CN103992789A - Preparation method of inorganic-organic composite fluorescent microsphere - Google Patents
Preparation method of inorganic-organic composite fluorescent microsphere Download PDFInfo
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- CN103992789A CN103992789A CN201410223363.1A CN201410223363A CN103992789A CN 103992789 A CN103992789 A CN 103992789A CN 201410223363 A CN201410223363 A CN 201410223363A CN 103992789 A CN103992789 A CN 103992789A
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Abstract
The invention provides a preparation method of an inorganic-organic composite fluorescent microsphere, belonging to the technical field of preparation of fluorescent materials. The inorganic-organic composite fluorescent microsphere (SiO2@MPS@Poly(AM-co-DVB)) with acrylamide (AM) as a monomer, allyl fluorescein as a fluorescent dye, divinyl benzene (DVB) as a crosslinking agent and 2,2'-azobisisobutyronitrile (AIBN) as an initiator is synthesized by utilizing precipitation polymerization. The prepared SiO2@MPS@Poly(AM-co-DVB) microsphere has the characteristics of narrow particle size distribution range, simplicity in synthesis, good dispersibility, strong fluorescence emission and the like.
Description
Technical field
The present invention relates to a kind of preparation method of inorganic-organic hybrid fluorescent microsphere, belong to fluorescent material preparing technical field.
Background technology
Fluorescent microsphere (Fluorescent microsphere) is as a kind of special functional microsphere, with its stable morphological structure and the stable and feature such as luminous efficiency efficiently, is more and more subject to the love of inclining of vast researcher.Fluorescent microsphere homogeneous grain diameter, monodispersity that newly-developed gets up are good, good stability, luminous efficiency are high.The surface that fluorescent microsphere refers generally to microballoon indicates the microballoon that fluorescent substance (comprising that surface is coated) or microsphere inner structure contain fluorescent substance (as embedding or polymerization), and being subject to outside energy stimulates and can inspire fluorescence.It is a kind of functional microsphere that is loaded with fluorescence molecule, and its profile can have any shape, and is generally spherical.In recent years, along with going deep into of fluorescent probe technique research, people can prepare the fluorescent microsphere of various particle diameters from nano level to submicron order.Fluorescent microsphere has more stable morphological structure and luminous behavior, the impact that is subject to the ambient conditionss such as solvent, heat, electricity, magnetic than pure fluorescent chemicals little a lot of but, because of its preparation process complexity, weak fluorescence, easily restriction of reunion and background fluorescence etc., makes the Application Areas of fluorescent microsphere receive strict restriction.Therefore, reasonably structure design and technological design to overcome seeming of these problems particularly important.
Fluorescent microsphere refers to that sphere diameter is between nanometer to tens micron, and surface or internal load have fluorescent substance, can send the particulate of fluorescence under extraneous conditioned stimulus.The profile of fluorescent microsphere mostly is spherical, also has other shape.The carrier of fluorescent microsphere can be polymkeric substance or inorganic materials, according to the difference of carrier and fluorescent substance, and general common two classes that are divided into: inorganic/organic fluorescence microballoon and organic/organic fluorescence microballoon.Normally used fluorescence dye, as rhodamine, fluorescein, Nile red dye etc. are often applied to preparing fluorescent balls.Rhodamine and fluorescein(e) dye have good bio-compatibility, high quantum production rate and very large optical extinction coefficient; Nile red dye Chang Zuowei environment sensitive type fluorescent probe is applied to detectable biomolecule.In addition, micron order material has larger surface-area, good dispersiveness is often applied to biomedicine and colloid science field.
To sum up, it is narrow that the inorganic-organic hybrid fluorescent microsphere the present invention relates to has particle size distribution range, synthetic simple, good dispersity, the feature such as fluorescent emission is strong.
Summary of the invention
Utilizing precipitation polymerization method to synthesize acrylamide (AM) is monomer, allyl group fluorescein is linking agent as fluorescent reagent, Vinylstyrene (DVB), the organic and inorganic composite S iO that 2,2'-Diisopropyl azodicarboxylate (AIBN) is initiator
2poly (AM-co-DVB) fluorescent microsphere.The SiO of preparation
2poly (AM-co-DVB) fluorescent microsphere has strong green fluorescence and thinner fluorescence shell.
the technical solution used in the present invention is:
A preparation method for inorganic-organic hybrid fluorescent microsphere, carries out according to following step:
(1) SiO
2the preparation of MPS nanometer ball:
Adopt hydrolysis method to prepare SiO
2nanometer ball.In ethanol and distilled water (1:1, v/v), add ammoniacal liquor, ultrasonic 15 minutes, magnetic agitation.Measure tetraethyl orthosilicate (TEOS) and slowly splash in above-mentioned solution, after dropwising, under room temperature condition, react 24 hours.Measure 3-methacryloxypropyl trimethoxy silane (MPS) and be slowly added drop-wise in the oyster white dispersion liquid of generation, continue to stir 24 hours.After reaction finishes, utilize supercentrifuge to collect SiO
2nanometer ball, dry 12h in vacuum drying oven.
2, SiO
2the preparation of MPSPoly (AM-co-DVB) microballoon:
By SiO
2mPS nanometer ball is ultrasonic to be scattered in acetonitrile, then adds respectively 2 ~ 4mmol acrylamide (AM), 0.036 ~ 0.072g allyl group fluorescein and 0.1 ~ 1.0 mL linking agent Vinylstyrene (DVB); After mixing, add 2.5% initiator Diisopropyl azodicarboxylate (AIBN) of the total amount of substance of monomer.Pass into 15 minutes excluding airs of nitrogen, at nitrogen atmosphere lower seal.Adopt thermal-initiated polymerization mode, be placed in 60 DEG C of thermostatical oil baths and heat 24 hours, after polymerization completes, obtain yellow thick product.Wash to washing lotion by alcohol immersion colourless, use spectrofluorometer detect washing lotion retain without luminophore.
Wherein in step (1), in every 50 mL ethanol and distilled water (1:1, v/v), add 2.0 mL ammoniacal liquor, measure the tetraethyl orthosilicate (TEOS) of 2.0 mL, finally add 1 mL3-methacryloxypropyl trimethoxy silane (MPS).
Wherein ultrasonic dispersion 250 mg SiO in every 60 mL acetonitriles in step (2)
2mPS nanometer ball, every 60 mL acetonitriles add respectively 2 ~ 4mmol AM, 0.036 ~ 0.072g allyl group fluorescein and 0.1 ~ 1.0 mL linking agent DVB.
technological merit of the present inventionthe fluorescein that is to use modified by vinyl, as fluorescence dye and monomer, copolymerzation with cross-linking, is dispersed in microballoon shell allyl group fluorescein, makes microballoon luminous evenly; Utilize precipitation polymerization method to prepare the narrow fluorescent microsphere of particle size distribution range.
Brief description of the drawings
fig. 1siO
2the transmission electron microscope (TEM) of MPSPoly (AM-co-DVB) microballoon.As can be seen from Figure, the diameter of microballoon is about 0.27 μ m, and shell thickness is about 5nm, and uniform particle diameter is better dispersed.
fig. 2siO
2the scanning electron microscope (SEM) of MPSPoly (AM-co-DVB) microballoon.As we know from the figure, microballoon has good spherical morphology, and particle diameter is homogeneous comparatively, and diameter is about 270 nm.
fig. 3siO
2mPSPoly (AM-co-DVB) fluorescence spectrum.As we know from the figure, the fluorescence emission peak of microballoon is 521 nm.
Embodiment
Below in conjunction with concrete embodiment, the present invention will be further described, but the invention is not restricted to these embodiment.
embodiment 1
Ultrasonic dispersion 250 mg SiO in every 60 mL acetonitriles
2mPS nanometer ball, every 60 mL acetonitriles add respectively AM, 0.036g allyl group fluorescein and the 0.1mL DVB of 2mmol; After mixing, add 2.5% initiator Diisopropyl azodicarboxylate (AIBN) of the total amount of substance of monomer.Pass into 15 minutes excluding airs of nitrogen, at nitrogen atmosphere lower seal.Adopt thermal-initiated polymerization mode, be placed in 60 DEG C of thermostatical oil baths and heat 24 h, after polymerization completes, obtain yellow thick product.Wash to washing lotion by alcohol immersion colourless, use spectrofluorometer detect washing lotion retain without luminophore.
embodiment 2
Ultrasonic dispersion 250 mg SiO2MPS nanometer balls in every 60 mL acetonitriles, every 60 mL acetonitriles add respectively 4mmol AM, 0.072g allyl group fluorescein and 1.0 mL DVB; After mixing, add 2.5% initiator Diisopropyl azodicarboxylate (AIBN) of the total amount of substance of monomer.Pass into 15 minutes excluding airs of nitrogen, at nitrogen atmosphere lower seal.Adopt thermal-initiated polymerization mode, be placed in 60 DEG C of thermostatical oil baths and heat 24 h, after polymerization completes, obtain yellow thick product.Wash to washing lotion by alcohol immersion colourless, use spectrofluorometer detect washing lotion retain without luminophore..
embodiment 3
Ultrasonic dispersion 250 mg SiO2MPS nanometer balls in every 60 mL acetonitriles, every 60 mL acetonitriles add respectively 3mmol AM, 0.054g allyl group fluorescein and 0.5mL DVB; After mixing, add 2.5% initiator Diisopropyl azodicarboxylate (AIBN) of the total amount of substance of monomer.Pass into 15 minutes excluding airs of nitrogen, at nitrogen atmosphere lower seal.Adopt thermal-initiated polymerization mode, be placed in 60 DEG C of thermostatical oil baths and heat 24 h, after polymerization completes, obtain yellow thick product.Wash to washing lotion by alcohol immersion colourless, use spectrofluorometer detect washing lotion retain without luminophore.TEM, SEM and fluorescence emission spectrum are shown in respectively Fig. 1, Fig. 2 and Fig. 3.
Claims (3)
1. a preparation method for inorganic-organic hybrid fluorescent microsphere, is characterized in that carrying out according to following step:
(1) SiO
2the preparation of MPS nanometer ball:
Adopt hydrolysis method to prepare SiO
2nanometer ball: in ethanol and distilled water (1:1, v/v), add ammoniacal liquor, ultrasonic 15 minutes, magnetic agitation;
Measuring tetraethyl orthosilicate (TEOS) slowly splashes in above-mentioned solution, after dropwising, under room temperature condition, react 24 hours, measuring 3-methacryloxypropyl trimethoxy silane (MPS) is slowly added drop-wise in the oyster white dispersion liquid of generation, continue to stir 24 hours, after reaction finishes, utilize supercentrifuge to collect SiO
2nanometer ball, dry 12h in vacuum drying oven;
(2) SiO
2the preparation of MPSPoly (AM-co-DVB) microballoon:
By SiO
2mPS nanometer ball is ultrasonic to be scattered in acetonitrile, then add respectively acrylamide AM, 0.036 ~ 0.072g allyl group fluorescein and 0.1 ~ 1.0 mL linking agent Vinylstyrene DVB, after mixing, add 2.5% initiator Diisopropyl azodicarboxylate (AIBN) of the total amount of substance of monomer, pass into 15 minutes excluding airs of nitrogen, at nitrogen atmosphere lower seal, adopt thermal-initiated polymerization mode, be placed in 60 DEG C of thermostatical oil baths and heat 24 hours, after polymerization completes, obtain yellow thick product; Wash to washing lotion by alcohol immersion colourless, use spectrofluorometer detect washing lotion retain without luminophore.
2. the preparation method of a kind of inorganic-organic hybrid fluorescent microsphere according to claim 1, it is characterized in that wherein every 50 mL ethanol and distilled water (1:1 in step (1), v/v) in, add 2.0 mL ammoniacal liquor, measure the tetraethyl orthosilicate (TEOS) of 2.0 mL, finally add 1 mL3-methacryloxypropyl trimethoxy silane (MPS).
3. the preparation method of a kind of inorganic-organic hybrid fluorescent microsphere according to claim 1, is characterized in that wherein in step (2) ultrasonic dispersion 250 mg SiO in every 60 mL acetonitriles
2mPS nanometer ball, every 60 mL acetonitriles add respectively 2 ~ 4mmol AM, 0.036 ~ 0.072g allyl group fluorescein and 0.1 ~ 1.0 mL linking agent DVB.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104388079A (en) * | 2014-10-28 | 2015-03-04 | 江苏大学 | Preparation method of composite fluorescent microspheres |
| CN107952403A (en) * | 2017-12-04 | 2018-04-24 | 济南大学 | A kind of fluorescent silicon dioxide method for preparing microsphere of Quantitative detection iron ion |
| CN108192596A (en) * | 2018-02-09 | 2018-06-22 | 中北大学 | A kind of cladded type carboxylated SiO2The preparation method of fluorescent nanosphere |
| CN110407986A (en) * | 2019-07-30 | 2019-11-05 | 中北大学 | A kind of preparation method of pH, temperature response type bivalve layer tiny balloon |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US20060276577A1 (en) * | 2005-06-01 | 2006-12-07 | Lee Chang S | Functional organic particle, and method for preparing the same |
| CN102618258A (en) * | 2012-02-23 | 2012-08-01 | 常州天合光能有限公司 | Fluorescent nanoparticle as well as preparation method and application thereof |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060276577A1 (en) * | 2005-06-01 | 2006-12-07 | Lee Chang S | Functional organic particle, and method for preparing the same |
| CN102618258A (en) * | 2012-02-23 | 2012-08-01 | 常州天合光能有限公司 | Fluorescent nanoparticle as well as preparation method and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| GUOLIANG LI ET AL.: "Facile Synthesis of Hollow Polymer Microspheres with Movable Cores with the Aid of Hydrogen-Bonding Interaction", 《J. PHYS. CHEM. B》 * |
| 刘霖 等: "空心聚合物微球的合成", 《天津工业大学学报》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104388079A (en) * | 2014-10-28 | 2015-03-04 | 江苏大学 | Preparation method of composite fluorescent microspheres |
| CN107952403A (en) * | 2017-12-04 | 2018-04-24 | 济南大学 | A kind of fluorescent silicon dioxide method for preparing microsphere of Quantitative detection iron ion |
| CN108192596A (en) * | 2018-02-09 | 2018-06-22 | 中北大学 | A kind of cladded type carboxylated SiO2The preparation method of fluorescent nanosphere |
| CN108192596B (en) * | 2018-02-09 | 2020-07-24 | 中北大学 | Coated carboxylated SiO2Preparation method of fluorescent nanosphere |
| CN110407986A (en) * | 2019-07-30 | 2019-11-05 | 中北大学 | A kind of preparation method of pH, temperature response type bivalve layer tiny balloon |
| CN110407986B (en) * | 2019-07-30 | 2021-07-30 | 中北大学 | Preparation method of pH and temperature response type double-shell hollow microspheres |
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