CN113248512B - Fluorescent probe for detecting trace water in organic solvent and preparation method and application thereof - Google Patents

Fluorescent probe for detecting trace water in organic solvent and preparation method and application thereof Download PDF

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CN113248512B
CN113248512B CN202110669839.4A CN202110669839A CN113248512B CN 113248512 B CN113248512 B CN 113248512B CN 202110669839 A CN202110669839 A CN 202110669839A CN 113248512 B CN113248512 B CN 113248512B
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organic solvent
fluorescent probe
water
water content
fluorescence
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CN113248512A (en
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谭天水
庄汝栋
汤日元
郝燕娟
邹建平
李丰
毓志超
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Guangzhou Zhihui Biotechnology Co ltd
Guangzhou Huibiao Testing Technology Center
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Guangzhou Huibiao Testing Technology Center
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    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D491/00—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00
    • C07D491/12—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00 in which the condensed system contains three hetero rings
    • C07D491/14—Ortho-condensed systems
    • C07D491/147—Ortho-condensed systems the condensed system containing one ring with oxygen as ring hetero atom and two rings with nitrogen as ring hetero atom
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    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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    • 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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    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
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    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1044—Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms
    • C09K2211/1048—Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms with oxygen
    • 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"
    • G01N2021/6432—Quenching

Abstract

The invention discloses a fluorescent probe for detecting trace water in an organic solvent, and a preparation method and application thereof, wherein the fluorescent probe is 7-nitrodibenzo [2', 3': 6',7']Oximeridine [4', 5': 4,5]Imidazo [1, 2-a ]]Pyridine, the structural feature of which is shown as formula I; the fluorescence probe and water molecules in the organic solvent form hydrogen bonds to cause fluorescence to weaken or quench, the fluorescence intensity of the fluorescence probe can weaken along with the increase of the water content in the organic solvent, the ratio of the water content in the organic solvent to the fluorescence intensity is measured by means of a fluorescence spectrophotometer, a standard curve is drawn, and qualitative and quantitative determination of trace water in the organic solvent is achieved.
Figure DEST_PATH_IMAGE001
Formula I.

Description

Fluorescent probe for detecting trace water in organic solvent and preparation method and application thereof
Technical Field
The invention relates to the field of organic solvent detection, in particular to a fluorescent probe for detecting trace water in an organic solvent and a preparation method and application thereof.
Background
Trace amount of water is one of the most common impurities in organic solvents, and the control of water content in organic solvents is of great significance in practical applications such as drug synthesis, food processing, biopharmaceuticals, environmental monitoring, and the like. For example, in the field of organic synthesis, trace amounts of water in the reaction solvent often affect the progress, selectivity, product and yield of the reaction; in the medical field, trace amounts of water in a medicament may cause a reduction in the efficacy of the medicament, or even cause unwanted side effects of the medicament; high-purity organic solvents are generally used for cleaning the integrated circuit board, and trace water can affect the performance of the circuit board. At present, the determination of the water content in the reagent is usually carried out by the conventional Karl Fischer titration method. However, this method has some disadvantages, such as cumbersome operation and use of toxic pyridine reagents.
In recent years, fluorescent probe technology has attracted much attention by researchers due to its high efficiency, sensitivity, real-time, and other properties. However, the research on the application of fluorescent probes to the detection of trace water in organic solvents has been relatively rare so far, and it is urgently needed to develop a fluorescent probe for detecting trace water in organic solvents and a fluorescent detection method for rapidly and effectively determining trace water in organic solvents.
Disclosure of Invention
The invention aims to provide a fluorescent probe for detecting trace water in an organic solvent and a preparation method and application thereof.
According to one aspect of the present invention, there is provided a fluorescent probe for detecting trace amounts of water in an organic solvent, the fluorescent probe being 7-nitrodibenzo [2', 3': 6', 7' ] oxaheptaridine [4', 5': the structural characteristics of the 4,5] imidazo [1, 2-a ] pyridine are shown in a formula I:
Figure 501899DEST_PATH_IMAGE001
formula I.
In some embodiments, a method for preparing a fluorescent probe for detecting trace amounts of water in an organic solvent comprises the following steps:
step 1, adding 2' -hydroxyacetophenone, 2-aminopyridine, zinc iodide, 1, 10-phenanthroline, anhydrous copper acetate and o-dichlorobenzene into a closed container, keeping air in the container, heating and stirring, and performing heating reflux reaction to obtain 2- (imidazo [1, 2a ] pyridine) phenol;
step 2, adding the 2- (imidazo [1, 2a ] pyridine) phenol obtained in the step 1, 2, 4-dinitrochlorobenzene, alkali and acetonitrile into a closed container, vacuumizing the closed container, filling inert gas for replacement, adding a dry reaction solvent into the closed container, sealing, heating and stirring, and performing heating reflux reaction to obtain an intermediate;
step 3, heating the intermediate to react, and obtaining a crude product mixed solution after the reaction is completed;
and 4, after the crude product mixed liquor is cooled, washing the closed container by using dichloromethane, transferring the crude product mixed liquor in the closed container to a separating funnel, washing the crude product mixed liquor by using saturated salt water, separating to obtain an organic phase layer, adding a drying agent into the organic phase layer, drying, performing suction filtration after drying, removing the drying agent to obtain a filtrate, concentrating the filtrate, loading the sample, and performing purification treatment through a silica gel column to obtain the fluorescent probe. The alkali is used as a catalyst in the reaction for preparing the fluorescent probe, and plays a catalytic role.
In some embodiments, the base is KHCO3、K2CO3、KOH、NaOH、NaHCO3Or Na2CO3In the step 2, the reaction solvent is one of acetonitrile, dimethylformamide, ethyl acetate, dichloromethane, tetrahydrofuran, 1, 4-dioxane or acetone.
In some embodiments, the temperature of the heating reflux reaction in step 2 is 60 ℃ to 100 ℃, the inert gas is nitrogen, and the temperature of the heating reaction in step 2 is 60 ℃ to 120 ℃.
In some embodiments, the molar ratio of 2- (imidazo [1, 2a ] pyridine) phenol to 2, 4-dinitrochlorobenzene in step 2 is: 1: 1, 1: 1.2, 1.2: 1, 1: 2 or 2: 1.
In some embodiments, the drying agent is anhydrous sodium sulfate, the eluent used in the purification treatment in step 3 is a mixture of dichloromethane and methanol, and the gradient mixing ratio of dichloromethane and methanol is as follows: 50:1, 25:1 and 10: 1.
In some embodiments, fluorescent probes are used to detect trace amounts of water in organic solvents.
In some embodiments, the organic solvent is an aprotic solvent, including N, N-dimethylformamide, N-dimethylacetamide, N-methylformamide, dimethylsulfoxide, tetrahydrofuran, 1, 4-dioxane, acetonitrile, acetone, and N-methylpyrrolidone.
In some embodiments, the qualitative detection method of trace amount of water in organic solvent is: using a fluorescent probe as a fluorescent indicator, respectively adding the fluorescent probe into an organic solvent to be detected and an organic solvent with standard water content, irradiating by using an ultraviolet lamp, and observing the fluorescent brightness of the organic solvent to be detected and the organic solvent with standard water content;
the qualitative judgment is as follows: if the fluorescence brightness of the organic solvent to be detected is not lower than that of the organic solvent with the standard water content, the water content of the organic solvent to be detected exceeds 0.5 percent of that of the standard organic solvent; and if the fluorescence brightness of the organic solvent to be detected is lower than that of the organic solvent with the standard water content, the water content of the organic solvent to be detected does not exceed 0.5 percent of that of the standard organic solvent.
In some embodiments, the detection of trace amounts of water in the organic solvent is by: the fluorescent probe is used as a fluorescent indicator, a standard curve is drawn by utilizing the linear relation between the content of trace water in the organic solvent and the fluorescence brightness of the fluorescent probe, and the trace water in the organic solvent is quantitatively detected.
The invention has the beneficial effects that: the fluorescent probe 7-nitrodibenzo [2', 3': 6', 7' ] oxaheptaridine [4', 5': 4,5] imidazo [1, 2-a ] pyridine, which can form hydrogen bonds with water molecules in organic solvents, leading to reduced or quenched fluorescence. The fluorescence intensity of the fluorescent probe is weakened along with the increase of the water content in the organic solvent, and the qualitative determination of trace water in the organic solvent is realized by comparing the fluorescence brightness between the organic solvent to be determined and the standard water content solvent through the irradiation of an ultraviolet lamp and the observation of naked eyes; and measuring the ratio of the water content to the fluorescence intensity in the organic solvent by using a fluorescence spectrophotometer, and drawing a standard curve to realize quantitative measurement of trace water in the organic solvent. The fluorescent probe is simple to prepare and operate, the fluorescent probe is easy to prepare, the qualitative determination method can be used for quickly carrying out preliminary screening on the organic solvent to be detected, the detection efficiency is improved, the quantitative determination method has the advantages of convenience, high efficiency, sensitivity and low detection limit, and the content of trace water in the organic solvent to be detected can be accurately determined.
Drawings
FIG. 1 is a quantitative standard curve for measuring trace water in tetrahydrofuran organic solvent, and a method for preparing the same and an application thereof according to an embodiment of the present invention.
FIG. 2 is a quantitative standard curve for measuring trace water in 1, 4-dioxane organic solvent, which is provided by the invention, and a fluorescent probe for detecting trace water in organic solvent, a preparation method and an application thereof.
FIG. 3 is a quantitative standard curve for measuring trace water in dimethyl sulfoxide organic solvent, and a method for preparing the same and an application thereof, according to an embodiment of the present invention.
FIG. 4 is a quantitative standard curve for measuring trace water in N, N-dimethylformamide organic solvent, and a method for preparing the fluorescent probe and a use thereof according to an embodiment of the present invention.
Detailed Description
The present invention will be described in further detail with reference to examples.
Example 1
In the present example, 2 '-hydroxyacetophenone was selected from analytically pure 2' -hydroxyacetophenone supplied by Anyiji chemical Co., Ltd, 2-aminopyridine was selected from analytically pure 2-aminopyridine supplied by Anyiji chemical Co., Ltd, zinc iodide was selected from analytically pure zinc iodide supplied by Anyiji chemical Co., Ltd, anhydrous copper acetate was selected from analytically pure anhydrous copper acetate supplied by Anyiji chemical Co., Ltd, 1, 10-phenanthroline was selected from analytically pure 1, 10-phenanthroline supplied by Anyiji chemical Co., Ltd, o-dichlorobenzene was selected from analytically pure o-dichlorobenzene supplied by Anyiji chemical Co., Ltd, 2, 4-dinitrochlorobenzene was selected from analytically pure 2, 4-dinitrochlorobenzene supplied by Anyiji chemical Co., Ltd, potassium hydrogen carbonate was selected from analytically pure potassium hydrogen carbonate supplied by national chemical Co., Ltd, potassium carbonate is analytically pure potassium carbonate supplied by national drug group chemical reagent limited, potassium hydroxide is analytically pure potassium hydroxide supplied by national drug group chemical reagent limited, sodium hydroxide is analytically pure sodium hydroxide supplied by national drug group chemical reagent limited, sodium bicarbonate is analytically pure sodium bicarbonate supplied by national drug group chemical reagent limited, sodium carbonate is analytically pure sodium carbonate supplied by national drug group chemical reagent limited, acetonitrile is analytically pure acetonitrile supplied by national drug group chemical reagent limited, dimethylformamide is analytically pure dimethylformamide supplied by national drug group chemical reagent limited, ethyl acetate is analytically pure ethyl acetate supplied by national drug group chemical reagent limited, dichloromethane is analytically pure dichloromethane supplied by national drug group chemical reagent limited, the tetrahydrofuran is analytically pure tetrahydrofuran supplied by national drug group chemical reagent company, the chromatographic pure 1, 4-dioxane supplied by 1, 4-dioxane national drug group chemical reagent company, the acetone is analytically pure acetone supplied by national drug group chemical reagent company, the anhydrous sodium sulfate is anhydrous sodium sulfate with the purity of 99% supplied by national drug group chemical reagent company, and the methanol is analytically pure methanol supplied by national drug group chemical reagent company.
The reagents of this example 1 were used in the following examples 2 to 9.
Example 2
The invention relates to a preparation method of a fluorescent probe for detecting trace water in an organic solvent, which comprises the following steps:
step 1, adding 1.2mmol of 2-aminopyridine, 1mmol of 2' -hydroxyacetophenone, 0.1mmol of zinc iodide, 0.1mmol of anhydrous copper acetate, 0.1mmol of 1, 10-phenanthroline and 2ml of o-dichlorobenzene into a 10ml sealed tube, reserving air in the sealed tube, sealing, heating and stirring at 120 ℃ for 24 hours, and carrying out heating reflux reaction. After the crude product mixed liquid is cooled, washing 10ml of sealed tube by using dichloromethane, transferring the crude product mixed liquid in the 10ml of sealed tube to a separating funnel, washing the crude product mixed liquid by using saturated salt water, separating to obtain an organic phase layer, adding anhydrous sodium sulfate into the organic phase layer, drying for 10 minutes, performing suction filtration after drying, removing the anhydrous sodium sulfate to obtain a filtrate, concentrating the filtrate, loading the sample, performing purification treatment through a silica gel column, performing gradient elution by using dichloromethane and methanol as eluent in the purification treatment, wherein the gradient mixing proportion of petroleum ether and ethyl acetate is as follows in sequence: 10:1, 5:1 and 2:1, purifying to obtain the 2- (imidazo [1, 2a ] pyridine) phenol.
And 2, adding 0.5mmol of 2- (imidazo [1, 2a ] pyridine) phenol, 0.6mmol of 2, 4-dinitrochlorobenzene and 1.0mmol of KOH obtained in the step 1 into a 10ml sealed tube, vacuumizing the 10ml sealed tube by using a pump, then filling nitrogen into the 10ml sealed tube for three times, adding 2ml of dry acetonitrile into the 10ml sealed tube, sealing, heating and stirring at 80 ℃ for 8 hours, and carrying out heating reflux reaction to obtain an intermediate, wherein the reaction formula in the step is as follows:
Figure 963842DEST_PATH_IMAGE002
and 3, heating the intermediate at 100 ℃ and stirring for 8 hours to perform reaction, performing self-cyclization reaction on the intermediate, and obtaining a crude product mixed solution after complete reaction, wherein the reaction formula of the step is as follows:
Figure 293192DEST_PATH_IMAGE003
step 4, after the crude product mixed liquid is cooled, washing 10ml of sealed tube by using dichloromethane, transferring the crude product mixed liquid in the 10ml of sealed tube to a separating funnel, washing the crude product mixed liquid by using saturated saline solution, separating to obtain an organic phase layer, adding anhydrous sodium sulfate into the organic phase layer, drying for 10 minutes, performing suction filtration after drying, removing the anhydrous sodium sulfate to obtain a filtrate, concentrating the filtrate, loading the sample, performing purification treatment through a silica gel column, and performing gradient elution by using dichloromethane and methanol as eluent in the purification treatment, wherein the gradient mixing proportion of the dichloromethane and the methanol is sequentially: 50:1, 25:1 and 10:1, and purifying to obtain the fluorescent probe, namely 7-nitrodibenzo [2', 3': 6', 7' ] oxaheptaridine [4', 5': 4,5] imidazo [1, 2-a ] pyridine. The prepared fluorescent probe 7-nitrodibenzo [2', 3': 6', 7' ] oxaheptaridine [4', 5': 4,5] imidazo [1, 2-a ] pyridine, which can form hydrogen bonds with water molecules in organic solvents, leading to reduced or quenched fluorescence.
Example 3
The invention relates to a preparation method of a fluorescent probe for detecting trace water in an organic solvent, which comprises the following steps:
step 1, adding 1.2mmol of 2-aminopyridine, 1mmol of 2' -hydroxyacetophenone, 0.1mmol of zinc iodide, 0.1mmol of anhydrous copper acetate, 0.1mmol of 1, 10-phenanthroline and 2ml of o-dichlorobenzene into a 10ml sealed tube, reserving air in the sealed tube, sealing, heating and stirring at 120 ℃ for 24 hours, and carrying out heating reflux reaction. After the crude product mixed liquid is cooled, washing 10ml of sealed tube by using dichloromethane, transferring the crude product mixed liquid in the 10ml of sealed tube to a separating funnel, washing the crude product mixed liquid by using saturated salt water, separating to obtain an organic phase layer, adding anhydrous sodium sulfate into the organic phase layer, drying for 10 minutes, performing suction filtration after drying, removing the anhydrous sodium sulfate to obtain a filtrate, concentrating the filtrate, loading the sample, performing purification treatment through a silica gel column, performing gradient elution by using dichloromethane and methanol as eluent in the purification treatment, wherein the gradient mixing proportion of petroleum ether and ethyl acetate is as follows in sequence: 10:1, 5:1 and 2:1, purifying to obtain the 2- (imidazo [1, 2a ] pyridine) phenol.
Step 2, 1.0mmol of 2- (imidazo [1, 2a ] is taken]Pyridine) phenol, 0.5mmol of 2, 4-dinitrochlorobenzene and 1.0mmol of NaHCO3Adding the mixture into a 10ml sealed tube, vacuumizing the 10ml sealed tube by using a pump, then filling nitrogen into the 10ml sealed tube for three times, adding 2ml of dried ethyl acetate into the 10ml sealed tube, sealing, heating and stirring for 8 hours at the temperature of 60 ℃, and carrying out heating reflux reaction to obtain an intermediate;
step 2, heating the intermediate at 70 ℃ and stirring for 8 hours to react to obtain a crude product mixed solution after the reaction is completed;
step 3, after the crude product mixed liquid is cooled, washing 10ml of sealed tube by using dichloromethane, transferring the crude product mixed liquid in the 10ml of sealed tube to a separating funnel, washing the crude product mixed liquid by using saturated saline solution, separating to obtain an organic phase layer, adding anhydrous sodium sulfate into the organic phase layer, drying for 10 minutes, performing suction filtration after drying, removing the anhydrous sodium sulfate to obtain a filtrate, concentrating the filtrate, loading the sample, performing purification treatment through a silica gel column, and performing gradient elution by using dichloromethane and methanol as eluent in the purification treatment, wherein the gradient mixing proportion of the dichloromethane and the methanol is sequentially: 50:1, 25:1 and 10:1, and purifying to obtain the fluorescent probe, namely 7-nitrodibenzo [2', 3': 6', 7' ] oxaheptaridine [4', 5': 4,5] imidazo [1, 2-a ] pyridine.
Example 4
The invention relates to a qualitative detection method of trace water content in an organic solvent, which comprises the following steps:
0.0033g of the fluorescent probe was weighed out and dissolved in 10ml of ethyl acetate for use. Respectively transferring 30ul of prepared ethyl acetate solution of the fluorescent probe to two test tubes, respectively drying the ethyl acetate in the two test tubes, then adding the same amount of N-methylpyrrolidone to be detected and N-methylpyrrolidone with standard water content, irradiating the solution by using a 365nm ultraviolet lamp, and observing the fluorescence brightness of the N-methylpyrrolidone to be detected and the N-methylpyrrolidone with standard water content;
the qualitative judgment is as follows: and judging that the content of trace water in the N-methyl pyrrolidone to be detected exceeds 0.5 percent of the water content in the N-methyl pyrrolidone standard solvent. The fluorescence intensity of the fluorescent probe is weakened along with the increase of the water content in the organic solvent, and the qualitative determination of the trace water in the organic solvent is realized by comparing the fluorescence brightness between the organic solvent to be determined and the standard water content solvent through the irradiation of an ultraviolet lamp and the observation of naked eyes.
Example 5
The invention relates to a qualitative detection method of trace water in an organic solvent, which comprises the following steps:
0.0033g of the fluorescent probe was weighed out and dissolved in 10ml of ethyl acetate for use. Respectively transferring 30ul of prepared ethyl acetate solution of the fluorescent probe to two test tubes, respectively drying the ethyl acetate in the test tubes, then adding equal amounts of acetone to be detected and acetone with standard water content, irradiating the solution by using a 365nm ultraviolet lamp, and observing the fluorescence brightness of the acetone to be detected and the acetone with standard water content;
the qualitative judgment is as follows: and (3) judging that the content of trace water in the acetone to be detected does not exceed 0.5% of the water content in the acetone standard solvent. The fluorescence intensity of the fluorescent probe is weakened along with the increase of the water content in the organic solvent, and the qualitative determination of the trace water in the organic solvent is realized by comparing the fluorescence brightness between the organic solvent to be determined and the standard water content solvent through the irradiation of an ultraviolet lamp and the observation of naked eyes.
Example 6
The invention relates to a quantitative detection method of trace water content in an organic solvent, which comprises the following steps:
step 1, preparing a standard curve:
0.0033g of the fluorescent probe was weighed out and dissolved in 10ml of ethyl acetate for use. Further, tetrahydrofuran solutions having water contents (v/v) of 0%, 0.5%, 0.99%, 1.48%, 1.96%, 2.44%, 2.91%, 3.38%, 3.85%, 4.31%, 4.76% were prepared and prepared for use. 30ul of the prepared ethyl acetate solution of the fluorescent probe is respectively transferred, the ethyl acetate is dried, and then the prepared tetrahydrofuran solution with the water content (v/v) of 0%, 0.5%, 0.99%, 1.48%, 1.96%, 2.44%, 2.91%, 3.38%, 3.85%, 4.31% and 4.76% is added to the solution until the volume is 1 ml. The fluorescence emission spectra of each solution were measured in a fluorescence spectrophotometer and the maximum fluorescence emission intensity of each solution was recorded.
Measurement conditions of spectral data: the excitation wavelength is 410nm, the slit width is 5nm, and the 1ml four-way transmission quartz cuvette is provided.
Based on the maximum fluorescence emission intensity recorded for each solution, a standard curve of fluorescence intensity ratio I0/I versus% water content v/v was prepared, the standard curve being: y =0.8892+1.2548x, see fig. 1, in which the y-axis (I0/I) represents the ratio of fluorescence intensities, I0 represents the fluorescence intensity of a solution with 0% water content, and I represents the fluorescence intensity of each solution with a different water content; the x-axis (v/v) represents the volume of water to volume of solution. The lowest detection limit of the fluorescent probe in tetrahydrofuran was calculated to be 0.017% according to the formula LOD =3.3 σ/k, where LOD represents the lowest detection limit of the fluorescent indicator, σ represents the standard deviation of each solution, and k is the slope of the standard curve.
Step 2, measuring trace water in the tetrahydrofuran organic solvent to be measured:
and respectively transferring 30ul of the prepared ethyl acetate solution of the fluorescent probe, drying the ethyl acetate, adding a tetrahydrofuran organic solvent to be detected, and fixing the volume to 1 ml. And (3) measuring the fluorescence emission spectrum of the solution in a fluorescence spectrophotometer, recording the maximum fluorescence emission intensity of the solution, substituting the maximum fluorescence emission intensity into a standard curve, and calculating to obtain the content of trace water in the tetrahydrofuran organic solvent to be measured, wherein the content of the trace water in the tetrahydrofuran organic solvent to be measured is 0.023%.
Example 7
The invention relates to a quantitative detection method of trace water content in an organic solvent, which comprises the following steps:
step 1, preparing a standard curve:
0.0033g of the fluorescent probe was weighed out and dissolved in 10ml of ethyl acetate for use. Further, 1, 4-dioxane solutions having water contents (v/v) of 0%, 0.5%, 0.99%, 1.48%, 1.96%, 2.44%, 2.91%, 3.38%, 3.85%, 4.31%, and 4.76% were prepared, respectively, and were prepared for use. 30ul of prepared ethyl acetate solution of the fluorescent probe is respectively transferred, the ethyl acetate is dried, and then the prepared 1, 4-dioxane solution with the water content (v/v) of 0%, 0.5%, 0.99%, 1.48%, 1.96%, 2.44%, 2.91%, 3.38%, 3.85%, 4.31% and 4.76% is added to the solution to fix the volume to 1 ml. The fluorescence emission spectra of each solution was then measured using a fluorescence spectrophotometer, and the maximum fluorescence emission intensity of each solution was recorded.
Measurement conditions of spectral data: the excitation wavelength is 410nm, the slit width is 5nm, and the 1ml four-way transmission quartz cuvette is provided.
From the maximum fluorescence emission intensity recorded for each solution, a standard curve of the fluorescence intensity ratio I0/I versus% water content v/v was made, standard curve: y =0.7452+1.3366x, see fig. 2, in which the y-axis (I0/I) represents the ratio of fluorescence intensities, I0 represents the fluorescence intensity of a solution with 0% water content, and I represents the fluorescence intensity of each solution with a different water content; the x-axis (v/v) represents the volume of water to volume of solution. According to the formula LOD =3.3 σ/k, the lowest detection limit of the fluorescent probe in the 1, 4-dioxane solvent is calculated to be 0.093%, wherein LOD represents the lowest detection limit of the fluorescent indicator, σ represents the standard deviation of each solution, and k is the slope of the standard curve.
Step 2, measuring trace water in the 1, 4-dioxane organic solvent to be measured:
and respectively transferring 30ul of the prepared ethyl acetate solution of the fluorescent probe, drying the ethyl acetate, adding the 1, 4-dioxane organic solvent to be detected, and fixing the volume to 1 ml. And measuring the fluorescence emission spectrum of the solution in a fluorescence spectrophotometer, recording the maximum fluorescence emission intensity of the solution, substituting the maximum fluorescence emission intensity into a standard curve, and calculating to obtain the content of trace water in the 1, 4-dioxane organic solvent to be measured, wherein the content of the trace water is 0.103%.
Example 8
The invention relates to a quantitative detection method of trace water content in an organic solvent, which comprises the following steps:
step 1, preparing a standard curve:
0.0033g of the fluorescent probe was weighed out and dissolved in 10ml of ethyl acetate for use. Further, dimethyl sulfoxide solutions having water contents (v/v) of 0%, 0.5%, 0.99%, 1.48%, 1.96%, 2.44%, 2.91%, 3.38%, 3.85%, 4.31%, and 4.76% were prepared, respectively, and prepared for use. 30ul of prepared ethyl acetate solution of the fluorescent probe is respectively transferred, the ethyl acetate is dried, and then the prepared dimethyl sulfoxide solution with the water content (v/v) of 0%, 0.5%, 0.99%, 1.48%, 1.96%, 2.44%, 2.91%, 3.38%, 3.85%, 4.31% and 4.76% is added to the solution to achieve the constant volume of 1 ml. The fluorescence emission spectra of each solution was then measured in a fluorescence spectrophotometer and the maximum fluorescence emission intensity of each solution was recorded.
Measurement conditions of spectral data: the excitation wavelength is 410nm, the slit width is 5nm, and the 1ml four-way transmission quartz cuvette is provided.
From the maximum fluorescence emission intensity recorded for each solution, a standard curve of the fluorescence intensity ratio I0/I versus% water content v/v was made, standard curve: y =0.09400+0.2782x, see fig. 3, in which the y-axis (I0/I) represents the ratio of fluorescence intensities, I0 represents the fluorescence intensity of a solution with 0% water content, and I represents the fluorescence intensity of each solution with a different water content; the x-axis (v/v) represents the volume of water to volume of solution. According to the formula LOD =3.3 σ/k, the lowest detection limit of the fluorescent probe in the dimethylsulfoxide solution is calculated to be 0.643%, wherein LOD represents the lowest detection limit of the fluorescent indicator, σ represents the standard deviation of each solution, and k is the slope of the standard curve.
Step 2, measuring trace water in the dimethyl sulfoxide organic solvent to be measured:
and respectively transferring 30ul of the prepared ethyl acetate solution of the fluorescent probe, drying the ethyl acetate, adding the dimethyl sulfoxide organic solvent to be detected, and fixing the volume to 1 ml. And (3) measuring the fluorescence emission spectrum of the solution in a fluorescence spectrophotometer, recording the maximum fluorescence emission intensity of the solution, substituting the maximum fluorescence emission intensity into a standard curve, and calculating to obtain the content of trace water in the dimethyl sulfoxide organic solvent to be measured, wherein the content of trace water in the dimethyl sulfoxide organic solvent to be measured is 0.758%.
Example 9
The invention relates to a quantitative detection method of trace water content in an organic solvent, which comprises the following steps:
step 1, preparing a standard curve:
0.0033g of the fluorescent probe was weighed out and dissolved in 10ml of ethyl acetate for use. Further, N-dimethylformamide solutions having a water content (v/v) of 0%, 0.5%, 0.99%, 1.48%, 1.96%, 2.44%, 2.91%, 3.38%, 3.85%, 4.31%, 4.76% were prepared, respectively, and prepared for use. 30ul of prepared ethyl acetate solution of the fluorescent probe is respectively transferred, the ethyl acetate is dried, and then the prepared N, N-dimethylformamide solution with the water content (v/v) of 0%, 0.5%, 0.99%, 1.48%, 1.96%, 2.44%, 2.91%, 3.38%, 3.85%, 4.31% and 4.76% is added to the solution to achieve the constant volume of 1 ml. The fluorescence emission spectra of each solution was then measured in a fluorescence spectrophotometer and the maximum fluorescence emission intensity of each solution was recorded.
Measurement conditions of spectral data: the excitation wavelength is 410nm, the slit width is 5nm, and the 1ml four-way transmission quartz cuvette is provided.
Based on the maximum fluorescence emission intensity recorded for each solution, a standard curve of fluorescence intensity ratio I0/I versus% water content v/v was prepared, the standard curve being: y =0.8055+0.6181x, see fig. 4, in which the y-axis (I0/I) represents the ratio of fluorescence intensities, I0 represents the fluorescence intensity of a solution with 0% water content, and I represents the fluorescence intensity of each solution with a different water content; the x-axis (v/v) represents the volume of water to volume of solution. According to the formula LOD =3.3 σ/k, the lowest detection limit of the fluorescent probe in the N, N-dimethylformamide solution is 0.569%, wherein LOD represents the lowest detection limit of the fluorescent indicator, σ represents the standard deviation of each solution, and k is the slope of the standard curve.
Step 2, measuring trace water in the N, N-dimethylformamide organic solvent to be measured:
and respectively transferring 30ul of the prepared ethyl acetate solution of the fluorescent probe, drying the ethyl acetate, adding an N, N-dimethylformamide organic solvent to be detected, and fixing the volume to 1 ml. And measuring the fluorescence emission spectrum of the solution in a fluorescence spectrophotometer, recording the maximum fluorescence emission intensity of the solution, substituting the maximum fluorescence emission intensity into a standard curve, and calculating to obtain the content of trace water in the N, N-dimethylformamide organic solvent to be measured, wherein the content of trace water in the N, N-dimethylformamide organic solvent to be measured is 0.591%.
As can be seen from the above examples, the detection limit of the quantitative detection method of the present invention for the content of trace water in the organic solvent is as follows: the detection limit of tetrahydrofuran was 0.017%, the detection limit of 1, 4-dioxane was 0.093%, the detection limit of N, N-dimethylformamide was 0.569%, and the detection limit of dimethyl sulfoxide was 0.643%. The fluorescent probe prepared by the invention has high sensitivity to trace water in an organic solvent, and the quantitative detection method has the advantages of convenience, high efficiency, sensitivity and low detection limit, and can be used for quantitatively determining the trace water in the organic solvent in batches and efficiently.
The fluorescent probe 7-nitrodibenzo [2', 3': 6', 7' ] oxaheptaridine [4', 5': 4,5] imidazo [1, 2-a ] pyridine, which can form hydrogen bonds with water molecules in organic solvents, leading to reduced or quenched fluorescence. The fluorescence intensity of the fluorescent probe is weakened along with the increase of the water content in the organic solvent, and the qualitative determination of trace water in the organic solvent is realized by comparing the fluorescence brightness between the organic solvent to be determined and the standard water content solvent through the irradiation of an ultraviolet lamp and the observation of naked eyes; and measuring the ratio of the water content to the fluorescence intensity in the organic solvent by using a fluorescence spectrophotometer, and drawing a standard curve to realize quantitative measurement of trace water in the organic solvent. The fluorescent probe is simple to prepare and operate, the fluorescent probe is easy to prepare, the qualitative determination method can be used for quickly carrying out preliminary screening on the organic solvent to be detected, the detection efficiency is improved, the quantitative determination method has the advantages of convenience, high efficiency, sensitivity and low detection limit, and the content of trace water in the organic solvent to be detected can be accurately determined.
The above description is only for the embodiments of the present invention, and it is obvious to those skilled in the art that various changes and modifications can be made without departing from the inventive concept of the present invention, and these changes and modifications are all within the scope of the present invention.

Claims (4)

1. The application of the fluorescent probe for detecting trace water in the organic solvent is characterized in that the fluorescent probe is 7-nitrodibenzo [2', 3': 6', 7' ] oxaheptaridine [4', 5': the structural characteristics of the 4,5] imidazo [1, 2-a ] pyridine are shown in a formula I:
Figure 385582DEST_PATH_IMAGE001
the fluorescent probe is used for detecting trace water in an organic solvent.
2. The use according to claim 1, wherein the organic solvent is an aprotic solvent, and the aprotic solvent is one of N, N-dimethylformamide, N-dimethylacetamide, N-methylformamide, dimethylsulfoxide, tetrahydrofuran, 1, 4-dioxane, acetonitrile, acetone, or N-methylpyrrolidone.
3. The use according to claim 2, characterized in that the qualitative detection of trace amounts of water in organic solvents is carried out by: the fluorescent probe is used as a fluorescent indicator, the fluorescent probe is respectively added into an organic solvent to be detected and an organic solvent with standard water content, an ultraviolet lamp is used for irradiating, and the fluorescent brightness of the organic solvent to be detected and the organic solvent with standard water content is observed;
the qualitative judgment is as follows: if the fluorescence brightness of the organic solvent to be detected is not lower than that of the organic solvent with the standard water content, the water content of the organic solvent to be detected exceeds 0.5 percent of that of the standard organic solvent; and if the fluorescence brightness of the organic solvent to be detected is lower than that of the organic solvent with the standard water content, the water content of the organic solvent to be detected does not exceed 0.5 percent of that of the standard organic solvent.
4. The use of claim 2, wherein the quantitative determination of trace amounts of water in the organic solvent is carried out by: and using the fluorescent probe as a fluorescent indicator, drawing a standard curve by utilizing the linear relation between the content of the trace water in the organic solvent and the fluorescence brightness of the fluorescent probe, and carrying out quantitative detection on the trace water in the organic solvent.
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011029459A1 (en) * 2009-09-10 2011-03-17 MAX-PLANCK-Gesellschaft zur Förderung der Wissenschaften e.V. Novel photoactivable fluorescent dyes for optical microscopy and image techniques
CN107275496A (en) * 2016-04-07 2017-10-20 三星显示有限公司 Organic luminescent device

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011029459A1 (en) * 2009-09-10 2011-03-17 MAX-PLANCK-Gesellschaft zur Förderung der Wissenschaften e.V. Novel photoactivable fluorescent dyes for optical microscopy and image techniques
CN107275496A (en) * 2016-04-07 2017-10-20 三星显示有限公司 Organic luminescent device

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
Bright photoactivatable fluorophores for single-molecule imaging;Jonathan B Grimm et al.;《Nature Methods》;20161024;第13卷(第12期);第985-988页 *
Heterocyclic Iodoniums for the Assembly of Oxygen-Bridged Polycyclic Heteroarenes with Water as the Oxygen Source;Daqian Zhu et al.;《Organic Letters》;20180727;第20卷(第16期);第4815-4818页 *
Rhodamines NN: A novel class of caged fluorescent dyes;Belov, Vladimir N. et al.;《Angewandte Chemie, International Edition》;20100409;第49卷(第20期);第3520-3523页 *
Synthesis and anti-enterovirus activity of new analogues of MDL-860;Georgi M. Dobrikov et al.;《Bioorganic & Medicinal Chemistry Letters》;20170830;第27卷(第19期);第4540-4543页 *

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