CN102175658A - Method for preparing reversible colorimetric oxygen sensing cloth label - Google Patents
Method for preparing reversible colorimetric oxygen sensing cloth label Download PDFInfo
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- CN102175658A CN102175658A CN 201110009169 CN201110009169A CN102175658A CN 102175658 A CN102175658 A CN 102175658A CN 201110009169 CN201110009169 CN 201110009169 CN 201110009169 A CN201110009169 A CN 201110009169A CN 102175658 A CN102175658 A CN 102175658A
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Abstract
The invention provides a method for preparing a reversible colorimetric oxygen sensing cloth label, relating to a colorimetric sensor is related, and providing a colorimetric oxygen sensing cloth label which has the characteristics of high brightness, good flexibility and simple structure and is capable of realizing visual fast measurement of oxygen concentration, and a preparation method thereof. The colorimetric oxygen sensing cloth label comprises two fluorescent dyes, a polystyrene micrballon and a cloth, wherein the two fluorescent dyes are wrapped in the polystyrene micrballon; one of the fluorescent dyes is sensitive to oxygen; and the polystyrene micrballon is fixed on the cloth. The preparation method comprises the following steps: preparing the polystyrene micrballon containing the two fluorescent dyes; and fixing the polystyrene micrballon on the cloth, so as to obtain the reversible colorimetric oxygen sensing cloth label. When being used, the colorimetric oxygen sensing cloth label prepared in the invention is only irradiated by one handhold ultraviolet light-emitting diode, and the colorimetric oxygen sensing cloth label emits quite bright colour lights; the blue fluorescent dye and the red fluorescent dye sensitive to the oxygen both can be excited by ultraviolet; the visual direct detection can be realized; and optical devices such as an optical filter and the like are not needed.
Description
Technical field
The present invention relates to colorimetric sensor, particularly a kind of reversible colorimetric oxygen sensing cloth label and preparation method thereof.
Background technology
Oxygen is a kind of important gas of keeping life on earth, and the detection of oxygen concentration is widely studied.Most in the past lambda sensor is based on galvanochemistry, pressure, photochemistry etc. and realizes quantitative measurement of oxygen content, has a wide range of applications in fields such as medicine, chemical industry, packaging for foodstuff, environmental science, life sciences.But existing these lambda sensors need scientific instrument auxiliary mostly, and the optics of very complicated and data analysis system have also limited their widespread uses in daily life.Visual oxygen inductor based on double-colored system possesses simple and visual detection mode, has caused people's attention in recent years.People such as Chen Xi (Wang, X.D., Chen, X., Xie, Z.X., Wang, X.R., Reversible optical sensor strip for oxygen[J] .AngewandteChemie-International Edition 2008,47:7450-7453) reported and use colourimetry to carry out the detection of oxygen content, realized detecting, can satisfy the needs of determination of oxygen content in the daily life without any need for the quick oxygen content of scientific instrument.Yet there are some defectives in they by the colorimetric lambda sensor of preparation: excitation source that needs are special and corresponding optical filter, the color that sensor presented is more shallow, the obvious aberration that the dyestuff of skewness can cause in the double-colored system.Therefore, be necessary to develop the colorimetric lambda sensor of a kind of practicality, safety and high brightness, realize need not the auxiliary visual colorimetric oxygen sensing detection of any optical device.
Summary of the invention
First purpose of the present invention is to provide that a kind of cost is low, brightness is high, sensitivity is good, simple structure, can realize the colorimetric oxygen sensing cloth label of the visual fast measuring of oxygen concentration.
Another object of the present invention is to provide a kind of preparation method of reversible colorimetric oxygen sensing cloth label.
Described reversible colorimetric oxygen sensing cloth label comprises two kinds of fluorescent dyes, polystyrene microsphere and cloth, and two kinds of fluorescent dyes are wrapped in the polystyrene microsphere, and wherein a kind of fluorescent dye is to the oxygen sensitivity, and polystyrene microsphere is fixed on the cloth.
Described two kinds of fluorescent dyes can be blue fluorescent dyes and red fluorescence dyestuff.Described blue fluorescent dyes can be the hydrophobicity fluorescent dye of emission wavelength between 400～500nm, as 2, and 2-(4, the 4-diphenylethyllene) dibenzoxazine etc.; Described red fluorescence dyestuff can be the oxygen responsive probe that emission wavelength is 630～700nm, as octaethylporphyrin platinum or octaethylporphyrin palladium etc.
The particle diameter of described polystyrene microsphere can be 1～3 μ m.Described cloth is preferably the cotton with fluorescer.
The preparation method of described a kind of reversible colorimetric oxygen sensing cloth label is: preparation contains the polystyrene microsphere of two kinds of fluorescent dyes, and is fixed on the cloth, promptly gets reversible colorimetric oxygen sensing cloth label.
The polystyrene microsphere that described preparation contains two kinds of fluorescent dyes can adopt the mark polymerization, and concrete steps are as follows:
1) with octaethylporphyrin platinum, 2,2-(4, the 4-diphenylethyllene) dibenzoxazine, 2,2-azoisobutyronitrile, methacrylic acid and styrene are pressed mass ratio and be (0.9～1.56): (1.2～4): (8～15): (8～12): 1000 mix, and get solution A;
2) polyvinyl pyrrolidone K-30 and ethanol are pressed mass ratio and be (9～20): 1000 mix, solution B;
3) with solution A and solution B (20～50) by volume: 100 mix, and carry out the lucifuge reaction after the mixed liquor deoxygenation, and reaction finishes the back cooling, separates, and removes accessory substance, promptly gets the polystyrene microsphere that contains two kinds of fluorescent dyes.
In step 3), the temperature of described lucifuge reaction can be 70～90 ℃, and the time of lucifuge reaction can be 20～28h.
Described fixing can be adopted following method: the polyurethane hydrogel is mixed with the ethanolic solution that contains polystyrene microsphere, mixed solution is applied on the cotton thread, cotton thread is embroidered on the cloth.
The colorimetric oxygen sensing cloth label of the present invention's preparation only need shine with a hand-held ultraviolet light-emitting diode in use, and colorimetric oxygen sensing cloth label can send very bright coloured light.In being exposed to the different oxygen concentrations environment, colorimetric oxygen sensing cloth label can present different colors, and its resolution can reach 1%.Colorimetric oxygen sensing cloth label among the present invention has following advantage: at first, its shape can change arbitrarily; Simultaneously, fluorescent dye wraps up by polystyrene microsphere, has avoided the self-quenching that causes because of the fluorescent material excessive concentration.The polystyrene microsphere size is even, and the color distribution that the cloth label of colorimetric oxygen sensing is presented is even, has improved the accuracy that detects.Blue fluorescent dyes and can be realized visual direct detection, without any need for optical devices such as optical filters by ultraviolet excitation to the responsive red fluorescence dyestuff of oxygen.
Embodiment
The present invention is further illustrated by the following examples.
Embodiment 1
Take by weighing 5.7mg octaethylporphyrin platinum, 7.64mg 2-(4, the 4-diphenylethyllene) dibenzoxazine and 50.9mg 2, the 2-azoisobutyronitrile, with the octaethylporphyrin platinum, 2 that weighs up, 2-(4, the 4-diphenylethyllene) dibenzoxazine and 2, the 2-azoisobutyronitrile is put into the vial of 10mL.Add in 7mL styrene and the 52 μ L methacrylic acids and dissolve, mixing gets solution A.
Take by weighing 0.177g polyvinyl pyrrolidone K-30 and put into the 50mL vial, add the 25mL dissolve with ethanol, mixing gets solution B.
Solution A joined in the solution B mix.And after in the 50mL vial, adding the magnet rotor stirring, be placed on the magnetic stirring apparatus, load onto thermometer, mixed liquor is with after the nitrogen deoxygenation 30min, at 70 ℃ of oil bath lucifuges reaction 20h.After being cooled to room temperature, product is transferred to the 50mL centrifuge tube,, use the ethanol centrifuge washing again 3 times at the centrifugal 5min of 3000rpm.Polystyrene microsphere with the oxygen sensitivity is dispersed in the 30mL ethanol at last.
Massfraction is that 5% polyurethane hydrogel is dissolved in ethanol and water (volume ratio of ethanol and water is 9: the 1) mixed liquor by polyurethane and makes, pipetting the ethanolic solution and the massfraction that are dispersed with polystyrene microsphere is 5% each 0.5mL of polyurethane hydrogel, and obtain mixed sols liquid C behind the mixing, mixed sols liquid C is coated on the cotton thread that does not have fluorescer, embroidering is not then having on the cotton of fluorescer, dry under room temperature, promptly get reversible colorimetric oxygen sensing cloth label.
Embodiment 2
Take by weighing 8mg octaethylporphyrin platinum, 14mg 2-(4, the 4-diphenylethyllene) dibenzoxazine and 65mg 2, the 2-azoisobutyronitrile, with the octaethylporphyrin platinum, 2 that weighs up, 2-(4, the 4-diphenylethyllene) dibenzoxazine and 2, the 2-azoisobutyronitrile is put into the vial of 10mL.Add in 7mL styrene and the 60 μ L methacrylic acids and dissolve, mixing obtains solution A.
Take by weighing 0.25g polyvinyl pyrrolidone K-30 and put into the 50mL vial, add the 25mL dissolve with ethanol, mixing obtains solution B.
Solution A joined in the solution B mix.And in the 50mL vial, add the magnet rotor stirring, and be placed on the magnetic stirring apparatus, load onto thermometer, mixed liquor is with after the nitrogen deoxygenation 30min, at 80 ℃ of oil bath lucifuges reaction 24h.After being cooled to room temperature, product is transferred to the 50mL centrifuge tube,, use the ethanol centrifuge washing again 3 times at the centrifugal 5min of 3000rpm.Polystyrene microsphere with the oxygen sensitivity is dispersed in the 30mL ethanol at last.
Massfraction is that 5% polyurethane hydrogel is dissolved in ethanol and water (volume ratio of ethanol and water is 9: the 1) mixed liquor by polyurethane and makes, pipetting the ethanolic solution and the massfraction that are dispersed with polystyrene microsphere is 5% each 0.5mL of polyurethane hydrogel, and obtain mixed sols liquid C behind the mixing, mixed sols liquid C is coated on the cotton thread that does not have fluorescer, embroidering is not then having on the cotton of fluorescer, dry under room temperature, obtain reversible colorimetric oxygen sensing cloth label.
Embodiment 3
Take by weighing 10mg octaethylporphyrin platinum, 25mg 2-(4, the 4-diphenylethyllene) dibenzoxazine and 95mg 2, the 2-azoisobutyronitrile, with the octaethylporphyrin platinum, 2 that weighs up, 2-(4, the 4-diphenylethyllene) dibenzoxazine and 2, the 2-azoisobutyronitrile is put into the vial of 10mL.Add in 7mL styrene and the 76 μ L methacrylic acids and dissolve, mixing obtains solution A.
Take by weighing 0.395g polyvinyl pyrrolidone K-30 and put into the 50mL vial, add the 25mL dissolve with ethanol, mixing obtains solution B.
Solution A joined in the solution B mix.And in the 50mL vial, add the magnet rotor stirring, and be placed on the magnetic stirring apparatus, load onto thermometer, mixed liquor is with after the nitrogen deoxygenation 30min, at 90 ℃ of oil bath lucifuges reaction 28h.After being cooled to room temperature, product is transferred to the 50mL centrifuge tube,, use the ethanol centrifuge washing again 3 times at the centrifugal 5min of 3000rpm.Polystyrene microsphere with the oxygen sensitivity is dispersed in the 30mL ethanol at last.
Massfraction is that 5% polyurethane hydrogel is dissolved in ethanol and water (volume ratio of ethanol and water is 9: the 1) mixed liquor by polyurethane and makes, pipetting the ethanolic solution and the massfraction that are dispersed with polystyrene microsphere is 5% each 0.5mL of polyurethane hydrogel, and obtain mixed sols liquid C behind the mixing, mixed sols liquid C is coated on the cotton thread that does not have fluorescer, embroidering is not then having on the cotton of fluorescer, dry under room temperature, obtain reversible colorimetric oxygen sensing cloth label.
The application is with blue fluorescent dyes (2,2-(4, the 4-diphenylethyllene) dibenzoxazine) and to the responsive red fluorescence dyestuff of oxygen (octaethylporphyrin platinum) is fixed in the polystyrene microsphere, polystyrene microsphere high concentration ground is fixed on the cotton thread, then cotton thread is embroidered on cotton.With a hand-held ultraviolet light-emitting diode irradiation cotton, under the oxygen atmosphere of variable concentrations, colorimetric oxygen sensing cloth label presents different colors, and its resolution can reach 1%.Colorimetric oxygen sensing cloth label shape among the present invention can change arbitrarily, and color distribution is even, does not need the characteristics of complicated optical devices such as optical filter, is very easy to the application in daily life of this type of sensor.
Claims (10)
1. reversible colorimetric oxygen sensing cloth label, it is characterized in that it comprises two kinds of fluorescent dyes, polystyrene microsphere and cloth, described two kinds of fluorescent dyes are wrapped in the polystyrene microsphere, and wherein a kind of fluorescent dye is to the oxygen sensitivity, and described polystyrene microsphere is fixed on the cloth.
2. a kind of reversible colorimetric oxygen sensing cloth label as claimed in claim 1 is characterized in that described two kinds of fluorescent dyes are blue fluorescent dyes and red fluorescence dyestuff.
3. a kind of reversible colorimetric oxygen sensing cloth label as claimed in claim 1, it is characterized in that described blue fluorescent dyes is the hydrophobicity fluorescent dye of emission wavelength between 400～500nm, described red fluorescence dyestuff is that emission wavelength is the oxygen responsive probe of 630～700nm.
4. as claim 2 or 3 described a kind of reversible colorimetric oxygen sensing cloth labels, it is characterized in that described blue fluorescent dyes is 2,2-(4, the 4-diphenylethyllene) dibenzoxazine, described red fluorescence dyestuff is octaethylporphyrin platinum or octaethylporphyrin palladium.
5. a kind of reversible colorimetric oxygen sensing cloth label as claimed in claim 1, the particle diameter that it is characterized in that described polystyrene microsphere is 1～3 μ m.
6. a kind of reversible colorimetric oxygen sensing cloth label as claimed in claim 1 is characterized in that described cloth is not for having the cotton of fluorescer.
7. the preparation method of a kind of reversible colorimetric oxygen sensing cloth label as claimed in claim 1 is characterized in that comprising: preparation contains the polystyrene microsphere of two kinds of fluorescent dyes, and is fixed on the cloth, promptly gets reversible colorimetric oxygen sensing cloth label.
8. the preparation method of a kind of reversible colorimetric oxygen sensing cloth label as claimed in claim 7 is characterized in that the polystyrene microsphere that described preparation contains two kinds of fluorescent dyes can adopt the mark polymerization.
9. the preparation method of a kind of reversible colorimetric oxygen sensing cloth label as claimed in claim 8 is characterized in that the concrete steps of described mark polymerization may further comprise the steps:
1) with octaethylporphyrin platinum, 2,2-(4, the 4-diphenylethyllene) dibenzoxazine, 2,2-azoisobutyronitrile, methacrylic acid and styrene are pressed mass ratio and be (0.9～1.56): (1.2～4): (8～15): (8～12): 1000 mix, and get solution A;
2) polyvinyl pyrrolidone K-30 and ethanol are pressed mass ratio and be (9～20): 1000 mix, and obtain solution B;
3) with solution A and solution B (20～50) by volume: 100 mix, and carry out the lucifuge reaction after the mixed liquor deoxygenation, and reaction finishes the back cooling, separates, and removes accessory substance, promptly gets the polystyrene microsphere that contains two kinds of fluorescent dyes.
10. the preparation method of a kind of reversible colorimetric oxygen sensing cloth label as claimed in claim 9 is characterized in that in step 3), and the temperature of described lucifuge reaction is 70～90 ℃, and the time of lucifuge reaction is 20～28h.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104262811A (en) * | 2014-09-19 | 2015-01-07 | 哈尔滨工业大学 | Preparation method and application of polystyrene fluorescent microspheres |
| CN108084366A (en) * | 2017-12-18 | 2018-05-29 | 哈尔滨工业大学 | Colorimetric fluorescent microsphere emulsion preparation method based on octaethylporphyrin platinum and the application in optical oxygen sensing micro-fluidic detection chip |
| CN110229261A (en) * | 2019-05-29 | 2019-09-13 | 天津大学 | A kind of fluorescent grain synthetic method for fluid trace |
| CN112730363A (en) * | 2020-12-27 | 2021-04-30 | 复旦大学 | Monodisperse fluorescent nano sensor for measuring dissolved oxygen in cell and preparation method thereof |
| CN112832038A (en) * | 2020-12-29 | 2021-05-25 | 江南大学 | Preparation method of textile color card for ultraviolet intensity detection |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US20050037512A1 (en) * | 2003-08-12 | 2005-02-17 | Ming-Hsiung Yeh | Microencapsulation of oxygen-sensing particles |
| CN1959381A (en) * | 2006-11-13 | 2007-05-09 | 湖南大学 | Fluorescence PII sensor with inner reference and comparison, and preparation method |
| US7534615B2 (en) * | 2004-12-03 | 2009-05-19 | Cryovac, Inc. | Process for detecting leaks in sealed packages |
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2011
- 2011-01-14 CN CN201110009169XA patent/CN102175658B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050037512A1 (en) * | 2003-08-12 | 2005-02-17 | Ming-Hsiung Yeh | Microencapsulation of oxygen-sensing particles |
| US7534615B2 (en) * | 2004-12-03 | 2009-05-19 | Cryovac, Inc. | Process for detecting leaks in sealed packages |
| CN1959381A (en) * | 2006-11-13 | 2007-05-09 | 湖南大学 | Fluorescence PII sensor with inner reference and comparison, and preparation method |
Non-Patent Citations (2)
| Title |
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| 《Talanta》 20050801 Sang Hyuk Im 等 Synthesis of polystyrene beads loaded with dual luminophors for self-referenced oxygen sensing 1-8 第67卷, * |
| 《Trends in Analytical Chemistry》 20101231 Xu-dong Wang 等 Optical oxygen sensors move towards colorimetric determination 全文 1-10 第29卷, 第4期 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104262811A (en) * | 2014-09-19 | 2015-01-07 | 哈尔滨工业大学 | Preparation method and application of polystyrene fluorescent microspheres |
| CN108084366A (en) * | 2017-12-18 | 2018-05-29 | 哈尔滨工业大学 | Colorimetric fluorescent microsphere emulsion preparation method based on octaethylporphyrin platinum and the application in optical oxygen sensing micro-fluidic detection chip |
| CN110229261A (en) * | 2019-05-29 | 2019-09-13 | 天津大学 | A kind of fluorescent grain synthetic method for fluid trace |
| CN112730363A (en) * | 2020-12-27 | 2021-04-30 | 复旦大学 | Monodisperse fluorescent nano sensor for measuring dissolved oxygen in cell and preparation method thereof |
| CN112832038A (en) * | 2020-12-29 | 2021-05-25 | 江南大学 | Preparation method of textile color card for ultraviolet intensity detection |
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