CN108164712A - A kind of Synthesis, Characterization of Polyphosphazenes fluorescent microsphere and preparation method thereof - Google Patents
A kind of Synthesis, Characterization of Polyphosphazenes fluorescent microsphere and preparation method thereof Download PDFInfo
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- CN108164712A CN108164712A CN201810012890.6A CN201810012890A CN108164712A CN 108164712 A CN108164712 A CN 108164712A CN 201810012890 A CN201810012890 A CN 201810012890A CN 108164712 A CN108164712 A CN 108164712A
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- acetone
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- fluorescent microsphere
- polyphosphazenes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G79/00—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule
- C08G79/02—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule a linkage containing phosphorus
- C08G79/025—Polyphosphazenes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/02—Making microcapsules or microballoons
- B01J13/06—Making microcapsules or microballoons by phase separation
- B01J13/14—Polymerisation; cross-linking
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
- G01N2021/6439—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes" with indicators, stains, dyes, tags, labels, marks
Abstract
The invention discloses a kind of preparation methods of Synthesis, Characterization of Polyphosphazenes fluorescent microsphere, belong to Functional polymer materials technology field.The method that the present invention uses reflux precipitation polymerization, with chlordene tripolyphosphazene, 4,4' dihydroxydiphenylsulisomers are monomer, and acetone is that the tertiary amines such as solvent, trioctylamine, triethylamine alkane compound is acid binding agent, it is loaded into fluorescent dye, cause chlordene tripolyphosphazene, the polymerization of 4,4' dihydroxydiphenylsulisomers, prepare the uniform micron-scale polyphosphazene fluorescent microsphere of monodisperse, pattern.The preparation method is simple, reaction temperature be 50 DEG C, the reaction time be 1 ~ 8 h, microballoon pattern uniform particle diameter obtained, stable structure.The fluorescent microsphere of the present invention is easily dispersed in water and ethyl alcohol, which contains a large amount of hydroxyl, is conducive to surface modification and is further modified, is had broad application prospects in terms of biological detection, particularly High throughput.
Description
Technical field
The invention belongs to Functional polymer materials technology fields, and in particular to a kind of system of Synthesis, Characterization of Polyphosphazenes fluorescent microsphere
Preparation Method.
Background technology
High molecular fluorescent microballoons have that large specific surface area, surface adsorption property be strong, designability of aggregate structure composition
The advantages that, while particle size is controllable, form of diverse, in the inspection of coating, paper surface coating, cosmetics to harmful metal ion
Survey with detaching, with the interaction of biomolecule, the detection of cell activity, the synthesis of chemiluminescent polypeptide object and antibody or antigen
The fields such as fixed, DNA/RNA separation detection have a wide range of applications.With high molecular fluorescent microballoons technology of preparing not
Disconnected development, from traditional emulsion polymerization, suspension polymerisation, dispersin polymerization, develop to emulsifier-free emulsion polymerization, seeded emulsion polymerization,
What seed swelling polymerization and macromonomer participated in distills the new preparation method such as precipitation polymerization and self assembly, however prepares shape
The technology of high performance polymer fluorescent microsphere that looks are uniform, size is controllable is still current a big difficulty and hot spot.
High molecular fluorescent microballoons are widely used in multivariate analysis because they have isotropism, it is easily operated simultaneously
And it can faster be reacted in homogeneous solution by suspension.The preparation method of fluorescence-encoded micro-beads has at present：Organic solvent is molten
Swollen method, self-assembled multilayer film method, investment, microflow control technique, membrane emulsification, sol-gel method etc..
The present invention is using reflux precipitation polymerization process, and with chlordene tripolyphosphazene, 4,4'- dihydroxydiphenylsulisomers are monomer, and third
Ketone is the tertiary amines such as solvent, trioctylamine, triethylamine alkane compound for acid binding agent, be loaded into FITC, phloxine B, R6G,
Single fluorescent molecular or the multiple combinations such as SRh101, phloxine and Liz peace rhodamine B, cause chlordene tripolyphosphazene, 4,4'-
Dihydroxydiphenylsulisomer polymerize, prepare monodisperse, pattern it is uniform, polyphosphazene fluorescent microsphere.The preparation method is simple, reaction temperature
Be 50 DEG C, the reaction time be 1 ~ 8 h, microballoon pattern uniform particle diameter obtained, stable structure.The fluorescent microsphere surface of the present invention
There is a large amount of hydroxyl, be conducive to surface modification and be further modified, have in terms of biological detection, particularly High throughput
Wide application prospect.
Invention content
It is an object of the invention to be directed to the sides such as current high molecular fluorescent microballoons preparation method, pattern control and luminescent properties
The deficiency in face provides a kind of high performance Synthesis, Characterization of Polyphosphazenes fluorescent microsphere and preparation method.Microballoon produced by the present invention has
The advantages of balling-up is good, pattern is uniform controllable, microsphere surface are conducive to further modification rich in great amount of hydroxy group, in biological detection,
It is had broad application prospects in terms of High throughput, and preparation process is easy, without adding surfactant.
To achieve the above object, the present invention is achieved by the following technical solutions：
Present invention application reflux precipitation polymerization method, with chlordene tripolyphosphazene and 4,4'- dihydroxydiphenylsulisomer for monomer, tertiary amine alkane
Hydrocarbon compound is acid binding agent, and acetone is solvent, is loaded into 5（6）Fluorescein isothiocynate（FITC）, phloxine B, rhodamine 6G
（R6G）, Sulforhodamine 101（SRh101）, a kind of or a combination thereof fluorescent dye in phloxine and Liz peace rhodamine B
Prepare high-performance polyphosphazene fluorescent microsphere.Preparation process is as follows：
（1）Various dye solutions are configured as 0.50 g/L； FITC （Solvent is ethyl alcohol）、R6G（Solvent is acetone）、SRh101
（Solvent is water）, phloxine（Solvent is acetone）Pacify rhodamine B with Liz（Solvent is acetone）；
（2）Precision balance weighs 0.1000 ~ 1.000 g 4, and 4'- dihydroxydiphenylsulisomers are added in three-necked flask, Ran Houjia
Enter 125 mL acetone solutions；
（3）20 ~ 5000 μ L fluorescent molecular solution is taken to be added in three-necked flask；
（4）The acid binding agent of 0.5 ~ 5.0 mL is taken to be added in three-necked flask；
（5）Three-necked flask is placed in water-bath, 50 DEG C of set temperature, 200 rpm of mechanical agitation, condensing reflux；
（6）Precision balance weighs 0.0500 ~ 0.6000 g chlordene tripolyphosphazenes, with 25 mL acetone solutions in test tube, ultrasound
Auxiliary dissolving, is then preheated to 50 DEG C；
（7）By step（6）Chlordene tripolyphosphazene solution is added to step（5）In three-necked flask, reaction starts；
（8）Reaction stops reaction after continuing 3 h, cleans precipitation three times with acetone, ethyl alcohol, distilled water respectively, is finally dried in vacuo
12 h。
The beneficial effects of the present invention are：
This method method therefor has the advantages that reaction process is simple, simple operation.The polyphosphazene being prepared in the present invention is glimmering
Light microballoon has the characteristics that compound with regular structure, monodisperse.Due to the great amount of hydroxy group in reaction monomers, be conducive to microsphere surface into one
The modified combination with large biological molecule of step can have wide answer in terms of biological detection, particularly High throughput
Use prospect.
Description of the drawings
Fig. 1 to Fig. 6 is respectively the polyphosphazene of the fluorescence of hair different colours that the method for the present invention is prepared in differential responses condition
Fluorescent microsphere fluorescence photo and launching light spectrogram（488 nm of excitation wavelength）.
Fig. 1 is the fluorescence photo of polyphosphazene fluorescent microsphere prepared by embodiment 1（Scale is 10 μm in figure）；
Fig. 2 is the launching light spectrogram of polyphosphazene fluorescent microsphere prepared by embodiment 1；
Fig. 3 is the fluorescence photo of polyphosphazene fluorescent microsphere prepared by embodiment 2（Scale is 10 μm in figure）；
Fig. 4 is the launching light spectrogram of polyphosphazene fluorescent microsphere prepared by embodiment 2；
Fig. 5 is the fluorescence photo of polyphosphazene microspheres prepared by embodiment 3（Scale is 10 μm in figure）；
Fig. 6 is the launching light spectrogram of polyphosphazene fluorescent microsphere prepared by embodiment 3.
Fig. 1 and Fig. 2 illustrates the fluorescent microsphere uniform particle diameter, and size is 3 μm, bright green light is invented, at 550 nm wavelength
With the good characteristics of luminescence；
Fig. 3 and Fig. 4 illustrates the fluorescent microsphere uniform particle diameter, and size is 5 μm, invents bright orange light, has at 574 nm wavelength
The good characteristics of luminescence；
Fig. 5 and Fig. 6 illustrates the fluorescent microsphere uniform particle diameter, and size is 4 μm, invents bright feux rouges, has at 601 nm wavelength
The good characteristics of luminescence.
Specific embodiment
Embodiment 1
（1）125 mL acetone, 0.8625 g 4,4'- dihydroxydiphenylsulisomers, 2500 μ L R6G (0.50 are added in three-necked flask
G/L) solution and 4.0 mL trioctylamines, setting bath temperature are 50 DEG C, 200 rpm of mechanical agitation, condensing reflux；
（2）0.6000 g chlordene tripolyphosphazenes are dissolved in 25 mL acetone, after being preheated to 50 DEG C, add in step（1）In three
In mouth flask, 3 h are reacted；
（3）By step（2）Product clean precipitation three times with acetone, ethyl alcohol and distilled water respectively, centrifuge, end product is true
Dry 12 h of sky.
Embodiment 2
（1）125 mL acetone, 0.8625 g 4,4'- dihydroxydiphenylsulisomers, 1000 μ L phloxines are added in three-necked flask
B (0.50 g/L) solution and 3.5 mL trioctylamines, setting bath temperature are 50 DEG C, 200 rpm of mechanical agitation, condensing reflux；
（2）0.6000 g chlordene tripolyphosphazenes are dissolved in 25 mL acetone, after being preheated to 50 DEG C, add in step（1）In three
In mouth flask, 3 h are reacted；
（3）By step（2）Product clean precipitation three times with acetone, ethyl alcohol and distilled water respectively, centrifuge, end product is true
Dry 12 h of sky.
Embodiment 3
（1）125 mL acetone, 0.8625 g 4,4'- dihydroxydiphenylsulisomers, 200 μ L SRh101 are added in three-necked flask
(0.50 g/L) solution and 3.5 mL trioctylamines, setting bath temperature are 50 DEG C, 200 rpm of mechanical agitation, condensing reflux；
（2）0.6000 g chlordene tripolyphosphazenes are dissolved in 25 mL acetone, after being preheated to 50 DEG C, add in step（1）In three
In mouth flask, 3 h are reacted；
（3）By step（2）Product clean precipitation three times with acetone, ethyl alcohol and distilled water respectively, centrifuge, end product is true
Dry 12 h of sky.
Embodiment 4
（1）125 mL acetone, 0.8625 g 4,4'- dihydroxydiphenylsulisomers, 100 μ L R6G (0.50 are added in three-necked flask
G/L) and 300 μ L SRh101 (0.50 g/L) solution and 3.5 mL trioctylamines, setting bath temperature are 50 DEG C, mechanical agitation
200 rpm, condensing reflux；
（2）0.6000 g chlordene tripolyphosphazenes are dissolved in 25 mL acetone, after being preheated to 50 DEG C, add in step（1）In three
In mouth flask, 3 h are reacted；
（3）By step（2）Product clean precipitation three times with acetone, ethyl alcohol and distilled water respectively, centrifuge, end product is true
Dry 12 h of sky.
Embodiment 5
（1）125 mL acetone, 0.8625 g 4,4'- dihydroxydiphenylsulisomers, 1000 μ L FITC are added in three-necked flask
(0.10 g/L), 20 μ L R6G (0.050 g/L) and 50 μ L SRh101 (0.50 g/L) solution and 4.0 mL trioctylamines,
It is 50 DEG C, 200 rpm of mechanical agitation to set bath temperature, condensing reflux；
（2）0.6000 g chlordene tripolyphosphazenes are dissolved in 25 mL acetone, after being preheated to 50 DEG C, add in step（1）In three
In mouth flask, it is protected from light 3 h；
（3）By step（2）Product clean precipitation three times with acetone, ethyl alcohol and distilled water respectively, centrifuge, end product is true
Dry 12 h of sky.
The preferred embodiment of the present invention described in detail above.It should be appreciated that the ordinary skill of this field is without wound
The property made labour, which according to the present invention can conceive, makes many modifications and variations.Therefore, all technician in the art
Pass through the available technology of logical analysis, reasoning, or a limited experiment on the basis of existing technology under this invention's idea
Scheme, all should be in the protection domain being defined in the patent claims.
Claims (4)
1. a kind of preparation method of Synthesis, Characterization of Polyphosphazenes fluorescent microsphere, it is characterised in that：The microballoon be with chlordene tripolyphosphazene, 4,
4'- dihydroxydiphenylsulisomers are monomer, and acetone is solvent, and tertiary amine alkane compound is acid binding agent, adds in fluorescent dye solution, leads to
The method for crossing reflux precipitation polymerization is made.
2. the preparation method of Synthesis, Characterization of Polyphosphazenes fluorescent microsphere according to claim 1, it is characterised in that：The tertiary amine
Alkane compound is trioctylamine or triethylamine.
3. the preparation method of Synthesis, Characterization of Polyphosphazenes fluorescent microsphere according to claim 1, it is characterised in that：The fluorescence
Dyestuff includes one or more in FITC, phloxine B, R6G, SRh101, phloxine and Liz peace rhodamine B.
4. according to the preparation method of any Synthesis, Characterization of Polyphosphazenes microballoons of claim 1-3, it is characterised in that：It specifically includes
Following steps：
（1）In the acetone of 125 mL, 0.1 ~ 1.0 g 4,4'- dihydroxydiphenylsulisomers, 0.001 ~ 2.5 mg fluorescent dyes are added in
With 0.5 ~ 5.0 mL acid binding agents, it is mixed, is then heated to 50 DEG C；
（2）Immediately to step（1）In mixture in add in 25 mL acetone solutions, 0.05 ~ 0.60 g chlordene trimerizations
200 rpm are stirred in the solution of phosphonitrile, then 50 DEG C of waters bath with thermostatic control, and condensing reflux reacts 3 h；
（3）By step（2）Product respectively with acetone, ethyl alcohol, distilled water clean precipitation three times, be finally dried in vacuo 12 h.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109053955A (en) * | 2018-08-20 | 2018-12-21 | 安徽理工大学 | A kind of water solubility and temperature-responsive fluorescent polymer and preparation method thereof based on sulfone |
| CN110893334A (en) * | 2018-09-12 | 2020-03-20 | 福州大学 | Polyphosphazene fluorescence-surface enhanced Raman coding microsphere and preparation method 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 |
| 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 |
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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 |
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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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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109053955A (en) * | 2018-08-20 | 2018-12-21 | 安徽理工大学 | A kind of water solubility and temperature-responsive fluorescent polymer and preparation method thereof based on sulfone |
| CN110893334A (en) * | 2018-09-12 | 2020-03-20 | 福州大学 | Polyphosphazene fluorescence-surface enhanced Raman coding microsphere and preparation method 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 |
| 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 |
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