CN108164712B - Polyphosphazene high-molecular fluorescent microsphere and preparation method thereof - Google Patents
Polyphosphazene high-molecular fluorescent microsphere and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a preparation method of polyphosphazene high-molecular fluorescent microspheres, and belongs to the technical field of functional high-molecular materials. The invention adopts a reflux precipitation polymerization method, takes hexachlorotriphosphazene, 4, 4 '-dihydroxy diphenyl sulfone as a monomer, acetone as a solvent, trioctylamine, triethylamine and other tertiary amine alkane compounds as acid-binding agents, and loads fluorescent dye to initiate polymerization of hexachlorotriphosphazene and 4, 4' -dihydroxy diphenyl sulfone, so as to prepare the monodisperse micron-sized polyphosphazene fluorescent microspheres with uniform appearance. The preparation method is simple, the reaction temperature is 50 ℃, the reaction time is 1-8 hours, and the prepared microspheres are uniform in shape and particle size and stable in structure. The fluorescent microsphere is easy to disperse in water and ethanol, contains a large amount of hydroxyl on the surface, is beneficial to surface modification and further modification, and has wide application prospect in biological detection, particularly in the aspect of high-throughput analysis technology.
Description
Technical Field
The invention belongs to the technical field of functional polymer materials, and particularly relates to a preparation method of polyphosphazene polymer fluorescent microspheres.
Background
The polymer fluorescent microsphere has the advantages of large specific surface area, strong surface adsorption performance, designability of aggregate structure composition and the like, has controllable particle size and various forms, and has wide application prospect in the fields of paint, paper surface coating, detection and separation of harmful metal ions from cosmetics, interaction with biomolecules, detection of cell activity, synthesis of polypeptide chemicals, fixation of antibodies or antigens, separation and detection of DNA/RNA and the like. With the continuous development of the preparation technology of the polymer fluorescent microspheres, the traditional preparation methods of emulsion polymerization, suspension polymerization, dispersion polymerization, soap-free emulsion polymerization, seeded swelling polymerization, distillation precipitation polymerization with participation of macromonomers, self-assembly and the like have been developed, however, the technology for preparing the high-performance polymer fluorescent microspheres with uniform appearance and controllable size is still a major difficulty and hot spot at present.
Polymeric fluorescent microspheres are widely used in multiplex assays because they are isotropic, easy to handle and can be reacted more quickly in a homogeneous solution by suspension. The current preparation method of the fluorescent coding microsphere comprises the following steps: organic solvent swelling method, layer-layer self-assembly method, embedding method, micro-fluidic technology, membrane emulsification method, sol-gel method, etc.
The invention adopts a reflux precipitation polymerization method, uses hexachlorotriphosphazene, 4, 4 '-dihydroxy diphenyl sulfone as monomers, acetone as a solvent, trioctylamine, triethylamine and other tertiary amine alkane compounds as acid-binding agents, and loads single fluorescent molecules or various combinations of FITC, fluorescent peach red B, R6G, SRh101, fluorescent peach red, LiseoAnrhodamine B and the like to initiate polymerization of hexachlorotriphosphazene and 4, 4' -dihydroxy diphenyl sulfone, so as to prepare the monodisperse uniform-morphology polyphosphazene fluorescent microspheres. The preparation method is simple, the reaction temperature is 50 ℃, the reaction time is 1-8 hours, and the prepared microspheres are uniform in shape and particle size and stable in structure. The fluorescent microsphere has a large number of hydroxyl groups on the surface, is favorable for surface modification and further modification, and has wide application prospect in biological detection, particularly in the aspect of high-throughput analysis technology.
Disclosure of Invention
The invention aims to provide a high-performance polyphosphazene high-molecular fluorescent microsphere and a preparation method thereof aiming at the defects of the conventional preparation method, morphology control, luminescent property and the like of the high-molecular fluorescent microsphere. The microsphere prepared by the method has the advantages of good balling performance and uniform and controllable appearance, the surface of the microsphere is rich in a large number of hydroxyl groups, the further modification is facilitated, the microsphere has wide application prospects in the aspects of biological detection and high-throughput analysis technology, the preparation process is simple and convenient, and no surfactant is required to be added.
In order to realize the purpose, the invention is realized by the following technical scheme:
the invention applies a reflux precipitation polymerization method, hexachlorotriphosphazene and 4, 4' -dihydroxy diphenyl sulfone are taken as monomers, tertiary amine alkane compound is taken as an acid-binding agent, acetone is taken as a solvent, and one or the combination of fluorescent dyes of 5 (6) -Fluorescein Isothiocyanate (FITC), fluorescent peach red B, rhodamine 6G (R6G), sulforhodamine 101 (SRh 101), fluorescent peach red and Liseantuo rhodamine B is loaded to prepare the high-performance polyphosphazene fluorescent microsphere. The preparation process comprises the following specific steps:
(1) preparing various dye solutions to be 0.50 g/L; FITC (ethanol as a solvent), R6G (acetone as a solvent), SRh101 (water as a solvent), fluorescent pink (acetone as a solvent) and Liseantuo rhodamine B (acetone as a solvent);
(2) weighing 0.1000-1.000 g of 4, 4' -dihydroxy diphenyl sulfone by using a precision balance, adding into a three-neck flask, and then adding 125 mL of acetone for dissolving;
(3) adding 20-5000 mu L of fluorescent molecule solution into a three-neck flask;
(4) adding 0.5-5.0 mL of acid-binding agent into a three-neck flask;
(5) placing the three-neck flask in a water bath kettle, setting the temperature at 50 ℃, mechanically stirring at 200 rpm, and condensing and refluxing;
(6) weighing 0.0500-0.6000 g of hexachlorotriphosphazene by a precision balance, dissolving the hexachlorotriphosphazene in a test tube by using 25 mL of acetone, dissolving the hexachlorotriphosphazene in the test tube by ultrasonic assistance, and then preheating the test tube to 50 ℃;
(7) adding the hexachlorotriphosphazene solution obtained in the step (6) into the three-neck flask obtained in the step (5), and starting reaction;
(8) and stopping the reaction after the reaction lasts for 3 hours, respectively washing the precipitate with acetone, ethanol and distilled water for three times, and finally drying in vacuum for 12 hours.
The invention has the beneficial effects that:
the method has the advantages of simple reaction process and convenient operation. The polyphosphazene fluorescent microspheres prepared by the method have the characteristics of regular structure, monodispersity and the like. Because of a large amount of hydroxyl in the reaction monomer, the surface of the microsphere is further modified and the biomacromolecule is combined, and the method has wide application prospect in biological detection, particularly in the aspect of high-throughput analysis technology.
Drawings
FIGS. 1 to 6 are a fluorescent photograph and an emission spectrum (excitation wavelength 488 nm) of polyphosphazene fluorescent microspheres which are prepared under different reaction conditions and emit fluorescence of different colors by the method of the present invention.
FIG. 1 is a fluorescent photograph (10 μm in scale) of polyphosphazene fluorescent microspheres prepared in example 1;
FIG. 2 is an emission spectrum of the polyphosphazene fluorescent microsphere prepared in example 1;
FIG. 3 is a fluorescent photograph (10 μm in scale) of the polyphosphazene fluorescent microspheres prepared in example 2;
FIG. 4 is an emission spectrum of the polyphosphazene fluorescent microsphere prepared in example 2;
FIG. 5 is a fluorescent photograph of polyphosphazene microspheres prepared in example 3 (10 μm is shown in the figure);
FIG. 6 is the emission spectrum of the polyphosphazene fluorescent microsphere prepared in example 3.
FIG. 1 and FIG. 2 show that the fluorescent microsphere has uniform particle size, 3 μm size, bright green light emission and good light emission characteristic at the wavelength of 550 nm;
FIGS. 3 and 4 show that the fluorescent microspheres have uniform particle size, 5 mu m size, bright orange light emission and good light emission characteristic at 574 nm wavelength;
FIGS. 5 and 6 show that the fluorescent microspheres have uniform particle size, 4 mu m size, bright red light emission and good light emission characteristic at 601 nm wavelength.
Detailed Description
Example 1
(1) 125 mL of acetone, 0.8625 g of 4, 4' -dihydroxydiphenyl sulfone, 2500 mu L R6G (0.50 g/L) solution and 4.0 mL of trioctylamine are added into a three-neck flask, the water bath temperature is set to be 50 ℃, the mechanical stirring is carried out at 200 rpm, and the condensation reflux is carried out;
(2) dissolving 0.6000 g of hexachlorotriphosphazene in 25 mL of acetone, preheating to 50 ℃, adding into the three-neck flask obtained in the step (1), and reacting for 3 h;
(3) and (3) washing the product obtained in the step (2) with acetone, ethanol and distilled water respectively for three times, performing centrifugal separation, and finally performing vacuum drying on the product for 12 hours.
Example 2
(1) 125 mL of acetone, 0.8625 g of 4, 4' -dihydroxy diphenyl sulfone, 1000 muL of fluorescent peach red B (0.50 g/L) solution and 3.5 mL of trioctylamine are added into a three-neck flask, the water bath temperature is set to be 50 ℃, mechanical stirring is carried out at 200 rpm, and condensation reflux is carried out;
(2) dissolving 0.6000 g of hexachlorotriphosphazene in 25 mL of acetone, preheating to 50 ℃, adding into the three-neck flask obtained in the step (1), and reacting for 3 h;
(3) and (3) washing the product obtained in the step (2) with acetone, ethanol and distilled water respectively for three times, performing centrifugal separation, and finally performing vacuum drying on the product for 12 hours.
Example 3
(1) 125 mL of acetone, 0.8625 g of 4, 4' -dihydroxydiphenyl sulfone, 200 mu of LSRh101(0.50 g/L) solution and 3.5 mL of trioctylamine are added into a three-neck flask, the water bath temperature is set to be 50 ℃, the mechanical stirring is carried out at 200 rpm, and the condensation reflux is carried out;
(2) dissolving 0.6000 g of hexachlorotriphosphazene in 25 mL of acetone, preheating to 50 ℃, adding into the three-neck flask obtained in the step (1), and reacting for 3 h;
(3) and (3) washing the product obtained in the step (2) with acetone, ethanol and distilled water respectively for three times, performing centrifugal separation, and finally performing vacuum drying on the product for 12 hours.
Example 4
(1) 125 mL of acetone, 0.8625 g of 4, 4' -dihydroxydiphenyl sulfone, 100 mu L R6G (0.50 g/L) and 300 mu L of SRh101(0.50 g/L) solution and 3.5 mL of trioctylamine are added into a three-neck flask, the water bath temperature is set to be 50 ℃, the mechanical stirring is carried out at 200 rpm, and the condensation and the reflux are carried out;
(2) dissolving 0.6000 g of hexachlorotriphosphazene in 25 mL of acetone, preheating to 50 ℃, adding into the three-neck flask obtained in the step (1), and reacting for 3 h;
(3) and (3) washing the product obtained in the step (2) with acetone, ethanol and distilled water respectively for three times, performing centrifugal separation, and finally performing vacuum drying on the product for 12 hours.
Example 5
(1) 125 mL of acetone, 0.8625 g of 4, 4' -dihydroxydiphenyl sulfone, 1000 muL of FITC (0.10 g/L), 20 muL of L R6G (0.050 g/L) and 50 muL of SRh101(0.50 g/L) solution and 4.0 mL of trioctylamine are added into a three-neck flask, the temperature of a water bath is set to be 50 ℃, mechanical stirring is carried out at 200 rpm, and condensation reflux is carried out;
(2) dissolving 0.6000 g of hexachlorotriphosphazene in 25 mL of acetone, preheating to 50 ℃, adding into the three-neck flask obtained in the step (1), and reacting for 3 hours in a dark place;
(3) and (3) washing the product obtained in the step (2) with acetone, ethanol and distilled water respectively for three times, performing centrifugal separation, and finally performing vacuum drying on the product for 12 hours.
The foregoing detailed description of the preferred embodiments of the invention has been presented. It should be understood that numerous modifications and variations could be devised by those skilled in the art in light of the present teachings without departing from the inventive concepts. Therefore, the technical solutions available to those skilled in the art through logic analysis, reasoning and limited experiments based on the prior art according to the concept of the present invention should be within the scope of protection defined by the claims.
Claims (2)
1. A preparation method of polyphosphazene high-molecular fluorescent microspheres is characterized by comprising the following steps: the method specifically comprises the following steps:
(1) adding 0.1-1.0 g of 4, 4' -dihydroxy diphenyl sulfone, 0.001-2.5 mg of fluorescent dye and 0.5-5.0 mL of acid-binding agent into 125 mL of acetone, mixing and stirring, and then heating to 50 ℃;
(2) adding a solution in which 0.05-0.60 g of hexachlorotriphosphazene is dissolved by 25 mL of acetone into the mixture in the step (1), then carrying out thermostatic water bath at 50 ℃, stirring at 200 rpm, carrying out condensation reflux, and reacting for 3 hours;
(3) washing and precipitating the product obtained in the step (2) with acetone, ethanol and distilled water for three times respectively, and finally performing vacuum drying for 12 hours;
the fluorescent dye comprises one or more of FITC, fluorescent peach red B, R6G, SRh101, fluorescent peach red and Liseiflammine B.
2. The preparation method of polyphosphazene polymeric fluorescent microspheres according to claim 1, wherein the preparation method comprises the following steps: the acid-binding agent is trioctylamine or triethylamine.
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| CN109053955B (en) * | 2018-08-20 | 2020-09-04 | 安徽理工大学 | Water-soluble and temperature-responsive fluorescent polymer based on sulfone and preparation method thereof |
| CN110893334A (en) * | 2018-09-12 | 2020-03-20 | 福州大学 | Polyphosphazene fluorescence-surface enhanced Raman coding microsphere and preparation method thereof |
| CN111363155A (en) * | 2020-03-09 | 2020-07-03 | 南华大学上虞高等研究院有限公司 | Hydroxyl-terminated polyphosphazene microsphere, preparation method and application thereof |
| CN111363156A (en) * | 2020-03-09 | 2020-07-03 | 南华大学上虞高等研究院有限公司 | Functionalized polyphosphazene microsphere, preparation method and application thereof |
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| CN101092484A (en) * | 2007-06-21 | 2007-12-26 | 上海交通大学 | Surface modified microballons of containing phosphazene, and preparation method |
| CN107523288A (en) * | 2017-07-24 | 2017-12-29 | 深圳清华大学研究院 | Near-infrared II areas high molecular fluorescent microballoons and preparation method thereof |
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| CN101092484A (en) * | 2007-06-21 | 2007-12-26 | 上海交通大学 | Surface modified microballons of containing phosphazene, and preparation method |
| CN107523288A (en) * | 2017-07-24 | 2017-12-29 | 深圳清华大学研究院 | Near-infrared II areas high molecular fluorescent microballoons and preparation method thereof |
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| Heteroatom Doped-Carbon Nanospheres as Anodes;George S. Pappas et.al;《materials》;20160109;第2页第3段 * |
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