CN111777704B - Preparation method of carboxylated polystyrene fluorescent microspheres - Google Patents
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Abstract
The invention discloses a preparation method of carboxylated polystyrene fluorescent microspheres, which specifically comprises the following steps: preparation of fluorescent substance-europium complex: will dissolve EuCl 3 ·6H 2 Adding ethanol solution of O into ethanol solution of TPPO for coordination reaction, and adding deprotonated ethanol solution of BTFA into Eu (TPPO) 4 Performing coordination reaction at high temperature, performing suction filtration and volatilization crystallization on the product after reaction to obtain europium complex Eu (BTFA) (TPPO) 3 (ii) a With the obtained europium complex Eu (BTFA) (TPPO) 3 Preparing the polystyrene fluorescent microspheres, and performing carboxylation treatment on the surfaces of the prepared polystyrene fluorescent microspheres to obtain the polystyrene fluorescent microspheres with carboxyl monomers on the surfaces.
Description
Technical Field
The invention relates to a preparation method of carboxylated polystyrene fluorescent microspheres, belonging to the technical field of synthesis of nano functional materials.
Background
Fluorescence refers to the cold luminescence phenomenon of photoluminescence. When incident light (usually ultraviolet rays or X rays) with a certain wavelength irradiates a certain normal-temperature substance, the substance enters an excited state after absorbing light energy, and is immediately excited and emits emergent light (usually with the wavelength in a visible light waveband) with the wavelength longer than that of the incident light; meanwhile, when the incident light stops, the substance light emission phenomenon also disappears immediately, the emitted light having such a property is called fluorescence, and the substance capable of emitting fluorescence is a fluorescent substance.
The fluorescent microsphere is a microsphere loaded with fluorescent materials in nanometer to micron scale, which is formed by adsorbing or coating the fluorescent materials on the surface of the microsphere or embedding the fluorescent materials in the microsphere through methods such as an embedding method, a physical adsorption method, a self-assembly method, a chemical bonding method or a copolymerization method. The microspheres are mostly spherical in shape, so the microspheres are called as fluorescent microspheres, have stable morphological structures, protection effect on fluorescent substances and surface modifiability, and have great application prospects in the fields of marking, detection, tracing, immune medicine, high-throughput drug screening and the like.
Disclosure of Invention
The purpose of the invention is as follows: the invention aims to solve the technical problem of providing a preparation method of carboxylated polystyrene fluorescent microspheres.
The technical scheme of the invention is as follows:
a preparation method of carboxylated polystyrene fluorescent microspheres specifically comprises the following steps:
(1) Preparation of fluorescent substance: europium complexes
Will dissolve EuCl 3 ·6H 2 Adding ethanol solution of O into ethanol solution of TPPO for coordination reaction, and adding deprotonated ethanol solution of BTFA into Eu (TPPO) 4 Performing coordination reaction at high temperature, performing suction filtration and volatilization crystallization on the product after reaction to obtain europium complex Eu (BTFA) (TPPO) 3 ；
(2) Europium complex Eu (BTFA) (TPPO) prepared in step (1) 3 Preparing the polystyrene fluorescent microspheres, and introducing a carboxyl monomer in the process of preparing the polystyrene fluorescent microspheres to realize the carboxylation of the surfaces of the microspheres to obtain the polystyrene fluorescent microspheres with the carboxyl monomer on the surfaces.
In the step (2), the concrete preparation process of the carboxylated polystyrene fluorescent microspheres is as follows: mixing europium complex Eu (BTFA) (TPPO) 3 Dispersing styrene and hydroxyethyl methacrylate in water containing a copolymerization emulsifier and sodium bicarbonate or ammonium bicarbonate, driving air in a reaction device by using inert gas, heating and stirring, adding a water-soluble thermal initiator for a microspherical reaction, adding the water-soluble thermal initiator and a carboxyl monomer for carboxylation after the reaction, cooling the solution to room temperature after condensation and reflux, centrifugally cleaning, and resetting the product in a storage solution.
Wherein, in the step (1), the reaction temperature is 70-75 ℃.
Wherein, in the step (2), the mixing volume ratio of the styrene to the hydroxyethyl methacrylate is 3:7; europium complex Eu (BTFA) (TPPO) 3 The addition mass-to-volume ratio of the mixed monomer to the mixed monomer is 2:1, namely, the addition volume of the mixed monomer is 0.5mL for every 1mg of the europium complex.
Wherein, in the step (2), the water-soluble thermal initiator is potassium persulfate or ammonium persulfate.
Wherein, in the step (2), the carboxyl monomer comprises maleic anhydride, methacrylic acid and acrylic acid.
Has the advantages that: the carboxylated polystyrene fluorescent microsphere prepared by the method adopts the europium complex as the fluorescent substance, and has the advantages of high fluorescence intensity, high quantum efficiency and high fluorescence stability; by introducing hydroxyethyl methacrylate capable of enhancing the fluorescence intensity of the europium complex as a comonomer in the process of preparing the polystyrene fluorescent microspheres, the fluorescence intensity of the fluorescent microspheres is enhanced, and the dispersity of the whole reaction system is enhanced, so that the polystyrene fluorescent microspheres with uniform particle size, stable fluorescence, long fluorescence life and high fluorescence intensity are obtained; in addition, the method controls the particle size of the polystyrene fluorescent microsphere through the selection of the copolymerization emulsifier in the preparation process of the polystyrene fluorescent microsphere, and does not need to remove the emulsifier additionally in the follow-up process, thereby saving the production cost; finally, the method adopts a core-shell mode to introduce the carboxyl monomer, so that the carboxyl content on the surface of the microsphere is greatly improved, and the microsphere has extremely strong protein coupling capacity.
The method of the invention overcomes the problems of uneven coating, insufficient coating amount, europium complex leakage and the like existing in the traditional method for preparing the fluorescent microsphere by adopting an embedding method, the solubility of the fluorescent substance in the monomer determines the coating amount and the coating uniformity, and Eu (BTFA) (TPPO) 3 The solubility in the monomer is higher than that of other europium complexes; carboxyl monomer is introduced in the reaction process, and the prepared microsphere has a core-shell structure, so that the europium complex can be prevented from leaking; the prepared carboxylated polystyrene fluorescent microsphere has high sphericity and good monodispersityThe polystyrene fluorescent microsphere has the advantages of uniform particle size, stable fluorescence, long fluorescence life and high fluorescence intensity, the copolymerization type emulsifier can improve the dispersibility of the microsphere and reduce the particle size of the microsphere, and the fluorescence intensity of the polystyrene fluorescent microsphere is derived from Eu (BTFA) (TPPO) 3 Fluorescence of Eu (BTFA) (TPPO) 3 Long fluorescence lifetime, high quantum efficiency; the carboxylated polystyrene fluorescent microspheres with high fluorescence intensity are prepared by a soap-free emulsion polymerization method, and have the fluorescence stability in a preservation solution which is equivalent to that of JSR microspheres, but have higher fluorescence intensity and higher surface carboxyl content; the carboxylated polystyrene fluorescent microspheres prepared by the method can be applied to time-resolved fluoroimmunoassay or test strips.
Drawings
FIG. 1 is a scanning electron micrograph of non-carboxylated polystyrene fluorescent microspheres of example 2 of the present invention;
FIG. 2 is a scanning electron micrograph of carboxylated polystyrene fluorescent microspheres according to example 3 of the present invention;
FIG. 3 is a scanning electron micrograph of carboxylated polystyrene fluorescent microspheres according to example 4 of the present invention;
FIG. 4 is a scanning electron micrograph of carboxylated polystyrene fluorescent microspheres according to example 5 of the present invention;
FIG. 5 is a graph of conductance titration of carboxyl content on the surface of carboxylated fluorescent microspheres in example 4 of the present invention;
FIG. 6 is a graph of conductance titration of carboxyl content on the surface of carboxylated fluorescent microspheres in example 5 of the present invention;
FIG. 7 is a graph showing the standard curve of the BCA method for measuring the ability of coupling Bovine Serum Albumin (BSA) to carboxylated fluorescent microspheres in example 4 of the present invention;
FIG. 8 is a graph showing the standard curve of the BCA method for measuring the ability of coupling Bovine Serum Albumin (BSA) to carboxylated fluorescent microspheres in example 5 of the present invention;
FIG. 9 is a fluorescence spectrum of carboxylated fluorescent microspheres in example 4 of the present invention;
FIG. 10 is a graph showing the comparison of fluorescence intensity of carboxylated fluorescent microspheres of example 4 of the present invention after being left standing for 3 months at room temperature;
FIG. 11 is a graph comparing the fluorescence intensity of the carboxylated fluorescent microspheres and the commercial fluorescent microspheres in example 4 of the present invention.
Detailed Description
The technical solution of the present invention is further explained below with reference to the specific embodiments and the accompanying drawings.
Example 1
Preparation of europium Complex Eu (BTFA) (TPPO) 3 ：
0.3519g (1 mmol) europium oxide was weighed and dissolved in 15mL concentrated hydrochloric acid, evaporated by heating at 85 ℃ in an oil bath until a white thin film solid was obtained, and the white solid was dissolved in ethanol to give EuCl3.6Hh 2 Ethanol solution of O; 1.1131g triphenylphosphine oxide (TPPO, 4 mmol) was weighed out and dissolved in 25mL ethanol; will dissolve EuCl 3 ·6H 2 Slowly dripping the ethanol solution of O into the ethanol solution dissolved with TPPO, and heating and refluxing for 12h at the temperature of 75 ℃; 0.2161g benzoyltrifluoroacetone (BTFA, 1 mmol) and 0.0561g potassium hydroxide (KOH, 1 mmol) were dissolved in 25mL ethanol to give a deprotonated BTFA ethanol solution, which was slowly added to Eu (TPPO) 4 Mixing and stirring the mixed solution at 70 ℃ for coordination reaction, adjusting the pH value of the reaction solution to 6.5-7 by using an ethanol solution dissolved with KOH, continuously heating, stirring and refluxing for 24 hours, cooling the obtained mixed solution to room temperature, performing suction filtration by using a Buchner funnel, and performing volatilization and crystallization at room temperature; finally, the crystal is cleaned and dried in vacuum to obtain europium complex Eu (BTFA) (TPPO) 3 。
Example 2
Europium complex Eu (BTFA) (TPPO) prepared in example 1 was used 3 Preparing the polystyrene fluorescent microspheres:
20mg of europium complex Eu (BTFA) (TPPO) are weighed out 3 0.7mL of styrene and 0.3mL of hydroxyethyl methacrylate were dissolved in 18mL of deionized water containing 5mg of a copolymerization emulsifier and 125mg of ammonium bicarbonate, the air in the reaction apparatus was purged with high-purity nitrogen gas for 30min, the temperature was raised to 80 ℃ and the mixture was heated and stirred, 2mL of an aqueous solution containing 50mg of initiator KPS was added to the mixture to carry out a microsphericization reaction, the mixture was refluxed for 12 hours by condensation, cooled to room temperature, centrifuged, washed, and replaced in a storage solution (100 mg/mL).
FIG. 1 is a scanning electron microscope image of 500 nm-sized non-carboxylated polystyrene fluorescent microspheres in example 2 of the present invention.
Example 3
Europium complex Eu (BTFA) (TPPO) prepared in example 1 was used 3 Preparing carboxylated polystyrene fluorescent microspheres:
20mg of europium complex Eu (BTFA) (TPPO) are weighed out 3 Dissolving 0.7mL of styrene and 0.3mL of hydroxyethyl methacrylate in 18mL of deionized water containing 5mg of a copolymerization emulsifier and 125mg of ammonium bicarbonate, driving air in a reaction device by using high-purity nitrogen, heating to 80 ℃ after 30min, stirring, adding 2mL of aqueous solution in which 50mg of an initiator KPS is dissolved into the mixture for carrying out a microsphericization reaction, adding 1mL of aqueous solution in which 25mg of the initiator KPS is dissolved and 0.1mL of Acrylic Acid (AA) -carboxyl monomer into the mixture after 30min of reaction, carrying out carboxylation treatment, cooling the solution to room temperature after 12h of condensation and reflux, carrying out centrifugal cleaning, and resetting in a preservation solution (100 mg/mL).
FIG. 2 is a scanning electron microscope image of a carboxylated polystyrene fluorescent microsphere with a size of 300nm in example 3 of the present invention, and by comparing with FIG. 1, it is found that the introduction of a carboxyl monomer can effectively reduce the particle size of the fluorescent microsphere.
Example 4
Europium complex Eu (BTFA) (TPPO) prepared in example 1 was used 3 Preparing carboxylated polystyrene fluorescent microspheres:
weighing 20mg of europium complex Eu (BTFA) (TPPO) 3 Dissolving 0.7mL of styrene and 0.3mL of hydroxyethyl methacrylate in 18mL of deionized water containing 5mg of a copolymerization emulsifier and 125mg of ammonium bicarbonate, driving air in a reaction device by using high-purity nitrogen, heating to 80 ℃ after 30min, stirring, adding 2mL of aqueous solution in which 50mg of initiator KPS is dissolved into the mixture for carrying out a microsphericization reaction, adding 1mL of aqueous solution in which 25mg of initiator KPS is dissolved and 0.1mL of methacrylic acid (MAA) -carboxyl monomer into the mixture after 30min of reaction, carrying out carboxylation treatment, cooling the solution to room temperature after 12h of condensation reflux, carrying out centrifugal cleaning, and resetting in a storage solution (100 mg/mL).
FIG. 3 is a scanning electron micrograph of 150 nm-sized carboxylated polystyrene fluorescent microspheres in example 4 of the present invention, and by comparing with FIG. 2, the fluorescent microspheres prepared from carboxyl monomer MAA are found to have smaller particle size.
Fig. 5 is a conductance titration graph of the carboxyl content on the surface of the carboxylated fluorescent microsphere in example 4 of the present invention, and it can be seen from fig. 5 that the carboxyl monomer content on the surface of the carboxylated polystyrene fluorescent microsphere prepared in example 4 is: COOH content =8.510638 × 10 -5 mmol/mg。
Fig. 7 is a standard curve diagram of the BCA method for measuring the ability of coupling Bovine Serum Albumin (BSA) to carboxylated fluorescent microspheres in example 4 of the present invention, and it can be seen from fig. 7 that the ability of coupling the carboxylated fluorescent microspheres in example 4 of the present invention to Bovine Serum Albumin (BSA) is: 0.147mg/ml; the capacity of coupling JSR carboxyl microspheres with the same mass to BSA is 0.124mg/ml.
Fig. 9 is a fluorescence spectrum of the carboxylated fluorescent microsphere of the embodiment 4 of the invention, and it can be seen from fig. 9 that the fluorescence intensity of the carboxylated fluorescent microsphere of the embodiment 4 is 180000a.
FIG. 10 is a comparison graph of fluorescence intensity of the carboxylated fluorescent microspheres of example 4 of the invention after standing for 3 months at room temperature, and it can be seen from FIG. 10 that the fluorescence intensity of the carboxylated fluorescent microspheres of example 4 is not affected substantially after standing for 3 months at room temperature.
FIG. 11 is a comparison graph of fluorescence intensity of the carboxylated fluorescent microspheres and the commercialized fluorescent microspheres in example 4 of the present invention, and it can be seen from FIG. 11 that the fluorescent microspheres prepared by the method have higher intensity than the commercially available commercialized fluorescent microspheres.
Example 5
Europium complex Eu (BTFA) (TPPO) prepared in example 1 was used 3 Preparing carboxylated polystyrene fluorescent microspheres:
weighing 20mg of europium complex Eu (BTFA) (TPPO) 3 Dissolving 0.7mL of styrene and 0.3mL of hydroxyethyl methacrylate in 18mL of deionized water containing 5mg of copolymerization emulsifier and 125mg of ammonium bicarbonate, driving air in a reaction device with high-purity nitrogen, heating to 80 ℃ after 30min, stirring, adding 2mL of aqueous solution containing 50mg of initiator KPS into the mixture for microspherical reaction, reacting for 30min, adding 1mL of aqueous solution containing 25mg of initiator KPS and 0.1mL of maleic anhydride into the mixtureThe Maleic Anhydride (MAH) -carboxyl monomer was carboxylated, and after 12h of reflux, the solution was cooled to room temperature, washed by centrifugation, and replaced in stock solution (100 mg/mL).
FIG. 4 is a scanning electron micrograph of 150 nm-sized carboxylated polystyrene fluorescent microspheres in example 5 of the invention, and by comparing with FIG. 3, the particle sizes of the fluorescent microspheres prepared from carboxyl monomers MAH and MAA are found to be similar.
Fig. 6 is a conductance titration graph of the carboxyl content on the surface of the carboxylated fluorescent microsphere in example 5 of the present invention, and it can be seen from fig. 6 that the carboxyl monomer content on the surface of the carboxylated polystyrene fluorescent microsphere prepared in example 5 is: COOH content =9.6 x 10 - 5 mmol/mg。
Fig. 8 is a standard curve diagram of the ability of the carboxylated fluorescent microspheres to couple to Bovine Serum Albumin (BSA) measured by the BCA method in example 5 of the present invention, and it can be seen from fig. 8 that the ability of the carboxylated fluorescent microspheres to couple to Bovine Serum Albumin (BSA) in example 5 of the present invention is: 0.147mg/ml; the capacity of coupling the JSR carboxyl microspheres with the same mass to BSA is 0.124mg/ml.
The invention forms stable europium complex fluorescent microsphere by coating europium complex in the microsphere in a monomer polymerization mode, and the prepared polystyrene fluorescent microsphere has good fluorescence intensity and fluorescence stability, and can be coupled with biomolecules (such as protein) through surface modified carboxyl so as to be used for time-resolved fluorescence immunoassay and test paper strips.
Claims (4)
1. A preparation method of carboxylated polystyrene fluorescent microspheres is characterized by comprising the following steps:
(1) Preparation of fluorescent substance: europium complexes
Will dissolve EuCl 3 .6H 2 Adding ethanol solution of O into ethanol solution of TPPO for coordination reaction, and adding deprotonated ethanol solution of BTFA into Eu (TPPO) 4 Performing coordination reaction at high temperature, filtering, volatilizing, and crystallizing to obtain europium complex Eu (BTFA) (TPPO) 3 (ii) a The reaction temperature is 70 to 75 ℃;
(2) Europium complex Eu (BTFA) (TPPO) prepared in step (1) 3 Preparing polystyrene fluorescent microspheres, and performing carboxylation treatment on the surfaces of the prepared polystyrene fluorescent microspheres to obtain polystyrene fluorescent microspheres with carboxyl monomers on the surfaces; the preparation process of the carboxylated polystyrene fluorescent microsphere comprises the following steps: mixing europium complex Eu (BTFA) (TPPO) 3 Dispersing styrene and hydroxyethyl methacrylate in water containing a copolymerization emulsifier and sodium bicarbonate or ammonium bicarbonate, driving air in a reaction device by using inert gas, heating and stirring, adding a water-soluble thermal initiator for a microspherical reaction, adding the water-soluble thermal initiator and a carboxyl monomer for carboxylation after the reaction, cooling the solution to room temperature after condensation and reflux, centrifugally cleaning, and resetting the product in a storage solution.
2. The preparation method of carboxylated polystyrene fluorescent microspheres according to claim 1, characterized in that: in the step (2), the mixing volume ratio of the styrene to the hydroxyethyl methacrylate is 3:7; europium complex Eu (BTFA) (TPPO) 3 The mass-to-volume ratio of the monomer mixture to the monomer mixture is 2:1.
3. The preparation method of carboxylated polystyrene fluorescent microspheres according to claim 1, characterized in that: in the step (2), the water-soluble thermal initiator is potassium persulfate or ammonium persulfate.
4. The preparation method of carboxylated polystyrene fluorescent microspheres according to claim 1, characterized in that: in the step (2), the carboxyl monomer comprises maleic anhydride, methacrylic acid and acrylic acid.
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| CN1475805A (en) * | 2002-08-15 | 2004-02-18 | 陕西西大北美基因股份有限公司 | Magnetic fluorescence microsphere and its preparation method and method of proceeding biomolecule detection using said magnetic fluorescence microsphere |
| CN101392172A (en) * | 2008-11-01 | 2009-03-25 | 厦门大学 | Carboxylic fluorescent encoding microsphere and synthetic method thereof |
| CN102432973A (en) * | 2010-08-20 | 2012-05-02 | 中国科学院成都有机化学有限公司 | Microspheres for screening high-flux medicaments and preparation method for microspheres |
| CN108084316A (en) * | 2017-12-15 | 2018-05-29 | 中北大学 | A kind of preparation method of carboxylated porous crosslinked polystyrene copolymerization fluorescent microsphere |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1475805A (en) * | 2002-08-15 | 2004-02-18 | 陕西西大北美基因股份有限公司 | Magnetic fluorescence microsphere and its preparation method and method of proceeding biomolecule detection using said magnetic fluorescence microsphere |
| CN101392172A (en) * | 2008-11-01 | 2009-03-25 | 厦门大学 | Carboxylic fluorescent encoding microsphere and synthetic method thereof |
| CN102432973A (en) * | 2010-08-20 | 2012-05-02 | 中国科学院成都有机化学有限公司 | Microspheres for screening high-flux medicaments and preparation method for microspheres |
| CN108084316A (en) * | 2017-12-15 | 2018-05-29 | 中北大学 | A kind of preparation method of carboxylated porous crosslinked polystyrene copolymerization fluorescent microsphere |
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