CN112851846B - Method for preparing surface carboxylation nano fluorescent microspheres by soap-free emulsion polymerization - Google Patents
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Abstract
A method for preparing surface carboxylated nano fluorescent microspheres by soap-free emulsion polymerization comprises the following steps: (1) preparing a fluorescent dye styrene solution: dissolving a polymerizable fluorescent dye monomer in styrene to obtain a fluorescent dye monomer styrene solution; (2) mixing a fluorescent dye monomer styrene solution, acrylic acid and water, and then carrying out ultrasonic emulsification; (3) and (3) introducing nitrogen into the reaction system for deoxidation treatment after ultrasonic emulsification, heating, adding an initiator, stirring, continuing to heat, continuing to react under the protection of nitrogen, centrifugally washing, and dispersing in water to obtain the carboxylated nano fluorescent microspheres. The method can prepare the polystyrene fluorescent microspheres only by a one-step method, does not need other redundant organic solvents in the preparation process, is environment-friendly and harmless, and meanwhile, fluorescent molecules are not easy to lose in the fluorescent microspheres in a bonded mode.
Description
Technical Field
The invention relates to a method for preparing surface carboxylation nano fluorescent microspheres by soap-free emulsion polymerization, belonging to the field of biomedical high polymer materials.
Background
The carboxylated polystyrene microsphere has the advantages of good dispersibility, large specific surface area, strong adsorbability, large agglutination effect, good mechanical property and biodegradability, and is widely applied to various fields of enzyme immobilization, chromatographic separation, drug delivery, biosensing and the like. The carboxyl polystyrene microsphere is easy to combine with amino due to the surface rich in carboxyl, thereby being widely concerned in the field of biological medical treatment and diagnosis. Fluorescent molecules are introduced into the carboxyl polystyrene microspheres, and the fluorescent microsphere can be applied to the fields of DNA detection, high-throughput drug screening, clinical rapid diagnosis and the like.
The traditional methods for preparing carboxyl polystyrene fluorescent microspheres are a swelling method and an emulsion/dispersion polymerization method. For example, Chinese patent with publication number CN104212087A discloses a preparation method of monodisperse fluorescent microspheres, which relates to the field of polymer material synthesis. The invention aims to solve the technical problems of complex preparation process and large addition amount of fluorescent substances in the existing method for preparing the fluorescent microspheres. The method comprises the following steps: firstly, adding a styrene monomer into ultrapure water, stirring, adding 1% of potassium persulfate, and condensing and refluxing to obtain polystyrene microspheres; uniformly dispersing the fluorescent indicator in an organic solvent to prepare a fluorescent indicator solution; and thirdly, placing the polystyrene microspheres in a brown sample bottle, adding a fluorescent indicator solution, performing ultrasonic dispersion, centrifuging, and washing with ultrapure water until no fluorescent indicator exists on the surfaces of the microspheres, thus completing the preparation. For example, chinese patent publication No. CN105295066A discloses a method for preparing polystyrene fluorescent microspheres by a swelling method, comprising the following steps: dispersing PS microsphere liquid in a swelling medium, dissolving Eu (DBM)3phen in a swelling agent, and then mixing together for a swelling reaction; removing the swelling agent by evaporation at a suitable temperature; after the swelling agent is evaporated, carrying out ultrasonic treatment on the PS microsphere solution for 1-15 min, and then diluting; and removing the swelling medium to obtain the PS fluorescent microsphere precipitate.
However, the fluorescence of the fluorescent microspheres prepared by the swelling method is weak, the seed microspheres are easy to dissolve and adhere, and the preparation process has great pollution to the environment. In addition, polystyrene microspheres are also porous, and fluorescent molecules are easy to leak, so that the application of the polystyrene microspheres is limited. The steps of removing the emulsifier and the dispersant in the emulsion/dispersion polymerization post-treatment are multiple and complex, and the residual emulsifier or dispersant can influence the service performance of the microspheres. Therefore, the fluorescent microspheres studied at home and abroad at present have the defects of unstable fluorescence, easy falling, leakage, low fluorescence efficiency and the like.
Disclosure of Invention
The invention aims to provide a method for preparing surface carboxylation nano fluorescent microspheres by soap-free emulsion polymerization, the method can prepare polystyrene fluorescent microspheres by a one-step method, other redundant organic solvents are not needed in the preparation process, the method is environment-friendly and harmless, and meanwhile, fluorescent molecules are bonded in the fluorescent microspheres and are not easy to lose.
The invention provides the following technical scheme:
a method for preparing surface carboxylated nano fluorescent microspheres by soap-free emulsion polymerization comprises the following steps:
(1) preparing a fluorescent dye styrene solution: dissolving a polymerizable fluorescent dye monomer in styrene to obtain a fluorescent dye monomer styrene solution;
(2) mixing a fluorescent dye monomer styrene solution, acrylic acid and water, and then carrying out ultrasonic emulsification;
(3) and (3) introducing nitrogen into the reaction system for deoxidation treatment after ultrasonic emulsification, heating, adding an initiator, stirring, continuing to heat, continuing to react under the protection of nitrogen, centrifugally washing, and dispersing in water to obtain the carboxylated nano fluorescent microspheres.
The polymerizable fluorescent dye monomer is a polymerizable fluorescent dye fluorescein monomer 1 and a naphthalimide monomer 2 which are respectively shown as a formula I and a formula II:
the polymerizable fluorescent dye is prepared into the fluorescent microspheres by a soap-free emulsion polymerization method, and soap-free emulsion polymerization is different from the traditional emulsion and dispersion polymerization, and an emulsifier is not required to be added in the reaction process, so that the influence of the emulsifier on the microspheres can be avoided. Meanwhile, fluorescent molecules are bonded into the fluorescent microspheres through the polymerizable fluorescent dye monomer, so that the fluorescent molecules can be prevented from being separated out in the storage and use processes of the microspheres. In the present invention, the outer surface of the polymer latex particle is hydrated by polymerizable hydrophilic monomer acrylic acid or methacrylic acid to serve as an emulsifier-like stabilization. In the polymerization reaction, the polymerizable fluorescent monomer is connected with styrene and acrylic acid in a bonding mode, so that the polystyrene fluorescent microsphere is assembled in water. Therefore, compared with the emulsion polymerization method for preparing the fluorescent microspheres, the method does not need to add an emulsifier, and the post-treatment is simple. Meanwhile, the fluorescent molecular monomer is bonded into the fluorescent microsphere in a polymerization mode, so that the phenomenon of dye leakage is avoided, and the performance is stable. The fluorescent microspheres have uniform particle size distribution, can combine macromolecules (such as antibodies) with different functions to the surfaces of the microspheres, and have good application scenes in the field of in vitro diagnosis.
In the step (1), 0.5-5% w/v of polymerizable fluorescent dye monomer is dissolved in 4.5 volume parts of styrene.
In the step (2), the amount of the acrylic acid added is 5 to 30 v/v% styrene.
In the step (3), the temperature is raised to 40-60 ℃, then an initiator is added, and after stirring, the temperature is raised to 70-80 ℃ continuously, and reaction is carried out for 6-10 h.
The initiator is selected from azodiisocyanato, azodiisocyanato or potassium persulfate, and the addition amount of the initiator is 1-15 w/w% of styrene.
When the polymerizable fluorescent dye monomer is the polymerizable fluorescent dye fluorescein monomer 1 shown in the formula I, the average particle size of the prepared surface carboxylated nano fluorescent microsphere is 100-500 nm, and the maximum emission wavelength is 515 nm.
When the polymerizable fluorescent dye monomer is the naphthalimide monomer 2 shown in the formula II, the average particle size of the prepared surface carboxylated nano fluorescent microsphere is 100-500 nm, and the maximum emission wavelength is 475 nm.
In the method provided by the invention: styrene, acrylic acid, initiator content and reaction temperature can affect the particle size of the microspheres, and reaction time can affect the conversion rate of reactants. According to experimental detection, the more the content of the dye added in the reaction is, the smaller the particle size of the microsphere is, and the higher the fluorescence intensity of the fluorescent microsphere is.
The invention aims to solve the problems that fluorescent molecules are easy to lose in microspheres prepared by a swelling method in the prior art and an emulsifier and a dispersing agent are required to be removed by an emulsion/dispersion polymerization method, and provides a method for preparing carboxylated high-molecular fluorescent microspheres by soap-free emulsion polymerization. Meanwhile, the fluorescent molecules are bonded in the fluorescent microspheres and are not easy to lose. In the emulsion polymerization, although most of the emulsifier is removed by the post-treatment, a trace amount of the emulsifier remains, and the emulsifier affects the immune reaction of the antibody antigen, which is not a problem in the soap-free emulsion polymerization.
Drawings
FIG. 1 is a structural formula of a polymerizable fluorescent dye fluorescein monomer 1 shown in formula I;
FIG. 2 shows the absorption and fluorescence spectra of the polymerizable fluorochrome fluorescein monomer 1 shown in formula I in example 1 and the prepared carboxylated fluorescein polystyrene fluorescent microspheres;
FIG. 3 is a graph showing the particle size distribution of carboxylated fluorescein polystyrene fluorescent microspheres with average particle sizes of 287nm, 165nm and 146nm in example 1, example 2 and example 3;
FIG. 4 is a transmission electron micrograph of carboxylated fluorescein polystyrene fluorescent microspheres with average particle diameters of 287nm, 165nm and 146nm in example 1, example 2 and example 3;
FIG. 5 is a structural formula of a polymerizable fluorescent dye naphthalimide monomer 2 shown in formula II;
FIG. 6 is a diagram II showing the absorption and fluorescence spectra of a polymerizable fluorescent dye naphthalimide monomer 2 and a prepared carboxylated naphthalimide polystyrene fluorescent microsphere;
FIG. 7 is a graph showing the distribution of particle size of 183nm carboxylated naphthalene imide polystyrene fluorescent microspheres in example 4;
FIG. 8 is a transmission electron micrograph of 183nm carboxylated naphthalimide polystyrene fluorescent microspheres in example 4.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be further described in detail with reference to the accompanying drawings and examples. It should be understood that the detailed description and specific examples, while indicating the scope of the invention, are intended for purposes of illustration only and are not intended to limit the scope of the invention.
The structural formula of the polymerizable fluorescent dye fluorescein monomer 1 shown in the formula I is shown in figure 1. The absorption and fluorescence spectrum analysis of the polymerizable fluorescent dye fluorescein monomer 1 by a microplate reader is shown in detail in (a) of FIG. 2. The results show that: the polymerizable fluorescent dye fluorescein monomer has stronger fluorescence intensity at the maximum excitation/emission wavelength of 460/530 nm.
2. The structural formula of the polymerizable fluorescent dye naphthalimide monomer 2 shown in the formula II is shown in figure 5. An absorption and fluorescence spectrum analysis test of a polymerizable fluorescent dye naphthalimide monomer 2 by using a microplate reader is shown in (a) in FIG. 6; the results show that: the synthesized polymerizable fluorescent dye naphthalimide monomer 2 has stronger fluorescence intensity at the maximum excitation/emission wavelength of 400/510 nm.
The polystyrene fluorescent microsphere provided by the invention is prepared by a soap-free emulsion method, and the preparation method comprises the following steps:
a. preparing a fluorescent dye styrene solution: dissolving a proper amount of polymerizable fluorescent dye fluorescein monomer 1 shown in a formula I or naphthalimide monomer 2 shown in a formula II in 3-5 ml of styrene to obtain a fluorescent dye styrene solution.
b. Adding a fluorescent dye styrene solution and 0.1-1.0 ml of acrylic acid into a 500ml three-neck flask containing 90-100 ml of purified water, and carrying out ultrasonic emulsification.
c. And introducing nitrogen into the reaction system for deoxidation, placing the flask in an oil bath, heating to 60 ℃, adding 0.1-1.0 g of initiator potassium persulfate, stirring at the speed of 200-300 r/min, continuously heating to 70-80 ℃, introducing nitrogen, reacting for 8-10 h, removing unreacted monomers by centrifugation, dispersing, washing and centrifuging for multiple times by using ethanol, and re-dispersing in purified water to obtain the carboxylated nano fluorescent microspheres.
Example 1
a. Preparing a fluorescent dye styrene solution: 0.023g of the polymerizable fluorescent dye fluorescein monomer 1 shown in the formula I is dissolved in 4.5ml of styrene to obtain a fluorescent dye fluorescein monomer styrene solution.
b. The fluorescent dye styrene solution, 0.5ml of acrylic acid, was added to a 500ml three-necked flask containing 95ml of purified water, and emulsified by sonication.
c. And introducing nitrogen into the reaction system for deoxidation, placing the flask in an oil bath, heating to 60 ℃, adding 0.5g of initiator potassium persulfate, stirring at the speed of 250r/min, continuously heating to 75 ℃, introducing nitrogen, reacting for 10h, removing unreacted monomers by centrifugation, dispersing, washing and centrifuging for multiple times by using ethanol, and re-dispersing in purified water to obtain the carboxylated nano fluorescent microspheres.
The carboxylated polystyrene fluorescent microspheres prepared in this example were subjected to absorption and fluorescence spectrum analysis tests using a microplate reader, which is shown in fig. 2 (b). The results show that: the prepared carboxylated polystyrene fluorescent microsphere has stronger fluorescence intensity at the maximum excitation/emission wavelength of 460/520 nm.
The particle size analysis of the carboxylated fluorescein polystyrene fluorescent microspheres was performed by a Malvern nanometer particle size analyzer, which is shown in (a) of fig. 3.
The morphology and particle size of the carboxylated fluorescein polystyrene fluorescent microspheres were tested by transmission electron microscopy, as shown in (a) of fig. 4. The results show that: the average grain diameter of the prepared carboxylated fluorescein polystyrene fluorescent microsphere is 287nm, and the polydispersity index PDI of the microsphere is 0.034. The carboxylated polystyrene fluorescent microspheres prepared in the embodiment have uniform particle size and narrow distribution.
Example 2
a. Preparing a fluorescent dye styrene solution: 0.045g of the polymerizable fluorescent dye fluorescein monomer represented by formula I was dissolved in 4.5ml of styrene to obtain a fluorescent dye fluorescein monomer 1 styrene solution.
b. The fluorescent dye styrene solution, 0.5ml of acrylic acid, was added to a 500ml three-necked flask containing 95ml of purified water, and emulsified by sonication.
c. And introducing nitrogen into the reaction system for deoxidation, placing the flask in an oil bath, heating to 60 ℃, adding 0.5g of initiator potassium persulfate, stirring at the speed of 250r/min, continuously heating to 75 ℃, introducing nitrogen, reacting for 10h, removing unreacted monomers by centrifugation, dispersing, washing and centrifuging for multiple times by using ethanol, and re-dispersing in purified water to obtain the carboxylated nano fluorescent microspheres.
And (3) performing absorption fluorescence spectrum analysis and test on the carboxylated polystyrene fluorescent microspheres by using a microplate reader. The results show that: the prepared carboxylated polystyrene fluorescent microsphere has stronger fluorescence intensity at the maximum excitation/emission wavelength of 460/520 nm.
Particle size analysis of the carboxylated fluorescein polystyrene fluorescent microspheres was performed using a Malvern nanometer particle size analyzer, as shown in (b) of fig. 3.
The morphology and particle size of the carboxylated fluorescein polystyrene fluorescent microspheres were tested by transmission electron microscopy, as shown in (b) of fig. 4. The results show that: the average grain diameter of the prepared carboxylated fluorescein polystyrene fluorescent microsphere is 165nm, and the polydispersity index PDI of the microsphere is 0.099. The carboxylated polystyrene fluorescent microspheres prepared in the embodiment have uniform particle size and narrow distribution.
Example 3
a. Preparing a fluorescent dye styrene solution: 0.068g of the polymerizable fluorescent dye fluorescein monomer 1 represented by the formula I was dissolved in 4.5ml of styrene to obtain a fluorescent dye fluorescein monomer 1 styrene solution.
b. The fluorescent dye styrene solution, 0.5ml of acrylic acid, was added to a 500ml three-necked flask containing 95ml of purified water, and emulsified by sonication.
c. And introducing nitrogen into the reaction system for deoxidation, placing the flask in an oil bath, heating to 60 ℃, adding 0.5g of initiator potassium persulfate, stirring at the speed of 250r/min, continuously heating to 75 ℃, introducing nitrogen, reacting for 10h, removing unreacted monomers by centrifugation, dispersing and centrifuging for multiple times by using ethanol, and re-dispersing in purified water to obtain the carboxylated nano fluorescent microspheres.
And (3) adopting an enzyme-labeling instrument to perform absorption and fluorescence spectrum analysis and test on the carboxylated polystyrene fluorescent microspheres. The results show that: the prepared carboxylated polystyrene fluorescent microsphere has stronger fluorescence intensity at the maximum excitation/emission wavelength of 460/520 nm.
The particle size analysis of the carboxylated fluorescein polystyrene fluorescent microspheres was performed by a Malvern nanometer particle size analyzer, which is shown in (c) of fig. 3.
The morphology and particle size of the carboxylated fluorescein polystyrene fluorescent microspheres were tested by transmission electron microscopy, as shown in (c) of fig. 4. The results show that: the average grain diameter of the prepared carboxylated fluorescein polystyrene fluorescent microspheres is 146nm, and the polydispersity index PDI of the microspheres is 0.070. The carboxylated polystyrene fluorescent microspheres prepared in the embodiment have uniform particle size and narrow distribution.
Example 4
a. Preparing a fluorescent dye styrene solution: 0.045g of polymerizable fluorescent dye naphthalimide monomer 2 shown as II is dissolved in 4.5ml of styrene to obtain a fluorescent dye naphthalimide monomer 2 styrene solution.
b. The naphthalimide monomer 2 styrene solution obtained in a and 0.5ml of acrylic acid were added to a 500ml three-necked flask containing 95ml portions of purified water, and subjected to ultrasonic emulsification.
c. And introducing nitrogen into the reaction system for deoxidation, placing the flask in an oil bath, heating to 60 ℃, adding 0.5g of initiator potassium persulfate, continuously heating to 75 ℃, stirring at the speed of 250r/min, continuously introducing nitrogen, reacting for 10 hours, centrifuging to remove unreacted monomers, dispersing and centrifuging for multiple times by using ethanol, and re-dispersing in purified water to obtain the carboxylated nano fluorescent microspheres.
The absorption fluorescence spectrum analysis test of the carboxylated polystyrene fluorescent microspheres is carried out by using a microplate reader, which is shown in (b) in fig. 6. The results show that: the prepared carboxylated polystyrene fluorescent microsphere has stronger fluorescence intensity at the maximum excitation/emission wavelength of 400/475 nm.
The particle size analysis of the carboxylated naphthalimide polystyrene fluorescent microspheres was carried out by a Malvern nanometer particle size analyzer, as shown in FIG. 7.
The morphology and particle size of the carboxylated naphthalimide polystyrene fluorescent microspheres were tested by transmission electron microscopy, as shown in detail in FIG. 8.
The results show that: the average grain diameter of the prepared carboxylated naphthalimide polystyrene fluorescent microsphere is 183nm, and the polydispersity index PDI of the microsphere is 0.041. The carboxylated polystyrene fluorescent microspheres prepared in the embodiment have uniform particle size and narrow distribution.
The above-mentioned embodiments are intended to illustrate the technical solutions and advantages of the present invention, and it should be understood that the above-mentioned embodiments are only the most preferred embodiments of the present invention, and are not intended to limit the present invention, and any modifications, additions, equivalents, etc. made within the scope of the principles of the present invention should be included in the scope of the present invention.
Claims (3)
1. A method for preparing surface carboxylation nanometer fluorescent microspheres by soap-free emulsion polymerization is characterized by comprising the following steps:
(1) preparing a fluorescent dye styrene solution: dissolving a polymerizable fluorescent dye monomer in styrene to obtain a fluorescent dye monomer styrene solution;
(2) mixing a fluorescent dye monomer styrene solution, acrylic acid and water, and then carrying out ultrasonic emulsification;
(3) introducing nitrogen into a reaction system for deoxidation after ultrasonic emulsification, heating, adding an initiator, stirring, continuing to heat, continuing to react under the protection of nitrogen, centrifugally washing, and dispersing in water to obtain the carboxylated nano fluorescent microspheres;
the polymerizable fluorescent dye monomer is a polymerizable fluorescent dye fluorescein monomer 1 and a naphthalimide monomer 2 which are respectively shown as a formula I and a formula II:
in the step (1), 0.5-5% w/v of polymerizable fluorescent dye monomer is dissolved in 4.5 volume parts of styrene;
in the step (2), the addition amount of the acrylic acid is 5-30 v/v% of styrene;
in the step (3), heating to 40-60 ℃, adding an initiator, stirring, and then continuously heating to 70-80 ℃ for reacting for 6-10 h;
the initiator is selected from azodiisopropyan, azodiisobutyan or potassium persulfate, and the addition amount of the initiator is 1-15 w/w% of styrene.
2. The method for preparing surface-carboxylated nano fluorescent microspheres by soap-free emulsion polymerization according to claim 1, wherein when the polymerizable fluorescent dye monomer is polymerizable fluorescent dye fluorescein monomer 1 shown in formula I, the average particle size of the prepared surface-carboxylated nano fluorescent microspheres is 100nm to 500nm, and the maximum emission wavelength is 515 nm.
3. The method for preparing surface-carboxylated nano fluorescent microspheres by soap-free emulsion polymerization according to claim 1, wherein when the polymerizable fluorescent dye monomer is the naphthalimide monomer 2 shown in formula II, the average particle size of the prepared surface-carboxylated nano fluorescent microspheres is 100nm to 500nm, and the maximum emission wavelength is 475 nm.
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| CN114181341B (en) * | 2021-12-30 | 2024-01-19 | 朱小波 | Method for preparing quantum dot fluorescent microspheres by ultrasonic initiation |
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| CN115260370B (en) * | 2022-08-06 | 2024-04-16 | 闽南师范大学 | Preparation method of fluorescent microsphere for detecting polystyrene in living body |
| CN115573167B (en) * | 2022-08-11 | 2024-02-20 | 武汉纺织大学 | Water-based fluorescent microsphere, water-based fluorescent microsphere textile, and preparation methods and application thereof |
| CN116903892B (en) * | 2023-09-13 | 2023-11-21 | 浙江大学 | Multicolor dye composite polymer microsphere, preparation method and application thereof |
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