CN1865935A - Fluorescent chemical sensor for detecting water content in organic solvent and application thereof - Google Patents
Fluorescent chemical sensor for detecting water content in organic solvent and application thereof Download PDFInfo
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- CN1865935A CN1865935A CN 200610031684 CN200610031684A CN1865935A CN 1865935 A CN1865935 A CN 1865935A CN 200610031684 CN200610031684 CN 200610031684 CN 200610031684 A CN200610031684 A CN 200610031684A CN 1865935 A CN1865935 A CN 1865935A
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- fluorescence
- water content
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- liquid water
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Abstract
The disclosed fluorescent chemical sensor for water content in organic solvent comprises: with acylation reaction, and introducing a terminal double bond to 4-amido -4'-N, N- dimethylaminochalcone to let it polymerize with film matrix monomer on glass surface or fiber head. This invention has simple structure, well stability and high sensitivity.
Description
Technical field
The present invention relates to a kind of fluorescent optical sensor, be specifically related to a kind of fluorescence chemical sensor that detects liquid water content in the organic solvent.
Background technology
The mensuration of water is an important analysis project in the organic solvent, and the sign of liquid water content is an important indicator in the products such as medicine, chemical industry, food, plastics, synthon.In order to guarantee product quality or to understand properties of product, usually need the water cut in the organic solvent is measured.The method of existing mensuration liquid water content adopts classical karl Fischer moisture assay method mostly.Yet along with the development of Detection Techniques and the progress of science and technology, especially in today of computer automatic control system widespread use, people are more and more higher to the requirement accurate and reliability that liquid water content is measured.But at present, be used for Optochemical sensor that the organic solvent liquid water content measures also seldom.Utilizations such as Bai contain the porous polyethylene resin of quaternary ammonium salt group and have developed a kind of fiber optic sensor of measuring liquid water content in the acetone in different different these character of the middle mutually reflectance spectrum of solvent that cause with swelling volume in the water of organic solvent.The diffraction colour that Blyth etc. utilize the gel holographic diffraction grating has proposed a kind of holographic water sensor with the relation that the variation of liquid water content in the organic solvent changes.But these methods can not realize reversible fast, that is to say to be used for real-time detection.
At present, fluorescent technique has been widely used among design and the development of Optochemical sensor of various types of, various detected objects.This is not only because of intrinsic sensitivity and the selectivity of fluorescence method, but also because enriching of fluorescence measurement signal reaches the easy of design.Wherein based on the fluorescence chemical sensor of Strength Changes have that response is rapid, reversible, advantage such as long-life, tested object are extensive.Therefore, design, synthetic a kind of fluorescence chemical sensor molecules that can respond minor amount of water realization fluorescence intensity in the organic solvent be challenging research work.
Summary of the invention
The fluorescence chemical sensor that the present invention is intended to make of a kind of chalcone derivative detects liquid water content in the organic solvent, to solve the technical matters that detects in real time fast of minor amount of water.
The technical scheme that the present invention solves the foregoing invention purpose is as follows:
Detect the fluorescence chemical sensor of liquid water content in the organic solvent; the slide or the optical fiber that comprise silanization; the membrane matrix monomer is attached to auroral poles film on slide or the optical fiber through photopolymerization; it is characterized in that the fluorescence carrier in the membrane matrix monomer is amino-the 4 '-N of 4-(methacryl) that the chalcone molecule is combined to through acyl group; N-dimethylamino chalcone; above-mentioned chalcone derivative is dissolved in N, in the dinethylformamide, adds acrylamide successively; hydroxyethyl methylacrylate; crosslinking chemical, three derivants are dissolved in N, in the dinethylformamide; add acrylamide successively; hydroxyethyl methylacrylate, crosslinking chemical, triethanolamine and photosensitizer; get the above-mentioned coating solution of 0.1～0.2ml on polyfluortetraethylene plate; with the slide of silanization or fiber cover thereon, behind uv photopolymerization, drying at room temperature is made.
Described fluorescence chemical sensor detects the method for liquid water content in the organic solvent, to be pack into the top of teflon circulation of sensor that fluorescence carrier is made with the chalcone derivative, testing sample is with the speed of 1.5ml/min input flow cell, and the maximum excitation wavelength of fluorescence carrier and transmitted wave strong point are measured fluorescence intensity and measured liquid water content in the organic solvent according to the correction equation formula in different organic solvents.Be described in further detail the present invention below in conjunction with accompanying drawing:
Description of drawings
Fig. 1 is a teflon flow cell structural drawing:
(A), flow cell pond body (B), cock (C), auroral poles film
(D), glass sheet (E), sensing chamber (F), both arms optical fiber
(G), sample channel is gone into and is exported.
Fig. 2 is the fluorescence response spectrogram of fluorescent optical sensor molecule in different organic solvents:
Ordinate is a fluorescence intensity, and horizontal ordinate is an emission wavelength,
Wherein (1), tetrahydrofuran (2), ethyl acetate (3), acetone
(4), acetonitrile (5), ethanol (6), water (7), methyl alcohol
Fig. 3 is the fluorescence response spectrogram of fluorescent optical sensor molecule in the acetone soln that contains different volumes water: wherein ordinate is a fluorescence intensity, and horizontal ordinate is a wavelength.Liquid water content is followed successively by (v/v%) from low to high: (1) 0 (2) 3.0 (3) 5.0 (4) 10.0 (5) 15.0 (6) 20.0 (7) 30.0 (8) 40.0
Fig. 4 fluorescence intensity that is the fluorescent optical sensor molecule when circulation feeds the acetone soln of different liquid water contents is situation over time: wherein ordinate is a fluorescence intensity, and horizontal ordinate is the time.Liquid water content is followed successively by (v/v%) from low to high: (a) 0 (b) 4.0 (c), 6.0 (d) 40.0
Fig. 5 is the fluorescence intensity of embodiment 1 and the graph of a relation of liquid water content;
Fig. 6 is the fluorescence intensity of embodiment 2 and the graph of a relation of liquid water content;
Fig. 7 is the fluorescence intensity of embodiment 3 and the graph of a relation of liquid water content.
This chalcone derivative is one and gives-receptor structure class fluorescent chemicals; have very high get fluorescence quantum yield and bigger Stokes (Stokes) displacement; 4-amino-4 '-N; N-dimethylamino chalcone is by the product after the acylation reaction; it possesses can be for the two keys of the end group of polymerization, and the compou nd synthesis step is as follows:
4-amino-4 '-N, N-dimethylamino chalcone (A) can be by document (natural science progress volume December the 9th in 1999 The 12nd phase supplementary issue) synthetic route in is synthetic. With 0.60g compound (A), the 70ml anhydrous tetrahydro furan, 0.70ml three Ethamine adds in the 250ml there-necked flask, starts agitator, slowly drips the 0.60ml methacrylic chloride in ice bath, drips off After at room temperature continued stirring reaction 4 hours, rotary evaporation was removed oxolane after reaction finished, and added 150ml distilled water, Last suction filtration obtains product (B) and is brown solid, productive rate 73.0%. Mass spectrum: base peak 334, [M+1]+335。
In above-mentioned fluorescence water sensor molecular compound structure, carbonyl be electron group, and N, the N-dimethylamino then It is electron-donating group. Have to-receptor structure compound for this class, intramolecular charge takes place easily shift (ICT). When compound molecule is stimulated, because shifting, strong intramolecular charge causes non-radiative decay, further cause just molten Activate the generation of mechanics effect. Simultaneously, its excited electronic state has bigger polarity than ground state, along with increasing of solvent polarity Greatly, excitation state comparison ground state is produced bigger stabilization, therefore, fluorescence spectrum increases with solvent polarity and to long wave Direction moves. When containing a small amount of water in organic solvent, the easy and water formation hydrogen bond compound of this fluorescence carrier molecule, and Make the fluorescence intensity rapid decrease. When changing such as water content in the acetone, fluorescence intensity changes thereupon, sees Fig. 3. Chalcone is derived The above-mentioned fluorescence response that thing produces in water-containing organic solvent can be used as fluorescent optical sensor, to realize few in the organic solvent The original position of water gaging, in real time detection. Preparation and the assay method of fluorescent optical sensor may further comprise the steps:
(1), quartzy slide (diameter 13mm) immerses in the chromic acid lotion and soaked 30 minutes, puts into successively then 3% hydrofluoric acid With respectively soaked in 10% hydrogenperoxide steam generator 20 minutes, cleaner with distilled water flushing. With 0.2ml 3-(trimethoxy silane Base) propyl methacrylate (TSPM), 2ml 0.2mol L-1PH is that acetic acid-acetic acid of 3.6 is received buffer solution and 8ml secondary Distilled water mixes, and stirs 5 minutes with preparation TSPM solution. Quartzy slide is immersed this solution 2 hours, use at last distilled water Rinse drying at room temperature well.
(2), chalcone derivative 15mg is dissolved in 0.2ml N, in the dinethylformamide, adds the 200mg acrylamide more successively, 0.4ml hydroxyethyl methylacrylate, 0.15ml crosslinking chemical, 0.15ml triethanolamine, 0.3ml photosensitizer.Get this coating solution of 0.1～0.2ml and drip on clean polyfluortetraethylene plate, cover thereon, use uviol lamp (254nm) irradiation 20 minutes again, last water and alcohol flushing, drying at room temperature with the slide that silanization is good.
(3), fluorescence measurement be the band computer data processing system PerkingElmer LS55 luminoscope on carry out, light source is a 150W atmosphere lamp, detecting device is a R928F infrared-sensitive photomultiplier.The quartzy slide that will adhere to the auroral poles film is fixed on homemade teflon flow cell (see figure 1) top by nut, and face makes the auroral poles film contact with sample solution down.A both arms optical fiber (diameter 8mm, length 1m) one terminates on the luminoscope other end and inserts flow cell and be close to the slide reverse side.The end of the radiation that excitation source sends by both arms optical fiber is transferred to and shines surface of glass slide in the flow cell, and excites the fluorescent material in the auroral poles film, and emitted fluorescence turns back to detecting device by other end transmission again, measures.Sample solution is by the speed input flow cell of peristaltic pump with 1.5ml/min, and auroral poles film and sample solution can get a stable fluorescence intensity level after reaching balance.Fluorescence chemical sensor of the present invention can be applicable to the mensuration of liquid water content in the various organic solvents.The fluorescence response spectrum of this sensor in different organic solvents is seen Fig. 2.
Fluorescent optical sensor molecule involved in the present invention, structure is simple relatively, be easy to synthesize, can be it is immobilized on glass surface or optical fiber head by the reactive group in the fluorescence chemical sensor molecule, realize device, make it be applied to the key component of fluorescence water sensor device.This fluorescence water sensor has good stability, and the fluorescence response time is short, and the characteristics that amplitude is big can be applicable to the original position of minor amount of water in the organic solvent, detection in real time, the detection sensitivity height.
Embodiment
Following example is the application of fluorescence chemical sensor proposed by the invention.But the present invention will be not limited to listed example.
Embodiment 1:
The fluorescence chemical sensor that makes is packed in the flow cell, and peristaltic pump is imported flow cell with the speed of 1.5ml/min with sample, and sample solution is the different acetone soln of water cut.Measure fluorescence intensity at maximum excitation wavelength 450nm and emission wavelength 536nm place, the excitation-emission slit is 5nm.Fluorescence intensity when record auroral poles film and sample solution reach balance is drawn auroral poles film fluorescence intensity and is seen Fig. 5 with the fluorescence response that liquid water content in the acetone changes, and presents certain linear between the two in liquid water content 0～6% scope.
Its correction equation is:
F＝-67.59[H
2O]+883.85 (R＝0.9984，[H
2O]＝0％-6％)
When feeding the acetone soln of different liquid water contents with sensor of the present invention circulation fluorescence intensity over time situation see Fig. 4, demonstrate reappearance and reversibility preferably as can be seen from Figure during the liquid water content of this sensor in measuring acetone soln.
Embodiment 2:
The fluorescence chemical sensor that makes is packed in the flow cell, and peristaltic pump is imported flow cell with the speed of 1.5ml/min with sample, and sample solution is the different ethanolic solution of water cut.Measure fluorescence intensity at maximum excitation wavelength 450nm and emission wavelength 544nm place, the excitation-emission slit is 5nm.Fluorescence intensity when record auroral poles film and sample solution reach balance is drawn auroral poles film fluorescence intensity and is seen Fig. 6 with the fluorescence response that liquid water content in the ethanol changes, and presents certain linear between the two in liquid water content 0～6% scope.
Its correction equation is:
F＝-53.83[H
2O]+635.49 (R＝0.9996，[H
2O]＝0％-6％)
Embodiment 3:
The fluorescence chemical sensor that makes is packed in the flow cell, and peristaltic pump is imported flow cell with the speed of 1.5ml/min with sample, and sample solution is the different acetonitrile solution of water cut.Measure fluorescence intensity at maximum excitation wavelength 450nm and emission wavelength 540nm place, the excitation-emission slit is 5nm.Fluorescence intensity when record auroral poles film and sample solution reach balance is drawn auroral poles film fluorescence intensity and is seen Fig. 7 with the fluorescence response that liquid water content in the acetonitrile changes, and presents certain linear between the two in liquid water content 0～6% scope.
Its correction equation is:
F＝-78.91[H
2O]+764.96 (R＝0.9983，[H
2O]＝0％-6％)
Claims (2)
1; a kind of fluorescence chemical sensor that detects liquid water content in the organic solvent; the slide or the optical fiber that comprise silanization; the membrane matrix monomer is attached to auroral poles film on slide or the optical fiber through photopolymerization; it is characterized in that the fluorescence carrier in the membrane matrix monomer is amino-the 4 '-N of 4-(methacryl) that the chalcone molecule is combined to through acyl group; N-dimethylamino chalcone; above-mentioned chalcone derivative is dissolved in N; in the dinethylformamide; add acrylamide successively; hydroxyethyl methylacrylate; crosslinking chemical; triethanolamine and photosensitizer are got the above-mentioned coating solution of 0.1～0.2ml on polyfluortetraethylene plate, with the slide of hexasilaneization or fiber cover thereon; behind uv photopolymerization, drying at room temperature is made.
2, a kind of fluorescence chemical sensor as claimed in claim 1 detects the method for liquid water content in the organic solvent, it is characterized in that: be sensor that fluorescence carrier the is made top, teflon circulation ground of packing into the chalcone derivative, testing sample is with the speed input flow cell of 1.5ml/min, the maximum excitation wavelength of fluorescence carrier and transmitted wave strong point are measured fluorescence intensity in different organic solvents, measure liquid water content in the organic solvent according to the correction equation formula.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102183551A (en) * | 2011-02-25 | 2011-09-14 | 华东理工大学 | Method for measuring trace water in organic solvent by using electro-active film impedance sensor |
| CN102746452A (en) * | 2012-07-18 | 2012-10-24 | 浙江大学 | Fluorescent sensor for detecting hydrosulfate ions as well as preparation method and application thereof |
| CN105572095A (en) * | 2016-03-18 | 2016-05-11 | 南京微瑞莱电子科技有限公司 | Detection reagent and quantitative detection method of human serum albumin |
| CN105651749A (en) * | 2016-01-19 | 2016-06-08 | 湖南科技大学 | Method for detecting water content in tetrahydrofuran through carbon nanoparticles |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2076709A1 (en) * | 1992-08-24 | 1994-02-25 | Ulrich J. Krull | Amplified fluorescence emission for chemical transduction |
| US6576192B1 (en) * | 1996-04-18 | 2003-06-10 | Novartis Ag | Fluoroionophores and their use in optical ion sensors |
| DE19925402C2 (en) * | 1999-06-02 | 2001-12-20 | Molecular Machines & Ind Gmbh | Screening of target-ligand interactions |
| JP2000356635A (en) * | 1999-06-15 | 2000-12-26 | Meidensha Corp | Concentration measuring method of chlorophyll a and device therefor |
| CN1237050C (en) * | 2003-07-14 | 2006-01-18 | 大连理工大学 | Synthesis of 2,6-diaminemethylpyridine derivative fluoescence chemical sensor molecule and its application |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102183551A (en) * | 2011-02-25 | 2011-09-14 | 华东理工大学 | Method for measuring trace water in organic solvent by using electro-active film impedance sensor |
| CN102183551B (en) * | 2011-02-25 | 2013-08-14 | 华东理工大学 | Method for measuring trace water in organic solvent by using electro-active film impedance sensor |
| CN102746452A (en) * | 2012-07-18 | 2012-10-24 | 浙江大学 | Fluorescent sensor for detecting hydrosulfate ions as well as preparation method and application thereof |
| CN102746452B (en) * | 2012-07-18 | 2014-01-15 | 浙江大学 | Fluorescent sensor for detecting hydrosulfate ions as well as preparation method and application thereof |
| 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 |
| CN105572095A (en) * | 2016-03-18 | 2016-05-11 | 南京微瑞莱电子科技有限公司 | Detection reagent and quantitative detection method of human serum albumin |
| CN105572095B (en) * | 2016-03-18 | 2018-12-18 | 南京微瑞莱电子科技有限公司 | A kind of detection reagent and quantitative detecting method of human serum albumins |
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| CN100483112C (en) | 2009-04-29 |
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