CN108192596A - A kind of cladded type carboxylated SiO2The preparation method of fluorescent nanosphere - Google Patents

A kind of cladded type carboxylated SiO2The preparation method of fluorescent nanosphere Download PDF

Info

Publication number
CN108192596A
CN108192596A CN201810135759.9A CN201810135759A CN108192596A CN 108192596 A CN108192596 A CN 108192596A CN 201810135759 A CN201810135759 A CN 201810135759A CN 108192596 A CN108192596 A CN 108192596A
Authority
CN
China
Prior art keywords
nanosphere
fluorescent
sio
allyl
carboxylated
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201810135759.9A
Other languages
Chinese (zh)
Other versions
CN108192596B (en
Inventor
刘清浩
郭金春
李瑞芳
刘红彦
胡志勇
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
North University of China
Original Assignee
North University of China
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by North University of China filed Critical North University of China
Priority to CN201810135759.9A priority Critical patent/CN108192596B/en
Publication of CN108192596A publication Critical patent/CN108192596A/en
Application granted granted Critical
Publication of CN108192596B publication Critical patent/CN108192596B/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B57/00—Other synthetic dyes of known constitution
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B57/00—Other synthetic dyes of known constitution
    • C09B57/02—Coumarine dyes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/59—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing silicon
    • C09K11/592—Chalcogenides

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Nanotechnology (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Physics & Mathematics (AREA)
  • Composite Materials (AREA)
  • Inorganic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Luminescent Compositions (AREA)
  • Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)

Abstract

The invention discloses a kind of cladded type carboxylated SiO2The preparation method of fluorescent nanosphere is using the allyl base fluorescent probe with double bond, methacrylic acid and silane coupling agent KH151 as raw material, and polymerisation obtains fluorescent polymer, by chemical bond, is grafted on SiO2The surface of nanosphere, cladded type carboxylated SiO is prepared2Fluorescent nanosphere.Cladded type carboxylated SiO prepared by the present invention2Fluorescent nanosphere morphosis is stable, monodispersity is good, luminous efficiency is high, good biocompatibility, not only has the function of carboxylated base, also with firm Si O Si keys, avoids the leakage of product fluorescence, is quenched.

Description

A kind of cladded type carboxylated SiO2The preparation method of fluorescent nanosphere
Technical field
The present invention relates to the preparation method of fluorescent nanosphere, more particularly to a kind of carboxylated SiO of cladded type2Fluorescence is received The preparation method of rice ball.
Background technology
Silicon dioxide microsphere prepares simple, property stabilization, surface is easily modified, good biocompatibility, and in physiological conditions It is non-degradable, it is widely used in ambits such as chemistry, engineering and biomedicines.The particularly silica of functionalization Fluorescent microsphere not only has superior optical property or outstanding biomaterial, it is passed through surface functional group and biology It after macromolecular specific binding, can realize that highly sensitive, highly selective targeting combines, applied to Molecular Tracing, be immunized and divide The biological fields such as analysis, optical instrument correction, drug release.
CN 1782020A disclose the preparation method of the silica fluorescent microballoon containing cadmium telluride fluorescence quantum, Using as the cadmium telluride physically trapping of fluorescence probe, in silicon dioxide microsphere, not only toxicity is big, also easily leaks, is quenched.CN 105037662A discloses the preparation method of europium bonding type nano silicon dioxide fluorescent microsphere, document (Colloids and Surfaces B:Biointerfaces, 2017,157,286-296) it also reports in amination silica nanosphere Surface introduces coumarin fluorescent compound by sulphonyl amine key, however, both fluorescent microsphere surfaces all lack functional group, The research of inconvenient subsequent biological etc..Tang Qianqian etc. (chemical journal, 2010,68,18,1925-1929) reports Mesoporous silicon oxide fluorescent microsphere is then to introduce fluorescein through disulfide bond, but disulfide bond is easily broken in glutathione solution, It is revealed so as to cause fluorescence.
In addition, the silica nanosphere of document report is mostly prepared using reverse microemulsion process, preparation process consumption When it is longer.
Invention content
The object of the present invention is to provide the cladded type carboxyls that a kind of morphosis is stable, monodispersity is good, luminous efficiency is high Change SiO2The preparation method of fluorescent nanosphere.
Cladded type carboxylated SiO of the present invention2The preparation method of fluorescent nanosphere is glimmering with the pi-allyl with double bond Light probe, methacrylic acid and silane coupling agent KH151 are raw material, and polymerisation obtains fluorescent polymer, then passes through chemical bond Effect, be grafted on SiO2The surface of nanosphere, cladded type carboxylated SiO is prepared2Fluorescent nanosphere.
Further, the present invention prepares the cladded type carboxylated SiO particular by following each steps2Fluorescence nano Ball.
1), water intaking, absolute ethyl alcohol and ammonium hydroxide are mixed evenly, and are added in ethyl orthosilicate, are stirred reaction at room temperature, are reacted Product obtains SiO with water and absolute ethyl alcohol washing, drying2Nanosphere.
2), allyl base fluorescent probe, silane coupling agent KH151, methacrylic acid and azodiisobutyronitrile are added in anhydrous In methanol, inertia protection is lower to carry out heating reflux reaction, be evaporated off obtaining after solvent methanol the allyl base fluorescent probe of carboxylated- KH151 polymer.
3) SiO, is added in dry toluene2Allyl base fluorescent probe-KH151 the polymer of nanosphere and carboxylated, it is lazy Property protection is lower carries out heating reflux reaction, cladded type carboxylated SiO is prepared2Fluorescent nanosphere.
In the above-mentioned preparation method of the present invention, the allyl base fluorescent probe is pi-allyl -4- methylcoumarins, pi-allyl Any one in fluorescein, pi-allyl rhodamine B, allyl carbazole.
SiO in step 1) of the present invention2In the preparation of nanosphere, the water, absolute ethyl alcohol, ammonium hydroxide and ethyl orthosilicate Volume ratio be 6~7: 15~16.5: 1.6~1.8: 1.
Still further, it is after the raw material is mixed, 0.5~3h of reaction is stirred at room temperature.
In step 2) of the present invention in the preparation of the allyl base fluorescent probe-KH151 polymer of carboxylated, the silane Coupling agent KH151, azodiisobutyronitrile, allyl base fluorescent probe, methacrylic acid mass ratio for 1: 0.4~0.7: 0.8~ 1.8: 1~2.
Still further, it is by the raw material at 65~70 DEG C 6~8h of back flow reaction.
In step 3) of the present invention, preferably by the allyl base fluorescent probe-KH151 polymer of excessive carboxylated with SiO2Nanosphere back flow reaction 20~for 24 hours at 105~115 DEG C.
Further, it is of the invention by SiO2Nanosphere and the allyl base fluorescent probe-KH151 polymer reflows of carboxylated are anti- Successively water and ethyl alcohol wash the reaction product answered repeatedly, until cleaning solution no longer detects fluorescence, are obtained after dry final Cladded type carboxylated SiO2Fluorescent nanosphere product.
The method that the present invention uses free radical polymerization first, allyl base fluorescent probe, methacrylic acid are polymerize with KH151 Obtain the allyl base fluorescent probe-KH151 polymer of carboxylated, then by high temperature dehydration condensation method, by the fluorescent polymer warp- Si-O-Si- keys chemical bond and in SiO2Nanometer ball surface, obtains cladded type carboxylated SiO2Fluorescent nanosphere.The fluorescent nanosphere Not only there is carboxylated base, also there is firm-Si-O-Si- keys, avoid the fluorescence leakage of product, be quenched.
Compared with prior art, preparation method of the present invention has the following advantages：1st, by pi-allyl fluorescent dye, metering system Acid and vinyltriethoxysilane (KH151) obtain fluorescent polymer, and pass through chemical bond by the fluorescence through free radical polymerization Polymer bonds and in SiO2Nanometer ball surface, makes fluorescent microsphere not only have carboxy functional group, it is ensured that higher microballoon Whole lighting efficiency, fluorescent dye are stabilized, it is not easy to be leaked, be quenched.2nd, the carrier of fluorescent nanosphere is inorganic material SiO2, with the incomparable characteristic of many high molecular materials, such as physical toughness, chemical stability, can be neglected in a solvent Swellability, nontoxicity, colloidal stability, high-biocompatibility, the easy functionalization of excellent optical clarity and surface etc., especially It is the SiO of surface carboxyl groups2Fluorescent nanosphere, pendant carboxylic group can be with a variety of inorganic ions or inorganic, organic, biomolecule It reacts, is with a wide range of applications in fields such as biochemistry, chemical analyses.3rd, the pi-allyl fluorescence that the present invention uses In dyestuff, allyl carbazole is near ultraviolet or navy blue fluorescence material, and pi-allyl fluorescein and allyl butylcoumariii are greenings The fluorescent material of light, pi-allyl rhodamine B is near-infrared or the fluorescent material that glows, and thus, it is possible to prepare to have indigo plant The cladded type carboxylated SiO of color, green and red fluorescence2Fluorescent nanosphere.4th, the present invention is prepared using sol-gel method SiO2Nanosphere, the operating time is short, and pyrocondensation method is used to introduce fluorescent polymer, easy to operate, and it is micro- to prepare fluorescence Ball it is of low cost.
Description of the drawings
Fig. 1 is SiO2Scanning electron microscope (SEM) figure of nanosphere.
Fig. 2 is SiO2Transmission electron microscope (TEM) figure of nanosphere.
Fig. 3 is carboxylated SiO2Fluorescent nanosphere (a) and SiO2The infrared spectrogram of nanosphere (b).
Fig. 4 is the ultraviolet spectrogram (illustration) of 1 pi-allyl 4- methylcoumarins of embodiment and fluorescence spectra and its SiO2 The fluorescence spectra (ethanol as solvent) of fluorescent nanosphere.
Fig. 5 is the ultraviolet spectrogram (illustration) of 2 pi-allyl fluorescein of embodiment and fluorescence spectra and its SiO2Fluorescence is received The fluorescence spectra (water as solvent) of rice ball.
Fig. 6 is the ultraviolet spectrogram (illustration) of 3 pi-allyl fluorescein of embodiment and fluorescence spectra and its SiO2Fluorescence is received The fluorescence spectra (water as solvent) of rice ball.
Fig. 7 is the ultraviolet spectrogram (illustration) of 4 allyl carbazole of embodiment and fluorescence spectra and its SiO2Fluorescence nano The fluorescence spectra (ethanol as solvent) of ball.
Fig. 8 is the shows fluorescent microscopy images of Examples 1 to 4.
Specific embodiment
Following embodiments are only the preferred technical solution of the present invention, are not used to carry out any restrictions to the present invention.For For those skilled in the art, the invention may be variously modified and varied.All within the spirits and principles of the present invention, made Any modification, equivalent substitution, improvement and etc., should all be included in the protection scope of the present invention.
Embodiment 1.
Distilled water 28mL, absolute ethyl alcohol 65mL, ammonium hydroxide 7mL are added in 100mL there-necked flasks, is mixed evenly, adds just Silester (TEOS) 4mL, at room temperature magnetic agitation reaction 1.5h.Product centrifuges, with water and absolute ethyl alcohol alternate repetition It washs, is dried in vacuo at 50 DEG C, obtains SiO2Nanosphere.
Fig. 1 and Fig. 2 is prepared SiO2SEM and the TEM figure of nanosphere, it is known that SiO2Nanosphere has good sphericity And monodispersity is good, lays a good foundation to prepare cladded type carboxylic fluorescent nanosphere.
Resorcinol 3.3g (30mmol) is weighed, concentrated sulfuric acid 60mL is slowly added under room temperature and is completely dissolved to resorcinol, It is placed in ice-water bath, ethyl acetoacetate 3.9mL (1.95mmol) is slowly added dropwise, after being added dropwise, the reaction was continued 1h.Then it rises It warms to room temperature, the reaction was continued for 24 hours, reaction solution is poured into the ice water of about 300mL and is vigorously stirred, pale precipitation occurs, takes out Filter, absolute ethyl alcohol recrystallize, acquisition pale solid, dry in 50 DEG C of vacuum drying chambers, obtain 4- methyl -7- hydroxyl tonka-beans Element.
Weigh 4-methyl-7-hydroxycoumarin 200mg (0.4mmol), tetrabutylammonium bromide (TBAB) 0.28g (0.8mmol) is dissolved with chloroform 30mL, adds in natrium carbonicum calcinatum 0.2g, a small amount of potassium iodide and deionized water 30mL, room temperature Lower stirring 15min, is slowly added dropwise 3- bromopropenes 0.11mL, and stir about 4h at 30~40 DEG C separates organic phase, water with separatory funnel Phase chloroform extraction merges organic phase, is dried over anhydrous sodium sulfate, greenish yellow solid is obtained after revolving, column chromatography obtains 4- methyl -7-O- allyl butylcoumariiis.
Weigh 4- methyl -7-O- allyl butylcoumariiis 0.030g, vinyltriethoxysilane (KH151) 0.0337g, first Base acrylic acid (MAA) 0.0337g, azodiisobutyronitrile (AIBN) 0.0138g and absolute methanol 10mL add in 100mL there-necked flasks In, stirred under nitrogen atmosphere is heated to 70 DEG C of back flow reaction 7h.Reaction product solvent evaporated methanol under vacuum, obtains carboxylic 4- methyl -7-O- allyl butylcoumariii-KH151 the polymer of base, is filled with nitrogen preservation.
Weigh SiO2Nanosphere 0.1g, with dry toluene 10mL by the 4- methyl -7-O- allyls butylcoumariii of carboxylated - KH151 polymer is transferred in there-necked flask, and the lower back flow reaction of nitrogen protection is for 24 hours.After reaction, it is product is anti-with second alcohol and water After backwashing is washed, and until supernatant does not have fluorescence, vacuum drying obtains cladded type carboxylated SiO2Fluorescent nanosphere.
Fig. 4 be 4- methyl -7-O- allyl butylcoumariiis ultraviolet spectrogram (illustration) and fluorescence spectra (a) and SiO2The fluorescence spectra (b) of fluorescent nanosphere.The fluorescence spectra is using ethyl alcohol as solvent, in excitation wavelength 321nm Under be measured.As seen from the figure, carboxylated SiO2The fluorescence emission spectrum of fluorescent nanosphere (b) is relative to 4- methyl -7-O- Red shift (13nm) has occurred in allyl butylcoumariii, it is possible thereby to show that 4- methyl -7-O- allyls butylcoumariiis successfully connect Branch is in SiO2The surface of nanosphere.
Embodiment 2.
Distilled water 21mL, absolute ethyl alcohol 48.75mL, ammonium hydroxide 5.25mL are added in 100mL there-necked flasks, is mixed evenly, then Ethyl orthosilicate (TEOS) 3mL is added in, at room temperature magnetic agitation reaction 2.5h.Product centrifuges, anti-with water and absolute ethyl alcohol After backwashing is washed, and is dried in vacuo at 50 DEG C, is obtained SiO2Nanosphere.
By document (J. Mater. Chem., 2009,19,2018-2025) method, by fluorescein 2.00g, 3- bromines third In alkene 2.42g and Anhydrous potassium carbonate 4.97g input reaction bulbs, solvent DMF 50mL is added in, catalyst iodine trace, polymerization inhibitor is to benzene Diphenol trace, under the conditions of anhydrous and oxygen-free, 71 DEG C of reaction 25h obtain pi-allyl fluorescein yellow crude, Gossypol recrystallized from chloroform, column color Compose to obtain pi-allyl fluorescein sterling.
Weigh pi-allyl fluorescein 0.0468g, KH151 0.0425g, MAA 0.0526g, AIBN 0.0186g and anhydrous Methanol 10mL is added in 100mL there-necked flasks, and stirred under nitrogen atmosphere is heated to 70 DEG C of back flow reaction 7h.Reaction product is in vacuum Under the conditions of solvent evaporated methanol, obtain the pi-allyl fluorescein-KH151 polymer of carboxylated, be filled with nitrogen preservation.
Weigh SiO2Nanosphere 0.1g is turned the pi-allyl fluorescein-KH151 polymer of carboxylated with dry toluene 10mL It moves in there-necked flask, the lower back flow reaction of nitrogen protection is for 24 hours.After reaction, product is washed repeatedly with second alcohol and water, until upper Until clear liquid does not have fluorescence, vacuum drying obtains cladded type carboxylated SiO2Fluorescent nanosphere.
Fig. 3 (a) is carboxylated pi-allyl fluorescein-KH151 grafting SiO2The infrared spectrum of fluorescent nanosphere, (b) are SiO2 The infrared spectrum of nanosphere.(a) it is compared with (b), in 1300~1750cm-1Between there is different peaks, and 1633cm-1For carboxylic Base characteristic peak, therefore carboxyl is successfully grafted on SiO2Nanometer ball surface.
Fig. 5 is the ultraviolet spectrogram (illustration) of pi-allyl fluorescein and fluorescence spectra (a) and SiO2Fluorescent nanosphere Fluorescence spectra (b).The fluorescence spectra is using water as solvent, is measured under excitation wavelength 454nm.From figure Find out, carboxylated SiO2Red shift (4nm) has occurred relative to pi-allyl fluorescein in the fluorescence emission spectrum of fluorescent nanosphere (b), It is possible thereby to show that pi-allyl fluorescein is successfully grafted on SiO2The surface of nanosphere.
Embodiment 3.
Distilled water 14mL, absolute ethyl alcohol 32.5mL, ammonium hydroxide 3.5mL are added in 100mL there-necked flasks, is mixed evenly, then is added Enter ethyl orthosilicate (TEOS) 2mL, at room temperature magnetic agitation reaction 3h.Product centrifuges, anti-with water and absolute ethyl alcohol alternating After backwashing is washed, and is dried in vacuo at 50 DEG C, is obtained SiO2Nanosphere.
By document (J. Mater. Chem., 2009,19,2018-2025) method, by rhodamine B 240g, carbonic acid In potassium 0.73g, 3- bromopropene 2.65g input reaction bulbs, solvent DMF 50mL is added in, catalyst iodine trace, polymerization inhibitor is to benzene two Phenol trace, under the conditions of anhydrous and oxygen-free, 71 DEG C of reaction 25h, synthesis of allyl rhodamine B crude product obtains pi-allyl sieve through column chromatography Red bright B sterlings.
Weigh pi-allyl rhodamine B 0.0555g, KH151 0.0486g, MAA 0.0676g, AIBN 0.023g and anhydrous Methanol 10mL is added in 100mL there-necked flasks, and stirred under nitrogen atmosphere is heated to 70 DEG C of back flow reaction 7h.Reaction product is in vacuum Under the conditions of solvent evaporated methanol, obtain the pi-allyl rhodamine-KH151 polymer of carboxylated, be filled with nitrogen preservation.
Weigh SiO2Nanosphere 0.1g is turned the pi-allyl rhodamine-KH151 polymer of carboxylated with dry toluene 10mL It moves in there-necked flask, the lower back flow reaction of nitrogen protection is for 24 hours.After reaction, product is washed repeatedly with second alcohol and water, until upper Until clear liquid does not have fluorescence, vacuum drying obtains cladded type carboxylated SiO2Fluorescent nanosphere.
Fig. 6 is the ultraviolet spectrogram (illustration) of pi-allyl rhodamine B and fluorescence spectra (a) and SiO2Fluorescence nano The fluorescence spectra (b) of ball.The fluorescence spectra is using water as solvent, is measured under excitation wavelength 558nm.From figure In find out, carboxylated SiO2Red shift has occurred relative to pi-allyl rhodamine B in the fluorescence emission spectrum of fluorescent nanosphere (b) (4nm), it is possible thereby to show that pi-allyl rhodamine B is successfully grafted on SiO2The surface of nanosphere.
Embodiment 4.
Distilled water 35mL, absolute ethyl alcohol 81.25mL, ammonium hydroxide 8.75mL are added in 100mL there-necked flasks, is mixed evenly, then Ethyl orthosilicate (TEOS) 5mL is added in, at room temperature magnetic agitation reaction 2h.Product centrifuges, and is replaced with water and absolute ethyl alcohol It washs repeatedly, is dried in vacuo at 50 DEG C, obtains SiO2Nanosphere.
Carbazole, potassium hydroxide and 3- bromopropenes are put into reaction bulb, solvent, catalyst and polymerization inhibitor are added in, anhydrous It is reacted under anaerobic and certain temperature, crude product is through column chromatography up to N- allyl carbazole sterlings.
Weigh N- allyl carbazoles 0.0528g, KH151 0.0561g, MAA 0.0612g, AIBN 0.0216g and anhydrous Methanol 10mL is added in 100mL there-necked flasks, and stirred under nitrogen atmosphere is heated to 70 DEG C of back flow reaction 7h.Reaction product is in vacuum Under the conditions of solvent evaporated methanol, obtain the allyl carbazole-KH151 polymer of carboxylated, be filled with nitrogen preservation.
Weigh SiO2Nanosphere 0.1g is shifted the allyl carbazole-KH151 polymer of carboxylated with dry toluene 10mL Into there-necked flask, the lower back flow reaction of nitrogen protection is for 24 hours.After reaction, product is washed repeatedly with second alcohol and water, until supernatant Until liquid does not have fluorescence, vacuum drying obtains cladded type carboxylated SiO2Fluorescent nanosphere.
Fig. 7 is the ultraviolet spectrogram (illustration) of allyl carbazole and fluorescence spectra (a) and SiO2Fluorescent nanosphere Fluorescence spectra (b).The fluorescence spectra is using ethyl alcohol as solvent, is measured under excitation wavelength 293nm.From figure Find out, carboxylated SiO2Red shift (2nm) has occurred relative to allyl carbazole in the fluorescence emission spectrum of fluorescent nanosphere (b), by This may indicate that allyl carbazole is successfully grafted on SiO2The surface of nanosphere.
Fig. 8 is the shows fluorescent microscopy images of Examples 1 to 4 successively.As seen from the figure, carboxylated SiO2Fluorescence nano ball There is strong luminescence feature, show that allyl base fluorescent probe is equably grafted on microsphere surface, stability is good.

Claims (8)

1. a kind of cladded type carboxylated SiO2The preparation method of fluorescent nanosphere, be first with the allyl base fluorescent probe with double bond, Methacrylic acid is raw material with silane coupling agent KH151, and polymerisation obtains fluorescent polymer, then by chemical bond, will It is grafted on SiO2The surface of nanosphere, cladded type carboxylated SiO is prepared2Fluorescent nanosphere.
2. cladded type carboxylated SiO according to claim 12The preparation method of fluorescent nanosphere, it is characterized in that using following It is prepared by method：
1), water intaking, absolute ethyl alcohol and ammonium hydroxide are mixed evenly, and are added in ethyl orthosilicate, are stirred reaction, reaction product at room temperature With water and absolute ethyl alcohol washing, drying, SiO is obtained2Nanosphere；
2) allyl base fluorescent probe, silane coupling agent KH151, methacrylic acid and azodiisobutyronitrile, are added in into absolute methanol In, inertia protection is lower to carry out heating reflux reaction, and the allyl base fluorescent probe-KH151 of carboxylated is obtained after solvent methanol is evaporated off Polymer；
3) SiO, is added in dry toluene2Allyl base fluorescent probe-KH151 the polymer of nanosphere and carboxylated, inertia protection Lower carry out heating reflux reaction, is prepared cladded type carboxylated SiO2Fluorescent nanosphere.
3. cladded type carboxylated SiO according to claim 1 or 22The preparation method of fluorescent nanosphere, it is characterized in that described Allyl base fluorescent probe be in pi-allyl -4- methylcoumarins, pi-allyl fluorescein, pi-allyl rhodamine B, allyl carbazole Any one.
4. cladded type carboxylated SiO according to claim 22The preparation method of fluorescent nanosphere, it is characterized in that the water, The volume ratio of absolute ethyl alcohol, ammonium hydroxide and ethyl orthosilicate is 6~7: 15~16.5: 1.6~1.8: 1.
5. cladded type carboxylated SiO according to claim 22The preparation method of fluorescent nanosphere, it is characterized in that the step 1) it is that 0.5~3h of reaction is stirred at room temperature in.
6. cladded type carboxylated SiO according to claim 22The preparation method of fluorescent nanosphere, it is characterized in that the silane Coupling agent KH151, azodiisobutyronitrile, allyl base fluorescent probe, methacrylic acid mass ratio for 1: 0.4~0.7: 0.8~ 1.8: 1~2.
7. cladded type carboxylated SiO according to claim 22The preparation method of fluorescent nanosphere, it is characterized in that the step 2) it is in 65~70 DEG C of 6~8h of back flow reaction in.
8. cladded type carboxylated SiO according to claim 22The preparation method of fluorescent nanosphere, it is characterized in that with excess Allyl base fluorescent probe-KH151 the polymer and SiO of carboxylated2Nanosphere back flow reaction 20~for 24 hours at 105~115 DEG C.
CN201810135759.9A 2018-02-09 2018-02-09 Coated carboxylated SiO2Preparation method of fluorescent nanosphere Expired - Fee Related CN108192596B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201810135759.9A CN108192596B (en) 2018-02-09 2018-02-09 Coated carboxylated SiO2Preparation method of fluorescent nanosphere

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201810135759.9A CN108192596B (en) 2018-02-09 2018-02-09 Coated carboxylated SiO2Preparation method of fluorescent nanosphere

Publications (2)

Publication Number Publication Date
CN108192596A true CN108192596A (en) 2018-06-22
CN108192596B CN108192596B (en) 2020-07-24

Family

ID=62592925

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201810135759.9A Expired - Fee Related CN108192596B (en) 2018-02-09 2018-02-09 Coated carboxylated SiO2Preparation method of fluorescent nanosphere

Country Status (1)

Country Link
CN (1) CN108192596B (en)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108930952A (en) * 2018-09-03 2018-12-04 天津永兴泰科技股份有限公司 A kind of high fluorescence cold light candle
CN109655442A (en) * 2019-03-14 2019-04-19 中国科学院烟台海岸带研究所 Three fluorescent emissive molecules trace sensors of one kind and its preparation and application
CN109799217A (en) * 2019-01-31 2019-05-24 中国科学院合肥物质科学研究院 A kind of highly sensitive ratio fluorescent probe and its preparation method and application based on cadmium telluride quantum dot Yu europium ion compound system
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 (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103992789A (en) * 2014-05-26 2014-08-20 江苏大学 Preparation method of inorganic-organic composite fluorescent microsphere
CN103694392B (en) * 2013-12-09 2016-08-17 中北大学 A kind of preparation method of carboxyl polystyrene copolymerization fluorescent microsphere
CN106929001A (en) * 2017-04-12 2017-07-07 中国农业科学院蔬菜花卉研究所 A kind of fluorescence SiO2The preparation method of Nano microsphere

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103694392B (en) * 2013-12-09 2016-08-17 中北大学 A kind of preparation method of carboxyl polystyrene copolymerization fluorescent microsphere
CN103992789A (en) * 2014-05-26 2014-08-20 江苏大学 Preparation method of inorganic-organic composite fluorescent microsphere
CN106929001A (en) * 2017-04-12 2017-07-07 中国农业科学院蔬菜花卉研究所 A kind of fluorescence SiO2The preparation method of Nano microsphere

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108930952A (en) * 2018-09-03 2018-12-04 天津永兴泰科技股份有限公司 A kind of high fluorescence cold light candle
CN109799217A (en) * 2019-01-31 2019-05-24 中国科学院合肥物质科学研究院 A kind of highly sensitive ratio fluorescent probe and its preparation method and application based on cadmium telluride quantum dot Yu europium ion compound system
CN109799217B (en) * 2019-01-31 2021-08-20 中国科学院合肥物质科学研究院 High-sensitivity ratio fluorescent probe based on cadmium telluride quantum dot and europium ion composite system and preparation method and application thereof
CN109655442A (en) * 2019-03-14 2019-04-19 中国科学院烟台海岸带研究所 Three fluorescent emissive molecules trace sensors of one kind and its preparation and application
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

Also Published As

Publication number Publication date
CN108192596B (en) 2020-07-24

Similar Documents

Publication Publication Date Title
CN108192596A (en) A kind of cladded type carboxylated SiO2The preparation method of fluorescent nanosphere
JP6661872B2 (en) Compound and color conversion film containing the same
Li et al. Highly luminescent hydrogels synthesized by covalent grafting of lanthanide complexes onto PNIPAM via one-pot free radical polymerization
CN103694992B (en) Hot activation delayed fluorescence material, its synthetic method and use the OLED of this hot activation delayed fluorescence material
CN108046236A (en) A kind of preparation method and application of high quantum production rate red carbon quantum dot
Xu et al. Visible light sensitized attapulgite-based lanthanide composites: microstructure, photophysical behaviour and biological application
CN109054039B (en) Synthesis and application of porous covalent organic framework material with imine structure
CN105669734B (en) A kind of pyrroles fluorescence molecule BCPA BODIPY of carbazyl triphenylamine fluorine boron two and its preparation method and application
Li et al. Aggregation-induced emission enhancement and cell imaging of a novel (carbazol-N-yl) triphenylamine–BODIPY
Zhang et al. Tunable white light emission of Eu, Tb, Zn-containing copolymers by RAFT polymerization
CN108558701B (en) Micromolecule AIEE luminescent material with triple stimulus responsiveness and preparation method thereof
CN108504348A (en) A kind of preparation and application of double fluorescent polymer quanta point materials
CN108358957B (en) Preparation method of rare earth-polymer nanospheres emitting white light
Yang et al. Lanthanide-centered luminescence evolution and potential anti-counterfeiting application of Tb 3+/Eu 3+ grafted melamine cyanurate hydrogen-bonded triazine frameworks
Cao et al. A novel and highly stable dual-emission carbon dots-based phosphor
Huang et al. An acrylate AIE-active dye with a two-photon fluorescent switch for fluorescent nanoparticles by RAFT polymerization: synthesis, molecular structure and application in cell imaging
Qu et al. Emission enhancement and self-healing of a hybrid hydrogel employing Au nanoclusters as cross-linkers
Wang et al. Tunable white light emission of an anti-ultraviolet rare-earth polysiloxane phosphors based on near UV chips
CN101445588B (en) Red and green light emitting conjugated polymer and preparation method as well as application thereof
CN107674669A (en) A kind of macromolecule composite coding microballoon and preparation method thereof
You et al. Solid-state fluorescent composite phosphor based on cellulose grafted with carbon dots for temperature sensing
CN111303862A (en) Dual-emission fluorescent temperature-sensitive polymer composite film and preparation method and application thereof
CN113527708B (en) Bridged tetraphenyl vinyl based supramolecular polymer light capture system, preparation and application
CN114409587A (en) Method for producing AIE molecules, AIE molecules and use thereof
CN104829471B (en) A kind of anthracene derivative and its preparation method and application and obtained UV photocuring light-emittings material and preparation method thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20200724

Termination date: 20210209

CF01 Termination of patent right due to non-payment of annual fee