CN103992789B - A kind of preparation method of inorganic-organic hybrid fluorescent microsphere - Google Patents
A kind of preparation method of inorganic-organic hybrid fluorescent microsphere Download PDFInfo
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- CN103992789B CN103992789B CN201410223363.1A CN201410223363A CN103992789B CN 103992789 B CN103992789 B CN 103992789B CN 201410223363 A CN201410223363 A CN 201410223363A CN 103992789 B CN103992789 B CN 103992789B
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Abstract
The preparation method of a kind of inorganic-organic hybrid fluorescent microsphere of the present invention, belongs to fluorescent material preparing technical field.This its method has been synthesized with acrylamide (AM) for monomer for utilizing precipitation polymerization method, allyl group fluorescein is linking agent as fluorescence dye, Vinylstyrene (DVB), 2,2 ˊ-azo two is butyronitrile (AIBN) inorganic-organic hybrid fluorescent microsphere (SiO that is initiator
2mPSPoly (AM-co-DVB)).The SiO of preparation
2it is narrow that MPSPoly (AM-co-EGDMA) microballoon has particle size distribution range, and synthesis is simple, good dispersity, the features such as fluorescent emission is strong.
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 (Fluorescentmicrosphere) is as a kind of special functional microsphere, and the morphological structure stable with it and the stable and feature such as luminous efficiency efficiently, be more and more subject to the love of inclining of vast researcher.The fluorescent microsphere homogeneous grain diameter that newly-developed gets up, monodispersity are good, good stability, luminous efficiency are high.The surface that fluorescent microsphere refers generally to microballoon indicates the microballoon that fluorescent substance (comprising Surface coating) 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 being 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 diameter from nano level to submicron order.Fluorescent microsphere has more stable morphological structure and luminescent behavior, impact by ambient conditionss such as solvent, heat, electricity, magnetic less than pure fluorescent chemicals a lot of but, because its preparation process is complicated, more weak fluorescence, restriction of easy reunion and background fluorescence etc., makes the Application Areas of fluorescent microsphere receive strict restriction.Therefore, to overcome seeming of these problems particularly important for rational structure design and technological design.
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, is commonly divided into two classes: 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 excellent 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 colloidal sciences.
To sum up, it is narrow that the inorganic-organic hybrid fluorescent microsphere that the present invention relates to has particle size distribution range, and synthesis is simple, good dispersity, the features such as fluorescent emission is strong.
Summary of the invention
Acrylamide (AM) is monomer to have utilized precipitation polymerization method to synthesize, allyl group fluorescein is linking agent as fluorescent reagent, Vinylstyrene (DVB), the Organic-inorganic composite SiO 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:
Hydrolysis method is adopted to prepare SiO
2nanometer ball.Ammoniacal liquor is added, ultrasonic 15 minutes, magnetic agitation in ethanol and distilled water (1:1, v/v).Measure tetraethyl orthosilicate (TEOS) slowly to instill in above-mentioned solution, after dropwising, react 24 hours under room temperature condition.Measuring 3-methacryloxypropyl trimethoxy silane (MPS) is slowly added drop-wise in the oyster white dispersion liquid of generation, continues stirring 24 hours.After reaction terminates, supercentrifuge is utilized 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 ultrasonic disperse, in acetonitrile, then adds 2 ~ 4mmol acrylamide (AM), 0.036 ~ 0.072g allyl group fluorescein and 0.1 ~ 1.0mL cross-linker divinylbenzene (DVB) respectively; The initiator Diisopropyl azodicarboxylate (AIBN) of 2.5% of the total amount of substance of monomer is added after mixing.Pass into nitrogen 15 minutes excluding airs, seal under nitrogen atmosphere.Adopt thermal-initiated polymerization mode, be placed in 60 DEG C of thermostatical oil baths and heat 24 hours, after being polymerized, obtain yellow thick product.Colourless to washing lotion with alcohol immersion washing, use spectrofluorometer to detect washing lotion and retain without luminophore.
Wherein add 2.0mL ammoniacal liquor in every 50mL ethanol and distilled water (1:1, v/v) in step (1), measure the tetraethyl orthosilicate (TEOS) of 2.0mL, finally add 1mL3-methacryloxypropyl trimethoxy silane (MPS).
Wherein ultrasonic disperse 250mgSiO in every 60mL acetonitrile in step (2)
2mPS nanometer ball, every 60mL acetonitrile adds 2 ~ 4mmolAM, 0.036 ~ 0.072g allyl group fluorescein and 0.1 ~ 1.0mL linking agent DVB respectively.
technological merit of the present inventionbe to use the fluorescein of modified by vinyl as fluorescence dye and monomer, copolymerzation with cross-linking, allyl group fluorescein is dispersed in microballoon shell, make microballoon evenly luminous; Precipitation polymerization method is utilized to prepare the narrow fluorescent microsphere of particle size distribution range.
Accompanying drawing explanation
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 μm, and shell thickness is about 5nm, uniform particle diameter, 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 comparatively homogeneous, and diameter is about 270nm.
fig. 3siO
2mPSPoly (AM-co-DVB) fluorescence spectrum.As we know from the figure, the fluorescence emission peak of microballoon is 521nm.
Embodiment
Below in conjunction with concrete embodiment, the present invention will be further described, but the invention is not restricted to these embodiments.
embodiment 1
Ultrasonic disperse 250mgSiO in every 60mL acetonitrile
2mPS nanometer ball, every 60mL acetonitrile adds AM, 0.036g allyl group fluorescein and the 0.1mLDVB of 2mmol respectively; The initiator Diisopropyl azodicarboxylate (AIBN) of 2.5% of the total amount of substance of monomer is added after mixing.Pass into nitrogen 15 minutes excluding airs, seal under nitrogen atmosphere.Adopt thermal-initiated polymerization mode, be placed in 60 DEG C of thermostatical oil baths and heat 24h, after being polymerized, obtain yellow thick product.Colourless to washing lotion with alcohol immersion washing, use spectrofluorometer to detect washing lotion and retain without luminophore.
embodiment 2
Ultrasonic disperse 250mgSiO2MPS nanometer ball in every 60mL acetonitrile, every 60mL acetonitrile adds 4mmolAM, 0.072g allyl group fluorescein and 1.0mLDVB respectively; The initiator Diisopropyl azodicarboxylate (AIBN) of 2.5% of the total amount of substance of monomer is added after mixing.Pass into nitrogen 15 minutes excluding airs, seal under nitrogen atmosphere.Adopt thermal-initiated polymerization mode, be placed in 60 DEG C of thermostatical oil baths and heat 24h, after being polymerized, obtain yellow thick product.Colourless to washing lotion with alcohol immersion washing, use spectrofluorometer to detect washing lotion and retain without luminophore..
embodiment 3
Ultrasonic disperse 250mgSiO2MPS nanometer ball in every 60mL acetonitrile, every 60mL acetonitrile adds 3mmolAM, 0.054g allyl group fluorescein and 0.5mLDVB respectively; The initiator Diisopropyl azodicarboxylate (AIBN) of 2.5% of the total amount of substance of monomer is added after mixing.Pass into nitrogen 15 minutes excluding airs, seal under nitrogen atmosphere.Adopt thermal-initiated polymerization mode, be placed in 60 DEG C of thermostatical oil baths and heat 24h, after being polymerized, obtain yellow thick product.Colourless to washing lotion with alcohol immersion washing, use spectrofluorometer to detect washing lotion and retain without luminophore.TEM, SEM and fluorescence emission spectrum are shown in Fig. 1, Fig. 2 and Fig. 3 respectively.
Claims (1)
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:
Hydrolysis method is adopted to prepare SiO
2nanometer ball: ethanol and distilled water by volume 1:1 add ammoniacal liquor, ultrasonic 15 minutes, magnetic agitation;
Measuring tetraethyl orthosilicate TEOS slowly instills in above-mentioned solution, after dropwising, react 24 hours under room temperature condition, measuring 3-methacryloxypropyl trimethoxy silane MPS is slowly added drop-wise in the oyster white dispersion liquid of generation, continue stirring 24 hours, after reaction terminates, supercentrifuge is utilized 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 ultrasonic disperse is in acetonitrile, then acrylamide AM, 0.036 ~ 0.072g allyl group fluorescein and 0.1 ~ 1.0mL cross-linker divinylbenzene DVB is added respectively, the initiator Diisopropyl azodicarboxylate AIBN of 2.5% of the total amount of substance of monomer is added after mixing, pass into nitrogen 15 minutes excluding airs, seal under nitrogen atmosphere, adopt thermal-initiated polymerization mode, be placed in 60 DEG C of thermostatical oil baths and heat 24 hours, after being polymerized, obtain yellow thick product; Colourless to washing lotion with alcohol immersion washing, use spectrofluorometer to detect washing lotion and retain without luminophore;
Wherein add 2.0mL ammoniacal liquor in every 50mL ethanol and distilled water in step (1), measure the tetraethyl orthosilicate TEOS of 2.0mL, finally add 1mL3-methacryloxypropyl trimethoxy silane MPS;
Wherein ultrasonic disperse 250mgSiO in every 60mL acetonitrile in step (2)
2mPS nanometer ball, every 60mL acetonitrile adds 2 ~ 4mmolAM, 0.036 ~ 0.072g allyl group fluorescein and 0.1 ~ 1.0mL linking agent DVB respectively.
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| 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 |
| CN108192596B (en) * | 2018-02-09 | 2020-07-24 | 中北大学 | Coated carboxylated SiO2Preparation method of fluorescent nanosphere |
| 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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Non-Patent Citations (2)
| Title |
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| Facile Synthesis of Hollow Polymer Microspheres with Movable Cores with the Aid of Hydrogen-Bonding Interaction;Guoliang Li et al.;《J. Phys. Chem. B》;20071018;第111卷(第44期);12781-12786 * |
| 空心聚合物微球的合成;刘霖 等;《天津工业大学学报》;20130815;第32卷(第4期);49-51 * |
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