CN101812293B - Preparation method of fluorescent nanoparticles with light stability - Google Patents
Preparation method of fluorescent nanoparticles with light stability Download PDFInfo
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- CN101812293B CN101812293B CN2010101692942A CN201010169294A CN101812293B CN 101812293 B CN101812293 B CN 101812293B CN 2010101692942 A CN2010101692942 A CN 2010101692942A CN 201010169294 A CN201010169294 A CN 201010169294A CN 101812293 B CN101812293 B CN 101812293B
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Abstract
The invention discloses a preparation method of fluorescent nanoparticles with light stability in the nano-technology field, which comprises the following steps of: weighting the polyion liquid and dissolving in water or polar solution, and stirring at room temperature for dissolving; weighing the fluorescent micromolecules and dissolving in water or polar solvent, and stirring until the pH value is between 7 and10; weighing the azo surfactant and dissolving the azo surfactant in water or polar solvent, and stirring until the azo surfactant is completely dissolved and the pH value is between 7 and 10; dripping the obtained fluorescent micromolecules into the stirred polyion liquid solution and continuing stirring; dripping the obtained azo surfactant solution into the mixed solution obtained by stirring and continuing stirring to obtain the fluorescent nanoparticles with light stability, wherein the average particle size of the nanoparticles is 20 to 150 nm. The preparation method is easy, environment-friendly and easy to operate, and the fluorescent nanoparticles have relatively high light stability.
Description
Technical field
The present invention relates to a kind of preparation method of field of nanometer technology, particularly a kind of preparation method who obtains fluorescent nanoparticles with light stability by the two-pack organic molecule through the ionic bonding polyelectrolyte.
Background technology
In recent years; Fluorescent nano particles has using value and prospect very widely at high-technology fields such as biosensor, delivery of drug, still, all has the photobleaching phenomenon as fluorescent substance; Photobleaching (photonic bleaching) phenomenon is meant; Fluorescent substance makes it that chemical reaction or conformational change take place under illumination condition, and loses the phenomenon of fluorescigenic characteristic, is exactly so-called bleaching.The photobleaching phenomenon also is the key issue of the Application Areas of restriction fluorescent substance.At present, comparatively common fluorescent substance, as: the noble metal nano particles of conjugated polymers, chromophoric group modification etc., it is applied to fields such as transmitter and has a lot of shortcomings, and for example: luminous intensity is not high, influences its sensing range; The photobleaching phenomenon that is difficult to avoid, its light stability is lower, and under the state of ultraviolet excitation, fluorescent quenching speed is very fast, has limited its range of application.How to prepare a kind of higher fluorescent emission intensity that has, and have the fluorescent nano material of higher stability to become the technical problem in current this field light.
Find through searching document; In order to solve the problem of the not high and light stability difference of fluorescent material luminous intensity; Terms of settlement commonly used is that covalent chemical compound method or the simple physics adulterating method through classics is incorporated into micromolecule additive in the fluorescent substance, but has many deficiencies, and for example: P.X.Jun etc. have delivered 1-(carboxamide methyl)-3H-indoles side acids dyestuff on " dyestuff and coating " (Dyes and Pigments) magazine: synthetic; Spectrum; Light stability and with the bonded article of Ox blood serum, mainly studied the synthetic of this type dyestuff, the research of character and light stability; But the products therefrom productive rate is very low, process is loaded down with trivial details, cost is higher, and utilizes some to pollute heavier chemical solvents in the process more; 0.0.Park Deng on " macromole news flash " (Macromolecular Rapid Communications) magazine, having delivered the article that improves the look fluorescent polymer light stability of turning blue through the doping golden nanometer particle; The golden nanometer particle of having studied the doping different ratios is to improving the influence of light stability; But this method consistency is relatively poor, is difficult to control the homogeneity that additive distributes in material.
Summary of the invention
The present invention is directed to the above-mentioned deficiency that prior art exists; A kind of preparation method of fluorescent nanoparticles with light stability is provided, the present invention can be as required through the length of the flexible chain of regulating assembly azo tensio-active agent or size and the luminous intensity that the substituting group hydrophilic and hydrophobic is regulated and control fluorescent nanoparticles with light stability.
The present invention realizes through following technical scheme:
The preparation method of the fluorescent nanoparticles with light stability that the present invention relates to comprises the steps:
(1) takes by weighing in the water-soluble or polar solvent of poly ion liquid, at room temperature stir, it is dissolved fully;
Poly ion liquid described in the step (1) is positively charged ion pyridine or imidazoles polymkeric substance, the perhaps cationic polyelectrolyte of radical polymerization.
Cationic polyelectrolyte described in the step (1) or to gather the poly ion liquid molecular weight be 5000-500000.
Water or polar solvent described in the step (1), water are the secondary redistilled water; Polar solvent is an ethanol, methyl alcohol, acetone or contain the mixing solutions of these solution.
Polar solvent concentration described in the step (1) is 0.1-100 μ mol/mL.
(2) take by weighing in the water-soluble or polar solvent of fluorescent small molecule and stir, to the pH value between the 7-10;
Fluorescent small molecule described in the step (2) is meant: at first contract and make 1-benzothiazole ianthone oxazole, imidazoles) base-2-hydroxyanilines, obtain the fluorescent small molecule that an end contains carboxylic acid with the Succinic anhydried reaction then, its general structure (being abbreviated as FL) is:
Wherein X is oxygen, nitrogen, sulphur.
Stirring described in the step (2), its temperature is: 20-80 ℃;
PH value described in the step (2) is meant with the 0.01-10mol/L sodium hydroxide solution and regulates; Concentration of sodium hydroxide solution is 0.1-50 μ mol/mL.
(3) take by weighing and be stirred to dissolving fully and pH value in the water-soluble or polar solvent of azo tensio-active agent between the 7-10;
Azo surfactant structure general formula (being abbreviated as Azo) described in the step (3) is:
Wherein Y is methoxyl group, trifluoromethyl, N, N-dimethyl-, itrile group, n=1,3,5,7,9,11.
Azo tensio-active agent described in the step (3), its concentration are 0.1-50 μ mol/mL;
Stirring described in the step (3), its temperature is: 20-80 ℃;
PH value described in the step (3) is meant with the 0.01-10mol/L sodium hydroxide solution and regulates; Concentration of sodium hydroxide solution is 0.1-50 μ mol/mL.
(4) after the fluorescent small molecule solution that step (2) is made splashes into the poly ion liquid solution that stirs, continue to stir;
(5) the azo surfactant soln that step (3) is made continues to stir after splashing into the mixing solutions that the step (4) that stirs makes, and obtains fluorescent nanoparticles with light stability, and the median size of this nanoparticle is 20-150nm.
Fluorescent small molecule solution described in the step (1,2) is 0.01: 1～0.5: 1 with the molar charge ratio of poly ion liquid solution.
Azo surfactant soln described in the step (1,3) is 0.01: 1～0.5: 1 with the molar charge ratio of poly ion liquid solution.
Stirring described in the step (4,5), its churning time 10-60 minute.
The fluorescent nanoparticles with light stability that the present invention obtains has advantage: compare with other fluorescent substances, the preparation method is simple, environmental friendliness, and operation is easy to realize; Can be as required length or the size and the luminous intensity that the substituting group hydrophilic and hydrophobic is regulated and control fluorescent nanoparticles with light stability of flexible chain through regulating assembly azo tensio-active agent; Fluorescent nano particles to light particularly UV-light higher light stability is arranged, expanded it as fluorescence sense modulator material range of application and application conditions.
Description of drawings
The fluorescence spectrum of the fluorescent nanoparticles with light stability that Fig. 1 embodiment 1 makes.
The sample that fluorescent nanoparticles with light stability that Fig. 2 embodiment 1, embodiment 2 make and reference test obtain is fluorescence intensity curve over time under the 365nm ultra violet lamp.
The SEM figure of the fluorescent nanoparticles with light stability that Fig. 3 embodiment 1 makes.
The SEM figure of the fluorescent nanoparticles with light stability that Fig. 4 embodiment 2 makes.
Embodiment
Below in conjunction with accompanying drawing embodiments of the invention are elaborated, present embodiment provided detailed embodiment and concrete operating process, but protection domain of the present invention is not limited to following embodiment being to implement under the prerequisite with technical scheme of the present invention.
Embodiment 1
(1) take by weighing that the laboratory is homemade and gather (bromination 1-normal-butyl-4-vinylpridine) soluble in water, at room temperature stir, it is dissolved fully, PIL concentration is 50 μ mol/mL.
(2) it is soluble in water to take by weighing fluorescent small molecule FL (structural formula see claim book, wherein X is a sulphur), stir down at 80 ℃, and with 1mol/L sodium hydroxide solution adjust pH to 7.0, concentration is 5 μ mol/mL.
(3) it is soluble in water to take by weighing azo surfactant A zo (structural formula see claim book, wherein Y is a methoxyl group, n is 3), stir down at 80 ℃, and with 1mol/L sodium hydroxide solution adjust pH to 7.0, concentration is 5 μ mol/mL.
(4) the FL solution that step (2) is made splashes in the PIL solution of vigorous stirring, dropwises continued and stirs 60 minutes, and FL solution is 0.1: 1 with the mole positive and negative charge ratio of PIL solution.
(5) the Azo solution that step (3) is made splashes in the mixing solutions that the step (4) of vigorous stirring makes, and continues to stir 60 minutes, and Azo solution is 0.1: 1 with the mole positive and negative charge ratio of PIL solution.Obtain fluorescent nanoparticles with light stability.
Fig. 1 has provided the fluorescence spectrum of the fluorescent nanoparticles with light stability that makes, and can find out, along with the concentration increase of Azo, fluorescent emission intensity constantly strengthens; Embodiment 1 curve from Fig. 2 can find out, with the ultra violet lamp of 365nm after 1 hour, a fluorescence cancellation about 20%, and with etc. the pure FL solution of volumetric molar concentration do in the reference test (the reference test curve among Fig. 2) the basic cancellation of fluorescence totally; Fig. 3 is the scanning electron microscope diagram sheet of the fluorescent nano particles that obtains.
Embodiment 2
(1) take by weighing that the laboratory is homemade and gather (bromination 1-ethyl-4-vinylpridine) soluble in water, at room temperature stir, it is dissolved fully, PIL concentration is 100 μ mol/mL.
(2) it is soluble in water to take by weighing fluorescent small molecule (structural formula see claim book, wherein X is an oxygen), stir down at 80 ℃, and with 0.5mol/L sodium hydroxide solution adjust pH to 8.0, concentration is 10 μ mol/mL.
(3) it is soluble in water to take by weighing azo tensio-active agent (structural formula see claim book, wherein Y is a trifluoromethyl, n is 5), stir down at 80 ℃, and with 0.5mol/L sodium hydroxide solution adjust pH to 8.0, concentration is 10 μ mol/mL.
(4) the FL solution that step (2) is made splashes in the PIL solution of vigorous stirring, dropwises continued and stirs 50 minutes, and FL solution is 0.2: 1 with the mole positive and negative charge ratio of PIL solution.
(5) the Azo solution that step (3) is made splashes in the mixing solutions that the step (4) of vigorous stirring makes, and continues to stir 50 minutes, and Azo solution is 0.2: 1 with the mole positive and negative charge ratio of PIL solution.Obtain fluorescent nanoparticles with light stability.
Embodiment 2 curves from Fig. 2 can be found out, compare fluorescence intensity with embodiment 1 and improve; With the ultra violet lamp of 365nm after 1 hour, a fluorescence cancellation about 20%, and with etc. the pure FL solution of volumetric molar concentration do in the reference test (reference test curve among Fig. 2) the basic cancellation of fluorescence totally; Fig. 4 is the scanning electron microscope diagram sheet of the fluorescent nano particles that obtains.
Embodiment 3
(1) take by weighing that the laboratory is homemade and gather (bromination 1-hexyl 4 vinyl pyridines) soluble in water, at room temperature stir, it is dissolved fully, PIL concentration is 10 μ mol/mL.
(2) it is soluble in water to take by weighing fluorescent small molecule (structural formula see claim book, wherein X is a nitrogen), stir down at 80 ℃, and with 5mol/L sodium hydroxide solution adjust pH to 9.0, concentration is 1 μ mol/mL.
(3) it is soluble in water to take by weighing azo tensio-active agent (structural formula see claim book, wherein Y is N, N-dimethyl-, n are 7), stir down at 80 ℃, and with 5mol/L sodium hydroxide solution adjust pH to 9.0, concentration is 1 μ mol/mL.
(4) the FL solution that step (2) is made splashes in the PIL solution of vigorous stirring, dropwises continued and stirs 20 minutes, and FL solution is 0.4: 1 with the mole positive and negative charge ratio of PIL solution.
(5) the Azo solution that step (3) is made splashes in the mixing solutions that the step (4) of vigorous stirring makes, and continues to stir 20 minutes, and Azo solution is 0.4: 1 with the mole positive and negative charge ratio of PIL solution.
When adding Y was the azo tensio-active agent of methoxyl group, the fluorescent emission intensity of fluorescent nano particles strengthened (Fig. 1) along with the increase of azo surfactant concentration among the embodiment; Under same concentrations, through regulating the fluorescent emission intensity that azo tensio-active agent substituting group (Y is methoxyl group, trifluoromethyl, N, the N-dimethyl-) is regulated fluorescent nano particles; Fluorescent nano particles is at the UV-irradiation of 365nm after 1 hour, still has 80% fluorescent emission intensity to be able to keep, and explains that the fluorescent nano particles that makes through this method has higher light stability (Fig. 2).
Claims (7)
1. the preparation method of a fluorescent nanoparticles with light stability is characterized in that, comprises the steps:
(1) takes by weighing in the water-soluble or polar solvent of poly ion liquid, at room temperature stir, it is dissolved fully;
(2) take by weighing in the water-soluble or polar solvent of fluorescent small molecule and stir, to the pH value between the 7-10;
(3) take by weighing and be stirred to dissolving fully and pH value in the water-soluble or polar solvent of azo tensio-active agent between the 7-10;
(4) after the fluorescent small molecule solution that step (2) is made splashes into the poly ion liquid solution that stirs, continue to stir;
(5) the azo surfactant soln that step (3) is made continues to stir after splashing into the mixing solutions that the step (4) that stirs makes, and obtains fluorescent nanoparticles with light stability, and the median size of this nanoparticle is 20-150nm;
Poly ion liquid described in the step (1) is positively charged ion pyridine or imidazoles polymkeric substance, the perhaps cationic polyelectrolyte of radical polymerization;
Described poly ion liquid molecular weight is 5000-500000;
Fluorescent small molecule described in the step (2) is meant: at first contract and make 1-benzothiazolyl-2-hydroxyanilines, obtain the fluorescent small molecule that an end contains carboxylic acid with the Succinic anhydried reaction then, its general structure is:
Wherein: X is oxygen, nitrogen, sulphur;
Azo surfactant structure general formula described in the step (3) is:
Wherein Y is methoxyl group, trifluoromethyl, N, N-dimethyl-, itrile group, n=1,3,5,7,9,11.
2. the preparation method of fluorescent nanoparticles with light stability according to claim 1 is characterized in that, water or the polar solvent described in the step (1), water are the secondary redistilled water, and polar solvent is an ethanol, methyl alcohol, acetone or contain the mixing solutions of these solution;
Described polar solvent concentration is 0.1-100 μ mol/mL.
3. the preparation method of fluorescent nanoparticles with light stability according to claim 1 is characterized in that, the pH value described in the step (2,3) is meant with the 0.01-10mol/L sodium hydroxide solution and regulates that concentration of sodium hydroxide solution is 0.1-50 μ mol/mL.
4. the preparation method of fluorescent nanoparticles with light stability according to claim 1 is characterized in that, the azo tensio-active agent described in the step (3), and its concentration is 0.1-50 μ mol/mL.
5. the preparation method of fluorescent nanoparticles with light stability according to claim 1 is characterized in that, described stirring, and the whipping temp described in the step (2,3) is: 20-80 ℃; Described in the step (4,5) churning time 10-60 minute.
6. the preparation method of fluorescent nanoparticles with light stability according to claim 1 is characterized in that, the fluorescent small molecule solution described in the step (1,2) is 0.01: 1～0.5: 1 with the molar charge ratio of poly ion liquid solution.
7. the preparation method of fluorescent nanoparticles with light stability according to claim 1 is characterized in that, the azo surfactant soln described in the step (1,3) is 0.01: 1～0.5: 1 with the molar charge ratio of poly ion liquid solution.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030224525A1 (en) * | 2002-05-30 | 2003-12-04 | The University Of Chicago | Enhanced photophysics of conjugated polymers |
| US20060216759A1 (en) * | 2004-10-29 | 2006-09-28 | Imad Naasani | Functionalized fluorescent nanocrystals, and methods for their preparation and use |
| CN101077974A (en) * | 2007-07-05 | 2007-11-28 | 清华大学 | Method of preparing nano-level sphere cerium activated yttrium aluminum garnet phosphor powder |
| CN101486903A (en) * | 2009-02-23 | 2009-07-22 | 东南大学 | Preparation of rare earth luminous nanoparticle based on pyridine dicarboxylic acid |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030224525A1 (en) * | 2002-05-30 | 2003-12-04 | The University Of Chicago | Enhanced photophysics of conjugated polymers |
| US20060216759A1 (en) * | 2004-10-29 | 2006-09-28 | Imad Naasani | Functionalized fluorescent nanocrystals, and methods for their preparation and use |
| CN101077974A (en) * | 2007-07-05 | 2007-11-28 | 清华大学 | Method of preparing nano-level sphere cerium activated yttrium aluminum garnet phosphor powder |
| CN101486903A (en) * | 2009-02-23 | 2009-07-22 | 东南大学 | Preparation of rare earth luminous nanoparticle based on pyridine dicarboxylic acid |
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