CN1916629A - Fluorescence carrier in use for preparing sensor in use for mensurating content of water in organic solvent - Google Patents
Fluorescence carrier in use for preparing sensor in use for mensurating content of water in organic solvent Download PDFInfo
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- CN1916629A CN1916629A CN 200610032166 CN200610032166A CN1916629A CN 1916629 A CN1916629 A CN 1916629A CN 200610032166 CN200610032166 CN 200610032166 CN 200610032166 A CN200610032166 A CN 200610032166A CN 1916629 A CN1916629 A CN 1916629A
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- water content
- organic solvent
- liquid water
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Abstract
A fluorescent carrier used for preparing transducer to determine water content in organic solvent is not sensitive to pH so transducer prepared by it can be used to determine water content in organic solvent under different pH condition properly and the prepared transducer also can be used on-line to determine water content in organic solvent in real time continuously.
Description
Technical field
The present invention relates to a kind of fluorescence carrier, be specifically related to measure the fluorescence carrier in the sensor of liquid water content in the organic solvent.
Background technology
Water is modal a kind of impurity of organic solvent, and the mensuration of liquid water content is an important problem analysis in field organic solvents such as some chemical industry, medicine, food.Measuring the classic methods of the water yield is exactly the karl Fischer titrimetry.Though this method has had very big improvement, have still that reagent preparation is loaded down with trivial details, configuration condition is harsh, can not realize shortcomings such as real-time, online detection truly.Also occurred some in addition and measured the sensor of liquid water content in the organic solvent, but this class sensor is subjected to the interference of electromagnetic field easily based on conductivity, change in dielectric constant.Fluorescent optical sensor has easily and fast, the characteristics of cheapness, and good sensitivity and selectivity are arranged, therefore in the interest that has also caused many researchers aspect the liquid water content mensuration.
In the design and development of various fluorescent optical sensors, the fluorescent optical sensor that changes based on fluorescence intensity has simple to operate, advantages such as response speed fast, good reversibility, life-span length.Similar report is also arranged in the document, is to disclose the fluorescence carrier in a kind of fluorescence chemical sensor that detects liquid water content in the organic solvent and the assay method of liquid water content thereof in 200610031684.7 the application for a patent for invention as application number.But the fluorescent optical sensor of these developments can be subjected to the influence of pH when detecting liquid water content in the organic solvent.
Therefore will make the scope that mensuration is not influenced by pH and further liquid water content is measured in raising of liquid water content in the organic solvent, developing a kind of new fluorescence carrier is highly significant.
Summary of the invention
The present invention is intended to develop synthetic a kind of new fluorescence carrier, and the fluorescent optical sensor that makes its preparation is not influenced by pH not only during liquid water content in measuring organic solvent, and improves the measurement range of liquid water content.
The present invention seeks to realize like this: the synthetic a kind of fluorescence carrier of development is N-allyl-4-morpholinyl-1, the 8-naphthalimide, and structural formula is as follows:
This compound is a yellow powder powder solid, molecular weight: 322, and fusing point: 125-127 ℃.
Be described in further detail the present invention below in conjunction with accompanying drawing.
Description of drawings
Fig. 1 is the fluorescence response spectrogram of fluorescent optical sensor molecule of the present invention to different pH.Wherein horizontal ordinate is the pH value, and ordinate is a fluorescence intensity.
Fig. 2 is a fluorescence intensity situation over time when circulation feeds the dioxane solution of different liquid water contents.Wherein horizontal ordinate is the time, and ordinate is a fluorescence intensity.Liquid water content is followed successively by (v/v) from low to high: (a) 0.00%; (b) 1.00%; (c) 5.00%; (d) 40.0%.
Fig. 3 is the fluorescence response spectrogram of fluorescent optical sensor molecule of the present invention in the different dioxane solution of liquid water content.Wherein horizontal ordinate is a wavelength, and ordinate is a fluorescence intensity.Liquid water content is followed successively by (v/v) from top to bottom: 0.00%; 0.20%; 1.40%; 3.00%; 5.00%; 10.0%; 20.0%; 30.0%; 40.0%; 50.0%; 60.0%; 70.0%; 80.0%; 90.0%; 100%.
Suitable fluorescence carrier is the key of preparation fluorescent optical sensor, and fluorescence carrier of the present invention is a kind of derivant of naphthalimide: N-allyl-4-morpholinyl-1,8-naphthalimide.1, the derivant of 8-naphthalimide has been widely used in aspects such as dyestuff, pigment, fluorescer, fluorescent ink, fluorescent paint, organic light-guide material.People utilize 1, and the derivant of 8-naphthalimide has prepared fluorescent optical sensors such as some metallic ion probes and picric acid, furantoin, pH, still, it is reported that nobody also is used for measuring the liquid water content in the organic solvent.Consider that the water in the organic solvent may have different pH values, so synthesized 4-morpholinyl-1, the 8-naphthalimide derivative, so that the mensuration of liquid water content is not subjected to the influence of pH in the organic solvent, simultaneously, on the N position, introduce allyl and be used for Covalent Immobilization, stoped the loss of fluorescence carrier effectively.
Prepare the fluorescent optical sensor of having fixed fluorescence carrier of the present invention through the silanization of slide, the configuration and the photopolymerization of coating solution, be applied to the mensuration of liquid water content in the organic solvent.
Fluorescence carrier of the present invention is a kind of naphthalimide derivative, and it synthesizes and is divided into three steps:
1, allyl amine is synthetic.With reference to handbook (chapter is thought rule, practical fine chemistry handbook. Beijing: Chemical Industry Press, 1996,101-105), synthetic by three-step reaction by vinylcarbinol, hydrobromic acid and sodium thiocyanate:
(1) vinylcarbinol synthetic bromide propylene: in reaction bulb, add the hydrobromic acid of 120ml 48%, stir the adding 60ml concentrated sulphuric acid down, and then add the 60g vinylcarbinol.Reflux 4 hours is then with its cooling.The cooling back adds some zeolites, changes distilling apparatus into, distillation.Collect 68 ℃～73 ℃ cuts.Then add anhydrous magnesium sulfate drying, suction filtration.69 ℃～71 ℃ cuts are collected in distillation once more, collect the 70ml bromopropene.
(2) allyl group isosulfocyanate is synthetic: the 30g sodium thiocyanate is joined in the 200ml acetone, add the 30ml bromopropene again, refluxed 2 hours, cooling.The elimination sodium bromide.Boil off acetone then.Add thermal distillation again, collect 152 ℃～154 ℃ cuts.Get the 30ml allyl group isosulfocyanate.
(3) allylamine is synthetic: get among the HCl that the 30ml allyl group isosulfocyanate joins 150ml 20% back flow reaction 10 hours.During the reaction beginning, solution is divided into two-phase, becomes homogeneous phase after 5 hours, continues this moment to reflux.H is arranged in the course of reaction
2S emits.After question response is finished, change reflux into distilling apparatus, steam water in the reactant liquor and excessive HCl.Add 30ml water then, and in solution, drip the KOH solution of 30ml 50%, in the dropping process, the product allylamine is steamed, and collect 50 ℃～86 ℃ cuts.The crude product of collecting is refining with fractionating process, collect 57 ℃～59 ℃ cut, get product 14.5ml.
Concrete synthesis path is as follows:
2, N-allyl-4-bromo-1,8-naphthalimide (ABN) synthetic.With 12.2g 4-bromo-1,8-naphthalene acid anhydride and 0.65ml allyl amine react in 50ml ethanol.Refluxed 2 hours, then with its cooling.After cooling solution is filtered, the gained solid washs with ethanol.Dry under 105 ℃ again, obtain light yellow solid at last and be ABN, productive rate is 87.6%.
3, N-allyl-4-morpholinyl-1,8-naphthalimide (AMN) synthetic.Be reactant and add a certain amount of CuSO with 500mg ABN and 0.4ml morpholine
45H
2O refluxed 2 hours in the 20ml glycol monoethyl ether.After the cooling of question response thing, add a large amount of water, separate out solid.Then with its standing over night.Solution filtered in second day, gained solid ethyl alcohol recrystallization, drying must lurid solid, is AMN.
Concrete synthesis path is as follows:
The preparation method of fluorescence chemical sensor is as follows:
1, the silanization of slide: with soaking 40 minutes in common slide (diameter 12.5mm) the immersion chromic acid lotion, put into 3%HF successively and soaked 30 minutes, totally make with distilled water flushing then and fully no longer speckle with 3% HF, add 10% H again
2O
2The middle immersion 30 minutes.Clean with distilled water flushing again.Measure 0.2ml propyl methacrylate (TSPM) with the transfer pipet of drying, the pH of 2ml 0.2mol/L is 3.6 acetic acid-sodium-acetate buffer and the mixing of 8ml distilled water, stirs TSPM is melted fully with preparation silanization solution.Slide immersed in this solution 2～3 hours, cleaned with distilled water then, and drying at room temperature is standby.
2, the preparation of coating solution: 10mg AMN is dissolved in 0.2ml N, in the dinethylformamide, adds the 200mg acrylamide successively, 0.4ml hydroxyethyl methylacrylate, 0.15ml crosslinking chemical, 0.15ml triethanolamine and 0.2ml photosensitizer.
3, photopolymerization: get the above-mentioned coating solution of 0.1～0.2ml on polyfluortetraethylene plate, with the slide lid of hexasilaneization on it, use about 20 minutes of uviol lamp (254nm) irradiation again, take out the good slide of photocuring successively water and alcohol flushing, till the loss that does not observe carrier, drying at room temperature is standby.
Measure the range of linearity of fluorescent optical sensor with ethanol, acetonitrile, dioxane solution.
Ethanol, acetonitrile, the dioxane solution of different liquid water contents are imported in the flow cell with the speed of 2.0ml/min respectively, be respectively 517nm, 510nm, 507nm place measurement fluorescence intensity at maximum excitation wavelength 400nm and emission wavelength, the excitation-emission slit is 5nm.Fluorescence intensity when record auroral poles film and solution reach balance is drawn the fluorescence response figure that auroral poles film fluorescence intensity changes with liquid water content in ethanol, acetonitrile, the dioxane.In liquid water content 0～4.4% (v/v) scope, present certain linear between the two.Their correction linear equation is respectively:
Ethanol: I=-22.42[H
2O]+538.69 (R=0.9985)
Acetonitrile: I=-52.10[H
2O]+540.26 (R=0.9933)
Dioxane: I=-40.23[H
2O]+661.69 (R=0.9975)
The fluorescence molecule of the present invention's design is easy to synthesize, and to pH insensitive (Fig. 1), the pH value is from 1～13, and fluorescence intensity remains unchanged substantially; Effectively stoped the loss of fluorescence carrier by the method for Covalent Immobilization; And this sensor construction is simple, has shown good stability, reappearance and reversibility (Fig. 2); Realized continuous, real-time, online mensuration, and the measurement range of liquid water content in the organic solvent has been reached 70% (v/v) (Fig. 3) liquid water content in the organic solvent.
Embodiment
Embodiment 1:
Under the condition of different pH, the mensuration of liquid water content in the dioxane solution.
Concrete steps: get the volumetric flask of three 100ml, drying adds the 50ml dioxane respectively, uses the NaOH difference constant volume of HCl, the pH=11 of distilled water and pH=2 then, measures its liquid water content.The result is as shown in table 1:
The different pH of table 1, the liquid water content in the dioxane solution
| Sample | [H 2O] a | [H 2O] b | Mean value | Error |
| Distilled water pH=2 pH=11 | 50.00％ 50.00％ 50.00％ | 50.12 50.24 50.35 49.98 50.07 50.20 49.89 50.01 50.13 | 50.24 50.08 50.06 | 0.24 0.08 0.06 |
Annotate: [H
2O]
aThe dioxane solution that pH is different manually adds liquid water content (v/v).
[H
2O]
bSensor of the present invention records liquid water content (v/v) for three times.
Embodiment 2:
Under the condition of different pH, the mensuration of liquid water content in the dichloromethane solution.
Concrete steps: get the volumetric flask of three 100ml, drying adds the 50ml methylene chloride respectively, uses the NaOH difference constant volume of HCl, the pH=9 of distilled water and pH=4 then, measures its liquid water content.The result is as shown in table 2:
The different pH of table 2, the liquid water content in the dichloromethane solution
| Sample | [H 2O] a | [H 2O] b | Mean value | Error |
| Distilled water pH=4 pH=9 | 5.00％ 5.00％ 5.00％ | 5.04％ 5.06％ 5.15％ 4.98％ 5.01％ 5.12％ 4.95％ 4.99％ 5.02％ | 5.08 5.04 4.99 | 0.08 0.04 -0.01 |
Annotate: [H
2O]
aThe dichloromethane solution that pH is different manually adds liquid water content (v/v).
[H
2O]
bSensor of the present invention records liquid water content (v/v) for three times.
Embodiment 3:
Under the condition of different pH, the mensuration of liquid water content in the toluene solution.
Concrete steps: get the volumetric flask of three 100ml, drying adds 50ml toluene respectively, uses the NaOH difference constant volume of HCl, the pH=10 of distilled water and pH=3 then, measures its liquid water content.The result is as shown in table 3:
Liquid water content in the toluene under table 3 condition of different pH
| Sample | [H 2O] a | [H 2O] b | Mean value | Error |
| Distilled water pH=3 pH=10 | 70.00％ 70.00％ 70.00％ | 70.09 70.13 70.19 70.11 70.25 70.30 69.87 69.91 70.02 | 70.14 70.22 69.93 | 0.14 0.22 -0.07 |
Annotate: [H
2O]
aThe toluene solution that pH is different manually adds liquid water content (v/v).
[H
2O]
bSensor of the present invention records liquid water content (v/v) for three times.
Claims (1)
1, a kind of fluorescence carrier that is used for the sensor of formation determination organic solvent liquid water content is characterized in that this fluorescence carrier is N-allyl-4-morpholinyl-1, the 8-naphthalimide, and structural formula is as follows:
This compound is a yellow powder powder solid, molecular weight: 322, and fusing point: 125-127 ℃.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105651749A (en) * | 2016-01-19 | 2016-06-08 | 湖南科技大学 | Method for detecting water content in tetrahydrofuran through carbon nanoparticles |
| CN111039892A (en) * | 2019-12-12 | 2020-04-21 | 华南师范大学 | Benzothiazole derivative, preparation method thereof and application of benzothiazole derivative in rapid visual recognition of alcoholic strength of white spirit |
| CN112679432B (en) * | 2020-12-29 | 2023-07-21 | 安徽理工大学环境友好材料与职业健康研究院(芜湖) | Naphthalimide-diphenyl sulfone derivative fluorescent probe and preparation method and application thereof |
-
2006
- 2006-09-01 CN CN 200610032166 patent/CN1916629A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105651749A (en) * | 2016-01-19 | 2016-06-08 | 湖南科技大学 | Method for detecting water content in tetrahydrofuran through carbon nanoparticles |
| CN105651749B (en) * | 2016-01-19 | 2018-09-14 | 湖南科技大学 | A kind of method that carbon nano-particles detect moisture in tetrahydrofuran |
| CN111039892A (en) * | 2019-12-12 | 2020-04-21 | 华南师范大学 | Benzothiazole derivative, preparation method thereof and application of benzothiazole derivative in rapid visual recognition of alcoholic strength of white spirit |
| CN112679432B (en) * | 2020-12-29 | 2023-07-21 | 安徽理工大学环境友好材料与职业健康研究院(芜湖) | Naphthalimide-diphenyl sulfone derivative fluorescent probe and preparation method and application thereof |
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