluorescence spectrum diagram of ethanol with different water contents in pyrene derivative fluorescence sensor solution; b is a standard curve of the fluorescence intensity ratio at 450nm and the corresponding water content.
FIG. 5 is a fluorescence spectrum and standard graph of water content in methanol; wherein a is a fluorescence spectrum diagram of methanol with different water contents in pyrene derivative fluorescence sensor solution; b is a standard curve of fluorescence intensity ratio at 456nm and corresponding water content.
Detailed Description
The following detailed description, in conjunction with the accompanying drawings, describes in detail, but it is to be understood that the scope of the invention is not limited to the specific embodiments. The raw materials and reagents used in the examples were commercially available unless otherwise specified.
Example 1
A fluorescence detection method for rapidly detecting the ratio of trace water in an organic solvent comprises the following specific operation steps:
(1) Preparation of pyrene derivative fluorescence sensor stock solution: 0.5756g (2.5 mmol) of 1-pyrene formaldehyde is dissolved in 10mL of tetrahydrofuran solution, stirred at room temperature to be completely dissolved, hydrazine hydrate with the volume percentage of 25 percent and the dosage of 4.85mL (25 mmol) is added, the mass ratio of the 1-pyrene formaldehyde to the hydrazine hydrate is 1:10, the mixture is stirred at room temperature for reaction for 12 hours, the product obtained by the reaction is decompressed, pumped and filtered, washed by diethyl ether and dried to obtain pyrene formaldehyde hydrazone; taking 0.2441g (1.0 mmol) of pyrene formaldehyde hydrazone and 0.2268g (1.1 mmol) of 4-tertiary butyl-2, 6-formylphenol, dissolving in 10mL of tetrahydrofuran, dropwise adding 100 mu L of glacial acetic acid, reacting for 24 hours at normal temperature, filtering, concentrating filtrate, separating and purifying by using a column chromatography, wherein the eluent of the column chromatography is petroleum ether and ethyl acetate, and the volume ratio of the eluent is 16:1, 12:1, 10:1,8:1,6:1,4:1 in sequence, standing to volatilize solvent, and finally obtaining pyrene derivative solid; the pyrene derivative obtained by preparation is subjected to mass spectrometry, and the result is shown in figure 1; 0.0864g of pyrene derivative solid is dissolved in 50mL of dimethyl sulfoxide to obtain 4X 10 -3 mol/L pyrene derivative solution, 0.5mL of pyrene derivative solution (4X 10 -3 mol/L) is gradually diluted to 50mL by adding dimethyl sulfoxide, and a storage solution of a pyrene derivative fluorescence sensor with the concentration of 40 mu mol/L is prepared; the volume ratio of the solvent dimethyl sulfoxide to water is 2:1;
(2) Preparing a standard solution: taking 5mL of ultrapure water, gradually adding 20mL of acetonitrile to obtain acetonitrile storage solution with the water content of 20%, taking the acetonitrile storage solution, adding acetonitrile to dilute respectively, and fixing the volume to obtain acetonitrile standard solutions with the water content of 0.2%,0.4%,0.8%,1.6%,2.0%,3.0%,4.0%,5.0%,6.0%,7.0%,8.0%,9.0%,10.0%,12.0%,16.0% and 20.0%; preparing standard solutions of N, N-dimethylformamide, ethanol and methanol with corresponding water contents according to the same method; ;
(3) Drawing a standard curve: using a fluorescence spectrophotometer of the 960MC type, the spectral scanning parameters were set as follows: the measurement mode is wavelength scanning, the scanning mode is an emission mode, the excitation wavelength is 360nm, the scanning speed is 1000nm/min, the scanning interval is 1nm, and the excitation bandwidth and the emission bandwidth are 2nm; mixing the storage solution (40 mu mol/L) of the pyrene derivative fluorescence sensor obtained in the step (1) with the acetonitrile solution obtained in the step (2) according to the volume ratio of 1:1, carrying out fluorescence emission spectrum scanning within the absorption wavelength range of 375-700 nm, recording spectra, drawing a standard curve by using a fluorescence intensity value measured at 456nm, and calculating to obtain a linear regression equation, wherein the concentration of the pyrene derivative fluorescence sensor is 20 mu mol/L, the content of acetonitrile is 0.1%,0.2%,0.4%,0.8%,1.0%,1.5%,2.0%,2.5%,3.0%,3.5%,4.0%,4.5%,5.0%,6.0%,8.0%,10.0%,440nm and 390nm are in good linear relation with the content of water within the range of 0-4.0% and 4.0-10.0%, the obtained linear regression equation is F 440nm/390nm＝0.4138+0.1618C1 (0-4.0%, correlation coefficient R 2＝0.9960),F440nm/390nm＝0.4638+0.3883C1 (4.0-10.0%, correlation coefficient R32%, 3.0%, 3=3725) and the water content of the fluorescence intensity of the fluorescence sensor is 35.0% at the position of the absorption wavelength of 375 nm is 375.0-700 nm, and the water content of the acetonitrile solution is 35:3;
The standard curves for the water content in N, N-dimethylformamide, ethanol and methanol were plotted in the same manner. Standard curve for water in N, N-dimethylformamide: the fluorescence intensity at 389nm and the water content at 0-2.5% are in good linear relation, the fluorescence intensity at 437nm and the water content at 3.0-6.0% are in good linear relation, a standard curve and a linear equation are obtained through calculation, the obtained linear equation is F 389nm＝671.00-135.39C2 (0-2.5%, correlation coefficient R 2＝0.9955),F437nm＝201.25+204.08C2 (3.0-6.0% and correlation coefficient R 2 =0.9975), wherein F 389nm is the fluorescence intensity at 389nm, F 437nm is the fluorescence intensity at 437nm, C 2 is the water content in N, N-dimethylformamide, and the detection limit is 0.046%;
standard curve for water in ethanol: the fluorescence intensity at 450nm and the water content at 0-10.0% are in good linear relation, a standard curve and a linear equation are obtained through calculation, and the obtained linear equation is F 450nm＝799.51+100.64C3 (0-10.0% and a correlation coefficient R 2 =0.9967) respectively; wherein F 450nm is fluorescence intensity at 450nm, C 3 is water content in ethanol, and the detection limit is: 0.082%;
Standard curve for water in methanol: the fluorescence intensity at 456nm and the water content at 0-8.0% are in good linear relation, a standard curve and a linear equation are obtained through calculation, and the obtained linear equation is F 456nm＝1158.57+104.09C4 (0-8.0% and a correlation coefficient R 2 = 0.9923) respectively; wherein F 456nm is fluorescence intensity at 456nm, C 4 is water content in methanol, and the detection limit is: 0.066%; substituting the measured fluorescence intensity of the sample into the linear equation of fig. 2-5 b;
In the process of actually detecting the water content in the organic solvent, directly taking purchased Acetonitrile (AR), N-dimethylformamide (AR), 95% ethanol (AR) and methanol (AR) as samples to be detected, and taking 2mL of samples; replacing the acetonitrile solution in the step (3) with a sample to be detected, performing fluorescence spectrum scanning within the wavelength range of 375-700 nm according to the same operation, recording the spectrum, substituting the measured related fluorescence data into the obtained linear regression equation, calculating the water content of different organic solvents in the sample to be detected, and calculating the standard adding recovery rate, wherein the result is shown in the table 1:
TABLE 1 Water content in commercial organic reagents labeled recovery determination results
From Table 1, the actual sample detection recovery rate is between 96.0 and 111.0%, which shows that the fluorescence detection method for the water content in the organic solvent provided by the invention has good practicability and accuracy.
Fig. 1 is a mass spectrum of the pyrene derivative biosolids prepared by the method (1), and from the mass spectrum shown in fig. 1, a proton peak appears at m/z= 433.19, which corresponds to the theoretical value of m/z= 433.18, and indicates that the pyrene derivative is successfully synthesized in the step (1).
FIG. 2a is a graph showing fluorescence spectra of acetonitrile with different water contents in pyrene derivative fluorescence sensor solutions. As shown in the figure, as the water content in acetonitrile increases, the fluorescence emission peak at 440nm gradually increases, and the fluorescence emission peak at 390nm gradually decreases; b is a standard curve of fluorescence intensity ratio at 440nm and 390nm and water content corresponding to the ratio; as shown in the figure, the water content in the range of 0-4.0% and 4.0-10.0% shows a good linear relationship, and the obtained linear regression equations are F 440nm/390nm＝0.4138+0.1618C1(0～4.0％),F440nm/390nm＝0.4638+0.3883C1 (4.0-10.0%).
FIG. 3a is a graph showing fluorescence spectra of N, N-dimethylformamide having different water contents in a pyrene derivative fluorescence sensor solution. As shown in the figure, with the increase of the water content in the N, N-dimethylformamide, the fluorescence emission peak at 437nm gradually increased, and the fluorescence emission peak at 389nm gradually decreased; b is a standard curve of fluorescence intensity at 437nm and 389nm with their corresponding water content. As shown in the figure, the fluorescence intensity at 389nm and the water content at 0-2.5% are in good linear relation, the fluorescence intensity at 437nm and the water content at 3.0-6.0% are in good linear relation, and a standard curve and a linear equation are calculated, wherein the obtained linear equations are F 389nm＝671.00-135.39C2 (0-2.5%, a correlation coefficient R 2＝0.9955),F437nm＝201.25+204.08C2 (3.0-6.0% and a correlation coefficient R 2 =0.9975) respectively.
FIG. 4a is a graph showing fluorescence spectra of ethanol with different water contents in pyrene derivative fluorescence sensor solutions. As shown in the figure, as the water content in ethanol increases, the fluorescence emission peak at 450nm increases gradually; b is the ratio of fluorescence intensity at 450nm and the standard curve of the corresponding water content. As shown in the figure, the fluorescence intensity at 450nm and the water content at 0-10.0% are in good linear relation, a standard curve and a linear equation are obtained through calculation, and the obtained linear equation is F 450nm＝799.51+100.64C3 respectively.
FIG. 5a is a graph showing fluorescence spectra of methanol with different water contents in pyrene derivative fluorescence sensor solutions; as shown in the figure, the fluorescence emission peak at 456nm is gradually increased with the increase of the water content in methanol; b is the ratio of fluorescence intensity at 456nm and the standard curve corresponding to the water content. As shown in the figure, the fluorescence intensity at 456nm has a good linear relationship with the water content of 0-8.0%, and a standard curve and a linear equation are calculated, wherein the obtained linear equation is F 456nm＝1158.57+104.09C4 respectively.
The fluorescence detection method has the characteristics of simple operation, low cost, quick response, short reaction time, good reproducibility and the like, and can be a reliable means for low-cost and quick detection of trace water content in an organic solvent.
The foregoing descriptions of specific exemplary embodiments of the present invention are presented for purposes of illustration and description. It is not intended to limit the invention to the precise form disclosed, and obviously many modifications and variations are possible in light of the above teaching. The exemplary embodiments were chosen and described in order to explain the specific principles of the invention and its practical application to thereby enable one skilled in the art to make and utilize the invention in various exemplary embodiments and with various modifications as are suited to the particular use contemplated. It is intended that the scope of the invention be defined by the claims and their equivalents.
Claims (6)
1. A fluorescence detection method for rapidly detecting the ratio of trace water in an organic solvent, which is characterized by comprising the following operation steps:
(1) Preparation of pyrene derivative fluorescence sensor stock solution: dissolving 1-pyrene formaldehyde in tetrahydrofuran solution, stirring to dissolve completely, adding hydrazine hydrate, stirring, filtering the reaction product, cleaning and drying to obtain pyrene formaldehyde hydrazone; dissolving the obtained pyrene formaldehyde hydrazone and 4-tertiary butyl-2, 6-formylphenol in tetrahydrofuran, dropwise adding glacial acetic acid, reacting for 24 hours at normal temperature, filtering, concentrating the filtrate, separating and purifying by using a column chromatography, and standing to volatilize a solvent to finally obtain a pyrene derivative solid; dissolving pyrene derivative solid in dimethyl sulfoxide to prepare a storage solution of a pyrene derivative fluorescence sensor;
(2) Preparing a standard solution: adding a certain amount of ultrapure water into acetonitrile to prepare acetonitrile storage solution with the mass concentration of 20%; taking acetonitrile storage solution, adding acetonitrile for respective dilution to obtain a series of acetonitrile standard solutions with water content; preparing standard solutions of N, N-dimethylformamide, ethanol and methanol with corresponding water contents according to the same method;
(3) Drawing a standard curve: mixing the storage solution of the pyrene derivative fluorescence sensor obtained in the step (1) with the acetonitrile solution obtained in the step (2), performing fluorescence emission spectrum scanning within the absorption wavelength range of 375-700 nm, recording the spectrum, drawing a standard curve by using the measured fluorescence intensity and water content value, and calculating to obtain a linear regression equation; in the process of actually detecting the water content in the organic solvent, replacing the standard solution with a sample to be detected, performing fluorescence spectrum scanning, recording a spectrum, substituting the measured related fluorescence data into the corresponding linear equation, and calculating to obtain the water content in the sample to be detected;
the linear equation is:
Standard curve for water in acetonitrile: the fluorescence intensity ratio at 440nm and 390nm is in good linear relation with the water content in the ranges of 0.2-4.0% and 4.0-10.0%, a standard curve and a linear equation are calculated, the obtained linear equation is F 440nm/390nm＝0.4138+0.1618C1 (0-4.0% and a correlation coefficient R 2＝0.9960),F440nm/390nm＝0.4638+0.3883C1 (4.0-10.0% and a correlation coefficient R 2 = 0.9966) respectively, wherein F 440nm/390nm is the fluorescence intensity ratio at 440nm and 390nm, C 1 is the water content in acetonitrile, and the detection limit is 0.0034% according to LOD=3SD/K;
The same procedure was used to plot the standard curves for water content in N, N-dimethylformamide, ethanol and methanol, and the standard curves for water in N, N-dimethylformamide: the fluorescence intensity at 389nm and the water content at 0-2.5% are in good linear relation, the fluorescence intensity at 437nm and the water content at 3.0-6.0% are in good linear relation, a standard curve and a linear equation are obtained through calculation, the obtained linear equation is F 389nm＝671.00-135.39C2 (0-2.5%, correlation coefficient R 2＝0.9955),F437nm＝201.25+204.08C2 (3.0-6.0% and correlation coefficient R 2 =0.9975), wherein F 389nm is the fluorescence intensity at 389nm, F 437nm is the fluorescence intensity at 437nm, C 2 is the water content in N, N-dimethylformamide, and the detection limit is 0.046%;
standard curve for water in ethanol: the fluorescence intensity at 450nm and the water content at 0-10.0% are in good linear relation, a standard curve and a linear equation are obtained through calculation, and the obtained linear equation is F 450nm＝799.51+100.64C3 (0-10.0% and a correlation coefficient R 2 =0.9967) respectively; wherein F 450nm is fluorescence intensity at 450nm, C 3 is water content in ethanol, and the detection limit is: 0.082%;
standard curve for water in methanol: the fluorescence intensity at 456nm and the water content at 0-8.0% are in good linear relation, a standard curve and a linear equation are obtained through calculation, the obtained linear equation is F 456nm＝1158.57+104.09C4 (0-8.0% and correlation coefficient R 2 = 0.9923), wherein F 456nm is the fluorescence intensity at 456nm, C 4 is the water content in methanol, and the detection limit is: 0.066%.
2. The fluorescence detection method for rapidly detecting the ratio of a trace amount of water in an organic solvent according to claim 1, wherein: the amount of 1-pyrene formaldehyde in the step (1) was 0.5756g (2.5 mmol), and the amount of tetrahydrofuran was 10mL.
3. The fluorescence detection method for rapidly detecting the ratio of a trace amount of water in an organic solvent according to claim 1, wherein: the volume percentage of the hydrazine hydrate in the step (1) is 25%, the dosage is 4.85mL (25 mmol), and the mass ratio of the 1-pyrene formaldehyde to the hydrazine hydrate is 1:10; the reaction time of 1-pyrene formaldehyde and hydrazine hydrate was 12 hours.
4. The fluorescence detection method for rapidly detecting the ratio of a trace amount of water in an organic solvent according to claim 1, wherein: in the step (1), the mass ratio relationship of pyrene formaldehyde hydrazone and 4-tertiary butyl-2, 6-formylphenol is 1:1.1; the reaction time of pyrene formaldehyde hydrazone and 4-tert-butyl-2, 6-formylphenol was 24 hours.
5. The fluorescence detection method for rapidly detecting the ratio of a trace amount of water in an organic solvent according to claim 1, wherein: the eluent of the column chromatography in the step (1) is petroleum ether and ethyl acetate, and the volume ratio of the eluent to the ethyl acetate is 16:1, 12:1, 10:1,8:1,6:1 and 4:1 in sequence.
6. The fluorescence detection method for rapidly detecting the ratio of a trace amount of water in an organic solvent according to claim 1, wherein: in the step (1), a reservoir solution of a pyrene derivative fluorescence sensor having a concentration of 40. Mu. Mol/L was prepared.
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