CN101550336B - Preparation method of green light emitted silicon dioxide nano-particle - Google Patents
Preparation method of green light emitted silicon dioxide nano-particle Download PDFInfo
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- CN101550336B CN101550336B CN2009100849101A CN200910084910A CN101550336B CN 101550336 B CN101550336 B CN 101550336B CN 2009100849101 A CN2009100849101 A CN 2009100849101A CN 200910084910 A CN200910084910 A CN 200910084910A CN 101550336 B CN101550336 B CN 101550336B
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Abstract
Preparation method of green light emitted silicon dioxide nano-particle belongs to materials technology field. The prior dye adulterated with nano silicon dioxide used as bioassay markers (and vectors) have poor distinguish effects. The invention provided green light emitted silicon dioxide nano-particle is prepared through dye preparation, synthesis of nano-particles by microemulsion, surface modification and reprocess. The invention prepared silicon dioxide nano-particle has high productivity of fluorescence quantum, and has advantages of easy recognition when used as bioassay markers (and vectors), good monodispersity and controllable particle diameter.
Description
Technical field
The invention belongs to the material technology field, be specifically related to a kind of monodispersive silica nanometer particle process method of green emission.
Background technology
Nano particles of silicon dioxide because of its good bio-compatibility be easy to characteristics such as preparation, have vast potential for future development in biological detection affinity tag (reaching carrier) field.Carried out multinomial research work both at home and abroad about dye adulterated nano silicon.But often more than 640nm, naked-eye observation is yellow or red partially for the emission wavelength of at present prepared dye adulterated nano silicon, and is poor as biological detection affinity tag (and carrier) resolving effect.
Up to now, also not relevant for the research report of the Nano particles of silicon dioxide of green emission.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of Nano particles of silicon dioxide of green emission.
The preparation method of the Nano particles of silicon dioxide of green emission provided by the present invention may further comprise the steps:
1) preparation aqueous dye solutions: Ran Liao perylene tetracid dianhydride is joined in the aqueous sodium hydroxide solution, and the mol ratio of dyestuff and sodium hydroxide 1: 4 behind the stirring 20min-2h, is removed solid, obtains aqueous dye solutions;
2) body fluid before the preparation microemulsion: hexanaphthene, normal hexane and tensio-active agent Triton 100 (TX-100) are mixed; Wherein, The volume ratio of hexanaphthene and normal hexane is 3.6～5.3: 1, and the volume ratio of hexanaphthene and Triton 100 is 3.2～5.2: 1, obtains the preceding body fluid of microemulsion;
3) after mixing in the body fluid before the microemulsion of preparation preparation nano particle micro emulsion: the aqueous dye solutions that obtains in the step 1) is added drop-wise to step 2); Adding tetraethyl orthosilicate mixes; Then add ammoniacal liquor, stirring reaction 8～24 hours obtains nano particle micro emulsion; Wherein, The magnitude relation that uses of each material is: the consumption of aqueous dye solutions as the microemulsion precursor liquids long-pending 3.5～6.0%; The consumption of tetraethyl orthosilicate for the microemulsion precursor liquids long-pending 0.5～1.67%, the volume ratio of tetraethyl orthosilicate and ammoniacal liquor is 1.0～2.0: 1;
4) finishing: add tetraethyl orthosilicate and substituted silane in the nano particle micro emulsion that in step 3), obtains; The consumption of tetraethyl orthosilicate and substituted silane (tetraethyl orthosilicate and substituted silane can arbitrary proportion mix) sum for the microemulsion precursor liquids long-pending 0.5～1.67%; Stirring reaction 8～24 hours obtains the nano particle micro emulsion of finishing;
5) purifies and separates: after adding the acetone breakdown of emulsion in the nano particle micro emulsion of the finishing that in step 4), prepares, solid-liquid separation, the washing gained precipitates, and obtains the Nano particles of silicon dioxide of green emission.
Wherein, the substituted silane described in the step 4) is selected from a kind of in aminopropyl trimethoxysilane or the propyloic silanetriol trisodium salt.
The present invention has following beneficial effect:
1) perylene tetracid dianhydride of selecting for use is an optical dye among the present invention, and prepared Nano particles of silicon dioxide fluorescence quantum yield is high, and the fluorescent emission wavelength is near 500 nanometers, and is shown in green luminous, is easy to identification as biological detection affinity tag (and carrier).
2) the prepared Nano particles of silicon dioxide monodispersity of the present invention is good, and particle diameter is controlled, and the surface has free amino group or carboxyl modified, is easy to further modify or combine with affinity tag.
Description of drawings
Sem (SEM) image of the Nano particles of silicon dioxide of the green emission of Fig. 1, embodiment 1 preparation.
Transmission electron microscope (TEM) image of the Nano particles of silicon dioxide of the green emission of Fig. 2, embodiment 1 preparation.
The fluorescence spectrum of the Nano particles of silicon dioxide of the green emission of Fig. 3, embodiment 1 preparation.
Sem (SEM) image of the Nano particles of silicon dioxide of the green emission of Fig. 4, embodiment 2 preparations.
Sem (SEM) image of the Nano particles of silicon dioxide of the green emission of Fig. 5, embodiment 3 preparations.
Below in conjunction with accompanying drawing and practical implementation method the present invention is described further, but protection scope of the present invention is not limited to following examples.
Embodiment
Embodiment 1
1) preparation aqueous dye solutions: 0.1 Ke perylene tetracid dianhydride solid is joined in the sodium hydroxide solution of 5 milliliters of 0.2M, and stirring reaction is 1 hour under the room temperature, obtains deep green De perylene tetracid (four) sodium salt solution, filters, and keeps clear liquid;
2) body fluid before the preparation microemulsion: after 20 milliliters in 91 milliliters of hexanaphthenes, 23 milliliters of normal hexanes and TX-100 tensio-active agent mixed in triangular flask, it was subsequent use to keep in Dark Place;
3) preparation nano particle micro emulsion: get before 11.8 milliliters of microemulsions body fluid in test tube, and use syringe to drip 480 microlitre aqueous dye solutions, in the ultrasonic pond ultrasonic 10 minutes; Place again and stir after 20 minutes on the magnetic stirring apparatus; Add 100 microlitre tetraethyl orthosilicates, magnetic agitation 20 minutes adds 60 microlitre ammoniacal liquor; Continue magnetic agitation 24 hours, and obtained nano particle micro emulsion;
4) finishing: in the nano particle micro emulsion that in step 3), obtains, add 50 microlitre tetraethyl orthosilicates and 10 microlitre aminopropyl trimethoxysilane, continue magnetic agitation reaction 24 hours, obtain the nano particle micro emulsion that amino surface is modified;
5) purifies and separates: in step 4), obtain adding 1 milliliter of acetone breakdown of emulsion in the nano particle micro emulsion that amino surface modifies; To all precipitate and change in the centrifuge tube; Under 3000 rev/mins rotating speed centrifugal 3 minutes, remove supernatant after, with the gained deposition with 95% ethanol supersound washing 3 times; With the absolute ethyl alcohol flushing once, obtain the Nano particles of silicon dioxide of green emission again.
Adopt ESEM and projection Electronic Speculum to characterize, as depicted in figs. 1 and 2, the particle diameter of gained Nano particles of silicon dioxide is 70nm, is monodisperse nanoparticle.The employing fluorescence spectrum characterizes, and as shown in Figure 3, the gained Nano particles of silicon dioxide has emission peak at 485nm and 516nm place.
Embodiment 2
1) preparation aqueous dye solutions: with the step 1) among the embodiment 1;
2) body fluid before the preparation microemulsion: after 18 milliliters in 90 milliliters of hexanaphthenes, 21.3 milliliters of normal hexanes and TX-100 tensio-active agent mixed in triangular flask, it was subsequent use to keep in Dark Place;
3) preparation nano particle micro emulsion: with the step 3) among the embodiment 1;
4) finishing: in the nano particle micro emulsion that in step 3), obtains, add 40 microlitre tetraethyl orthosilicates and 60 microlitre propyloic silanetriol trisodium salts, continue magnetic agitation reaction 12 hours, obtain the nano particle micro emulsion of carboxyl finishing;
5) purifies and separates:, obtain the Nano particles of silicon dioxide of green emission with the step 5) among the embodiment 1.
Adopt ESEM to characterize, as shown in Figure 4, the particle diameter of gained Nano particles of silicon dioxide is 65nm, is monodisperse nanoparticle.
Embodiment 3
1) preparation aqueous dye solutions: with the step 1) among the embodiment 1;
2) body fluid before the preparation microemulsion: after 18 milliliters in 90 milliliters of hexanaphthenes, 21.3 milliliters of normal hexanes and TX-100 tensio-active agent mixed in triangular flask, it was subsequent use to keep in Dark Place;
3) preparation nano particle micro emulsion: with the step 3) among the embodiment 1;
4) finishing: in the nano particle micro emulsion that in step 3), obtains, add 40 microlitre tetraethyl orthosilicates and 60 microlitre propyloic silanetriol trisodium salts, continue magnetic agitation reaction 24 hours, obtain the nano particle micro emulsion of carboxyl finishing;
5) purifies and separates:, obtain the Nano particles of silicon dioxide of green emission with the step 5) among the embodiment 1.
Adopt ESEM to characterize, as shown in Figure 5, the particle diameter of gained Nano particles of silicon dioxide is 70nm, is monodisperse nanoparticle.
The Nano particles of silicon dioxide of the green emission that the present invention is prepared is as the application of biomarker:
1) with the Nano particles of silicon dioxide of green emission and sheep anti-mouse igg 4 degrees centigrade stir down hatch 4 hours after; In the phosphate buffered saline buffer of pH=6.8, dialyse, changed phosphate buffered saline buffer in per 1.5 hours, changes three times after taking-up; Concentrate in the Macrogol 2000 0, obtain marking fluid;
2) marking fluid being diluted at the 520nm place absorbancy with the PBST of pH=7.2 (add in the phosphate buffered saline buffer 1% Triton 100) is 0.2 to be advisable, and obtains diluting marking fluid;
3) coat 96 hole enzyme plates respectively with mouse IgG and bovine serum albumin: get each 1 milligram of mouse I gG and bovine serum albumin; Respectively after the 50 milliliters of dissolvings of phosphate buffered saline buffer with pH=6.8; Add respectively in the 96 hole enzyme plates; Every hole adds 200 microlitres, hatch 2 hours under 37 degrees centigrade after, clean with phosphate buffered saline buffer and to remove not attachment protein twice;
4) with step 2) in marking fluid after the dilution add in the step 3) enzyme plate that coats with mouse I gG respectively and the enzyme plate that coats with bovine serum albumin in, hatch 30 minutes under 37 degrees centigrade after, clean once with phosphate buffered saline buffer.Coat enzyme plate with mouse IgG and have green emitting in the sun, coating enzyme plate with bovine serum albumin does not then have, and show that mouse IgG is positive, and bovine serum albumin is negative.
Claims (1)
1. the preparation method of the Nano particles of silicon dioxide of a green emission is characterized in that, may further comprise the steps:
1) preparation aqueous dye solutions: Ran Liao perylene tetracid dianhydride is joined in the aqueous sodium hydroxide solution, and the mol ratio of dyestuff and sodium hydroxide 1: 4 behind the stirring 20min-2h, is removed solid, obtains aqueous dye solutions;
2) body fluid before the preparation microemulsion: hexanaphthene, normal hexane and tensio-active agent Triton 100 are mixed; Wherein, The volume ratio of hexanaphthene and normal hexane is 3.6～5.3: 1, and the volume ratio of hexanaphthene and Triton 100 is 3.2～5.2: 1, obtains the preceding body fluid of microemulsion;
3) after mixing in the body fluid before the microemulsion of preparation preparation nano particle micro emulsion: the aqueous dye solutions that obtains in the step 1) is added drop-wise to step 2); Adding tetraethyl orthosilicate mixes; Then add ammoniacal liquor, stirring reaction 8～24 hours obtains nano particle micro emulsion; Wherein, The magnitude relation that uses of each material is: the consumption of aqueous dye solutions as the microemulsion precursor liquids long-pending 3.5～6.0%; The consumption of tetraethyl orthosilicate for the microemulsion precursor liquids long-pending 0.5～1.67%, the volume ratio of tetraethyl orthosilicate and ammoniacal liquor is 1.0～2.0: 1;
4) finishing: add tetraethyl orthosilicate and substituted silane in the nano particle micro emulsion that in step 3), obtains; The consumption sum of tetraethyl orthosilicate and substituted silane for the microemulsion precursor liquids long-pending 0.5～1.67%; Stirring reaction 8～24 hours obtains the nano particle micro emulsion of finishing;
5) purifies and separates: after adding the acetone breakdown of emulsion in the nano particle micro emulsion of the finishing that in step 4), prepares, solid-liquid separation, the washing gained precipitates, and obtains the Nano particles of silicon dioxide of green emission;
Substituted silane described in the step 4) is selected from a kind of in aminopropyl trimethoxysilane or the propyloic silanetriol trisodium salt.
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| CN101805603A (en) * | 2010-03-17 | 2010-08-18 | 上海大学 | FITC-doped silica fluorescent nanoparticle and preparation method thereof |
| CN103194210A (en) * | 2013-04-15 | 2013-07-10 | 北京工业大学 | Preparation method for SiO2-based organic-inorganic hybridized fluorescent material |
| CN105419784B (en) * | 2015-12-11 | 2017-06-23 | 吉林大学 | The preparation method of alcohol sensible 9,10 (diphenyl) acetenyl anthracene doped Nano particles of silicon dioxide |
| CN114989629B (en) * | 2022-05-18 | 2023-06-27 | 苏州大学 | Silicon dioxide nano particle with photo-thermal conversion function and preparation method and application thereof |
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| CN1978553A (en) * | 2005-12-02 | 2007-06-13 | 中国科学院化学研究所 | Surface grafting organic functional molecular nano silicon dioxide, and its preparing method |
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