CN109266324A - Dendroid silica@carbon dots composite nanometer particle and preparation method thereof - Google Patents
Dendroid silica@carbon dots composite nanometer particle and preparation method thereof Download PDFInfo
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- CN109266324A CN109266324A CN201811207646.1A CN201811207646A CN109266324A CN 109266324 A CN109266324 A CN 109266324A CN 201811207646 A CN201811207646 A CN 201811207646A CN 109266324 A CN109266324 A CN 109266324A
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- 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
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/65—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing carbon
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- 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
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- G01N21/643—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes" non-biological material
Abstract
The invention discloses a kind of dendroid silica@carbon dots composite nanometer particles and preparation method thereof; the method successfully prepares dendroid silica@carbon dots composite nanometer particle, and CDs load capacity is high, while the preparation method is easy to operate; yield is big, is easily formed large-scale production.The preparation method is that, carbon dots are added into the aqueous dispersions of dendroid nano SiO 2 particle, it adjusts after pH is 7.5~14 and the silane coupling agent with amido functional group is added, gained reaction mixture reacts 3~24 hours at 25~40 DEG C, obtain the dendroid silica@carbon dots composite nanometer particle, in the reaction mixture, the concentration of the dendroid nano SiO 2 particle is 3.0 × 10‑4~5.5mol/L, the concentration of carbon dots are 1.0 × 10‑3~10mol/L, the concentration of the 3- TSL 8330 are 8.0 × 10‑7~2.0 × 10‑4mol/L。
Description
Technical field
The present invention relates to inorganic nano composite material technical field, in particular to a kind of dendroid silica@carbon dots are multiple
Close nano particle and preparation method thereof.
Background technique
Carbon dots (CDs) have stable optical property, water solubility, toxicity, biocompatibility, chemical inertness, are easy to functionalization
The advantages that, one it is found that cause the extensive concern of scientist immediately.CDs is a kind of minimum (in 10nm or less) near-spherical of size
Carbon particle, its advantageous property to be expected to be applied to numerous areas, for example, bio-imaging, medical diagnosis, catalysis with
And optoelectronic device etc..
But CDs encounters some technical difficulties in biomedical applications.Most distinct issues are light, the rulers of CDs
Very little all very small (usually less than 10nm), and constituted based on carbon, CDs and biological molecular mass difference are little, this is just CDs
Post-processing and biologic applications bring difficulty.Especially after CDs has been coupled the biomolecule such as gene, albumen, targeting unit,
It is difficult to separate from coupling system.At present have only using dialysis the methods of, but during sub-argument CDs and biological micromolecule loss
Larger (loss that 70% can be reached sometimes).Generally expensive in view of biological components such as genes, the post-processing approach of CDs is significantly
Ground increases cost.Ultracentrifugation is a kind of more efficiently CDs separation method.But 20,000 turns or more of speed is usually required,
Not only energy consumption is high in this way, but also is possible to destroy the coupling of quantum dot and biological micromolecule, and the biology for influencing biomolecule is living
Property.In addition, since that there are sizes is small (in 10nm or less) by CDs, exist applied to cell or organism be not easy to be detained, Yi Beidai
The problems such as thanking short discharge, biological half-life, high concentration aggregation fluorescent quenching.Therefore CDs is supported on the particle of larger size,
It makes it easier to post-process, is one of the effective ways solved the problems, such as.
Have the report of some synthetic silicas Yu CDs composite nanometer particle at present, but there is low output mostly, fluorescence
The disadvantages of intensity is weaker, the mass for being unfavorable for product generate.Chinese patent literature CN103484111A discloses a kind of mesoporous
Mesoporous silicon face is first modified with silane coupling agent, is then mixed in a solvent with carbon matrix precursor by the preparation method of luminescence from silicon material
It after conjunction, is carbonized by hydro-thermal reaction, generates carbon dots in mesoporous silicon surface in situ, mesoporous silicon fluorescent material is made.This Jie
Hole luminescence from silicon material has stable fluorescence property, carbon dots load is particularly due on silica, so that composite particles are just
In centrifuge separation, post-processing step is simplified.
In various nano structural materials, organic dendritic macromole have tree-shaped branch's three-dimensional manometer mesostructure with
Spherical geometry.Due to its unique branched structure and a large amount of functional group, organic dendritic macromole can be encapsulated or directly
The a large amount of functional units of conjugation are connect, and can be with the group of targeting modification and stable particle surface.Recently, the medicine based on dendroid
Object delivery system has proven to be the nano-carrier of very promising biomedical applications.It is opened by organic dendrimer
Hair, silica inorganic dendrimer should also become design and build having for various advanced delivery systems and solid catalyst
Sharp support platform, because they have similar design feature and attractive inherent physicochemical properties.Researcher
It is prepared for the dendritic silica micrometer/nanometer particle with central radial pore structure.Dendroid particle is by titanium dioxide
Silica fibre or fold composition, as building unit, along radially direction arrangement (that is: from inside particles to particle surface).With
Traditional mesoporous silicon oxide is compared, the 3D dendritic structure of their unique openings, has huge hole path and height that can connect
Close surface area.The pore channel of center radiation is gradually increased inside particle to particle surface, and fiber or wrinkle are also just natural
It is formed.On the basis of inventor's preparation method disclosed in Chinese patent literature CN103484111A, raw material mesoporous silicon is replaced
At dendroid nano SiO 2 particle, by found after high temperature hydro-thermal reaction dendroid nano SiO 2 particle pattern by
It destroys, is unable to get successfully the dendroid silica composite nano materials of load C Ds.
In the implementation of the present invention, the inventors discovered that in the prior art the prior art has at least the following problems: having no utilization
Dendroid nano SiO 2 particle and CDs compound report.Develop a kind of easy to operate, simple process dendroid titanium dioxide
The synthetic method of silicon@carbon dots composite nanometer particle, is beneficial to the biological medicine application of CDs.
Summary of the invention
In consideration of it, the present invention provides a kind of dendroid silica@carbon dots composite nanometer particle and preparation method thereof, it is described
Method successfully prepares dendroid silica@carbon dots composite nanometer particle, and CDs load capacity is high, not only solves CDs due to size
It is not easy to be detained in small (in 10nm or less) organism, the problem of limiting its application the disadvantages of high concentration aggregation fluorescent quenching, and
The excellent fluorescence property of CDs is remained, is particularly due to CDs load on silica, so that composite particles are convenient for centrifugation point
From greatly optimizing and simplify CDs post-processing step in use.The preparation method is easy to operate simultaneously, and yield is big, easily
In formation large-scale production.
Specifically, including technical solution below:
According to the first aspect of the invention, it receives the embodiment of the invention provides a kind of dendroid silica@carbon dots are compound
The preparation method of rice grain,
Carbon dots are added into the aqueous dispersions of dendroid nano SiO 2 particle, adjusts after pH is 7.5~14 and tool is added
There is the silane coupling agent of amido functional group, gained reaction mixture reacts 3~24 hours at 25~40 DEG C, obtains the branch
Shape silica@carbon dots composite nanometer particle,
In the reaction mixture, the concentration of the dendroid nano SiO 2 particle is 3.0 × 10-4~5.5mol/
L, the concentration of carbon dots are 1.0 × 10-3~10mol/L, the concentration of the 3- TSL 8330 are 8.0 × 10-7~
2.0×10-4mol/L。
Preferably, the CDs is the CDs that surface has carboxyl, and the silane coupling agent with amido functional group is 3-
TSL 8330 or aminopropyl triethoxysilane.
Preferably,
The CDs aqueous dispersions that hydrothermal synthesis method obtains are added into the aqueous dispersions of dendroid nano SiO 2 particle,
It adjusts after pH is 7.5~14 and the silane coupling agent with amido functional group is added, gained reaction mixture is anti-at 25~40 DEG C
It answers 3~24 hours, obtains the dendroid silica@carbon dots composite nanometer particle.
It is further preferred that
The CDs aqueous dispersions that the hydrothermal synthesis method obtains obtain in accordance with the following steps: by citric acid 1.05g and ethylenediamine
670 μ L are added in 10mL water, and hydro-thermal reaction 1-12h at 180-240 DEG C obtains CDs aqueous dispersions.
The dendroid nano SiO 2 particle can be according to prior art preparation, for example, being two using ethyl orthosilicate
Siliconoxide precursor, with cationic surfactant cetyl trimethylammonium bromide and anionic surfactant sodium salicylate
The two is that mixed templates synthesize (Huang L., Liao T., Wang J., Ao L., Su W., Hu J.Brilliant
pitaya-type silica colloids with central-radial and high-density quantum dots
incorporation for ultrasensitive fluorescence immunoassays[J]
.Adv.Funct.Mater., 2017,1705380:1-11).Specific step are as follows: triethanolamine 68mg is added in 25mL water,
80 DEG C are persistently stirred 30min；Cetyl trimethylammonium bromide 380mg and sodium salicylate 168mg is added, stirs 1h；It is added just
Silester 4mL, 80 DEG C of stirring 2h；Purification, obtains the dendroid nano SiO 2 particle.
According to the second aspect of the invention, the embodiment of the invention also provides the resulting dendroid dioxies of above-mentioned preparation method
SiClx@carbon dots composite nanometer particle.
The beneficial effect of technical solution provided in an embodiment of the present invention includes at least:
1, the present invention realizes for the first time is supported on dendroid silica for CDs using the hydrothermal synthesis method of lower temperature
Surface prepares dendroid silica@carbon dots composite nanometer particle, and preparation method is simple for this, and yield is big, high-efficient, is easy to
Form large-scale production.
Although hydro-thermal method has been reported that the synthesis for carbon dots, but using less in terms of carbon dots composite material synthesis, mainly
It is because hydro-thermal method synthetic reaction is more rapid, the reaction time is shorter, and CDs is not easy to be bonded to silica surface, and CDs is used
When measuring excessive, the CDs of synthesis is easier to assemble without fluorescence.The present invention is connected in dendroid silica particles first
Functional group, to increase the load capacity of CDs, makes branch so that CDs is easy to through chemical bonds in silica surface
The enhancing of shape silica@carbon dots composite nanometer particle fluorescence intensity.By optimization silica nanoparticle surface functional group,
The parameters such as the dosage and temperature of CDs, reaction time, the dendroid silica@carbon dots of high fluorescent have been synthesized with hydro-thermal method
Composite nanometer particle.
2, synthesize dendroid silica@carbon dots composite nanometer particle both remained the excellent fluorescence property of CDs, also by
On silica in CDs load, composite nanometer particle is more convenient for being centrifugated, the step of optimizing and simplify post-processing.
3, the dendroid silica@carbon dots composite nanometer particle that preparation method of the present invention obtains is as biomarker fluorescence
Fluorescent material in material, biosensor fluorescent material or fluorescence immune chromatography test paper bar is in use, in addition to the glimmering of CDs
Except optical property, can also after a test, or fluorescent material and biomolecule coupling post-processing in, by simply from
Heart processing makes fluorescent material and system or bio-molecular separation, keeps separation process more convenient, convenient, efficient, not only reduces expensive
The loss of biomolecule can also carry out detection again, reuse, improve the availability of fluorescent material.
Detailed description of the invention
To describe the technical solutions in the embodiments of the present invention more clearly, make required in being described below to embodiment
Attached drawing is briefly described, it should be apparent that, drawings in the following description are only some embodiments of the invention, for
For those of ordinary skill in the art, without creative efforts, it can also be obtained according to these attached drawings other
Attached drawing.
Fig. 1 is the transmission electron microscope and stereoscan photograph of dendroid nano SiO 2 particle described in embodiment 1, wherein
Figure A is transmission electron microscope photo, and figure B is stereoscan photograph；
Fig. 2 is the transmission electron microscope photo of 1 gained dendroid silica@carbon dots composite nanometer particle of embodiment；
Fig. 3 is the dendroid silica@carbon dots composite nanometer particle photo under the irradiation of different light sources, wherein figure A is day
The dendroid nano SiO 2 particle irradiated under light, figure B are the dendroid silica@carbon dots composite Nanos under solar radiation
Particle, figure C are the dendroid silica@carbon dots composite nanometer particles that (wavelength 365nm) irradiates under ultraviolet lamp；
Fig. 4 is the fluorescence pattern of dendroid silica@carbon dots composite nanometer particle and its dilution；
Fig. 5 is the transmission electron microscope photo of 1 gained composite nanometer particle of comparative example；
Fig. 6 is the comparative diagram of embodiment 1 and 1 gained composite nanometer particle fluorescence pattern of comparative example；
Fig. 7 is the dendroid silica@carbon dots composite nanometer particle of various concentration and the cell that HepG2 cell is incubated for altogether
Active histogram；
Fig. 8 is under Hydrogen Peroxide, and various concentration dendroid silica@carbon dots composite nanometer particle and HepG2 are thin
The cell activity histogram that born of the same parents are incubated for altogether.
Specific embodiment
To make the object, technical solutions and advantages of the present invention clearer, below in conjunction with attached drawing to embodiment party of the present invention
Formula is described in further detail.
According to the first aspect of the invention, it receives the embodiment of the invention provides a kind of dendroid silica@carbon dots are compound
The preparation method of rice grain,
Carbon dots are added into the aqueous dispersions of dendroid nano SiO 2 particle, adjusts after pH is 7.5~14 and tool is added
There is the silane coupling agent of amido functional group, gained reaction mixture reacts 3~24 hours at 25~40 DEG C, obtains the branch
Shape silica@carbon dots composite nanometer particle,
In the reaction mixture, the concentration of the dendroid nano SiO 2 particle is 3.0 × 10-4~5.5mol/
L, the concentration of carbon dots are 1.0 × 10-3~10mol/L (preferably 1.0 × 10-2~10mol/L), the 3- aminopropyl front three
The concentration of oxysilane is 8.0 × 10-7~2.0 × 10-4mol/L。
The concentration of dendroid nano silica and carbon dots is true through calibration means commonly used in the art in the reaction mixture
It is fixed.
Preferably, the CDs is the CDs that surface has carboxyl, and the silane coupling agent with amido functional group is 3-
TSL 8330 or aminopropyl triethoxysilane.
Preferably,
The CDs aqueous dispersions that hydrothermal synthesis method obtains are added into the aqueous dispersions of dendroid nano SiO 2 particle,
It adjusts after pH is 7.5~14 and the silane coupling agent with amido functional group is added, gained reaction mixture is anti-at 25~40 DEG C
It answers 3~24 hours, obtains the dendroid silica@carbon dots composite nanometer particle.
It is further preferred that
The CDs aqueous dispersions that the hydrothermal synthesis method obtains obtain in accordance with the following steps: by citric acid 1.05g and ethylenediamine
670 μ L are added in 10mL water, and hydro-thermal reaction 1-12h at 180-240 DEG C obtains CDs aqueous dispersions.
The dendroid nano SiO 2 particle can be according to prior art preparation, for example, being two using ethyl orthosilicate
Siliconoxide precursor, with cationic surfactant cetyl trimethylammonium bromide (CTAB) and anionic surfactant water
Both poplar acid sodiums are that mixed templates synthesize (Huang L., Liao T., Wang J., Ao L., Su W., Hu
J.Brilliant pitaya-type silica colloids with central-radial and high-density
quantum dots incorporation for ultrasensitive fluorescence immunoassays[J]
.Adv.Funct.Mater., 2017,1705380:1-11).Specific step are as follows: triethanolamine 68mg is added in 25mL water,
80 DEG C are persistently stirred 30min；Cetyl trimethylammonium bromide 380mg and sodium salicylate 168mg is added, stirs 1h；It is added just
Silester 4mL, 80 DEG C of stirring 2h；Purification, obtains the dendroid nano SiO 2 particle.
According to the second aspect of the invention, the embodiment of the invention also provides the resulting dendroid dioxies of above-mentioned preparation method
SiClx@carbon dots composite nanometer particle.
The embodiment of the present invention successfully prepares dendroid silica@carbon dots composite nanometer particle, and CDs load capacity is high, no
Only solve CDs due to being not easy to be detained in small (in the 10nm or less) organism of size, high concentration aggregation fluorescent quenching the disadvantages of limit
The problem of it is applied, and the excellent fluorescence property of CDs is remained, CDs load is particularly due on silica, so that multiple
Particle is closed convenient for centrifuge separation, greatly optimizes and simplifies CDs post-processing step in use.Preparation method behaviour simultaneously
Make simply, yield is big, is easily formed large-scale production.
In following embodiments, agents useful for same information is as follows:
In following embodiments, test method is as follows:
(1) cytotoxicity of dendroid silica@carbon dots composite nanometer particle
Diluted cell suspension inoculation is passed in 96 orifice plates, incubator through cell to cultivate for 24 hours；By a series of various concentrations
The dSC phosphate buffer dispersion liquid of gradient is added in hole (control group dSC concentration is 0), continues to cultivate for 24 hours in incubator；24h
Later, concentration is added in each hole respectively is 0.5mg mL-1MTT20 μ L, cell continue be incubated for 4h；The culture in hole is sucked out
150 μ L of DMSO is added in base；Microplate reader detects absorbance value and obtains cell activity according to MTT test method at 492nm.
(2) under Hydrogen Peroxide, various concentration dendroid silica@carbon dots composite nanometer particle protection cell disappears
Except active oxygen radical acts on
The cell suspension inoculation digested is incubated for for 24 hours in 96 orifice plates, incubator；By a series of various concentration gradients
DSC phosphate buffer dispersion liquid is added in hole (control group dSC concentration is 0), and continuation is incubated for for 24 hours in the incubator；For 24 hours it
Afterwards, the hydrogen peroxide that 20mM is added in every hole is incubated for 3h altogether；Phosphate buffer washs 3 times later, carries out MTT test detection cell
Relative activity illustrates under Hydrogen Peroxide that the protection of various concentration dendroid silica@carbon dots composite nanometer particle is thin with this
Born of the same parents, elimination activity Scavenging Oxygen Free Radical.
Embodiment 1
(1) dendroid nano SiO 2 particle is prepared
Triethanolamine (TEA) 68mg is added in 25mL water, 80 DEG C are persistently stirred 30min；CTAB 380mg and water is added
Poplar acid sodium 168mg (molar ratio 1: 1) stirs 1h；Ethyl orthosilicate 4mL, 80 DEG C of stirring 2h is added；It is centrifuged 12000r
5min, ethyl alcohol (Beijing Chemical Plant, analysis is pure, 100%) washing 2 times, Centrifugal dispersion is in hydrochloric acid/methyl alcohol mixed liquor (volume ratio
It is 1: 9) in；60 DEG C of stirring 6h are centrifuged, and washing obtains dendroid nano SiO 2 particle.The dendroid silica is received
Rice grain is dispersed in 100mL ethyl alcohol, obtains the alcohol dispersion liquid of dendroid nano SiO 2 particle.
Fig. 1 shows the transmission electron microscope (TEM) of gained dendroid nano SiO 2 particle and scanning electron microscope (SEM) is shone
Piece, the results showed that, dendroid nano SiO 2 particle is successfully prepared, dendroid silica spheres are put with clearly center
Penetrate shape duct, single favorable dispersibility.
(2) carbon dots nano particle is prepared
Citric acid 1.05g and 670 μ L of ethylenediamine is added in 10mL water, hydro-thermal 2h at 200 DEG C, obtains surface with carboxyl
CDs aqueous dispersions.
(3) dendroid silica@carbon dots composite nanometer particle is prepared
Dendroid nano SiO 2 particle obtained by (1) is dispersed in water, the aqueous dispersions of CDs obtained by (2), tree is added
The concentration of dendritic nano SiO 2 particle is 3.0 × 10-2The concentration of mol/L, CDs are 1.0 × 10-1mol/L.With 1.0 × 10-1Mol/L ammonium hydroxide adjusts the pH value of solution (since ammonium hydroxide additional amount is few, to be influenced less, herein for 14 on concentration is respectively formed in system
It is omitted), add 8.0 × 10-5Mol/L 3- TSL 8330 (Beijing lark prestige Science and Technology Ltd.).
Gained reaction mixture reacts 24 hours at 30 DEG C；It is finally centrifuged, separates, washing, gained precipitates drying, obtains dendroid
Silica@carbon dots composite nanometer particle.Method commonly used in the art can be used in drying means, is such as lyophilized.
Embodiment 2
(1) prepare dendroid nano SiO 2 particle (with embodiment 1)
(2) prepare carbon dots nano particle (with embodiment 1)
(3) dendroid silica@carbon dots composite nanometer particle is prepared
In aqueous solution by the dispersion of dendroid nano SiO 2 particle obtained by (1), the water dispersion of CDs obtained by (2) is added
Liquid, the concentration of dendroid nano SiO 2 particle are 5.5mol/L, and the concentration of CDs is 1.0 × 10-1mol/L.With 1.0 × 10-1The pH value that mol/L ammonium hydroxide adjusts solution is 14, adds 2.0 × 10-4Mol/L 3- TSL 8330.Gained
Reaction mixture reacts 3 hours at 25 DEG C；It is finally centrifuged, separates, washing, gained precipitates drying, obtains dendroid dioxy
SiClx@carbon dots composite nanometer particle.
Embodiment 3
(1) prepare dendroid nano SiO 2 particle (with embodiment 1)
(2) prepare carbon dots nano particle (with embodiment 1)
(3) dendroid silica@carbon dots composite nanometer particle is prepared
In aqueous solution by the dispersion of dendroid nano SiO 2 particle obtained by (1), the water dispersion of CDs obtained by (2) is added
Liquid, the concentration of dendroid nano SiO 2 particle are 3.0 × 10-4The concentration of mol/L, CDs are 10mol/L.With 1.0 × 10- 1The pH value that mol/L ammonium hydroxide adjusts solution is 14, adds 8.0 × 10-7Mol/L3- TSL 8330.Gained is anti-
Mixed liquor is answered to react 24 hours at 25 DEG C；It is finally centrifuged, separates, washing, gained precipitates drying, obtains dendroid titanium dioxide
Silicon@carbon dots composite nanometer particle.
Embodiment 4
(1) prepare dendroid nano SiO 2 particle (with embodiment 1)
(2) prepare carbon dots nano particle (with embodiment 1)
(3) dendroid silica@carbon dots composite nanometer particle is prepared
In aqueous solution by the dispersion of dendroid nano SiO 2 particle obtained by (1), the water dispersion of CDs obtained by (2) is added
Liquid, the concentration of dendroid nano SiO 2 particle are 5.0 × 10-4The concentration of mol/L, CDs are 1.0 × 10-2mol/L.With
1.0×10-1The pH value that mol/L ammonium hydroxide adjusts solution is 14, adds 8.0 × 10-6Mol/L 3- aminopropyl trimethoxy silicon
Alkane.Gained reaction mixture reacts 12 hours at 40 DEG C；It is finally centrifuged, separates, washing, gained precipitates drying, obtains tree
Dendritic silica@carbon dots composite nanometer particle.
Fig. 2 shows the transmission electron microscopes (TEM) of 1 gained dendroid nano SiO 2 particle of embodiment, the results showed that, institute
Obtaining dendroid silica@carbon dots composite nanometer particle has clearly central radial duct, single favorable dispersibility；
Fig. 3 is the 1 gained dendroid silica@carbon dots composite nanometer particle photo of embodiment under the irradiation of different light sources,
Wherein figure A is the dendroid nano SiO 2 particle irradiated under daylight, and figure B is the dendroid silica@under solar radiation
Carbon dots composite nanometer particle, figure C are the dendroid silica@carbon dots composite Nanos that (wavelength 365nm) irradiates under ultraviolet lamp
Grain, the results showed that gained dendroid silica@carbon dots composite nanometer particle has fluorescence；
Fig. 4 is the fluorogram of 1 gained dendroid silica@carbon dots composite nanometer particle dispersion liquid of various concentration embodiment
Spectrum (wherein dSC refers to the alcohol dispersion liquid that embodiment 1 obtains, and dilution is diluted with ethyl alcohol), the results showed that, gained branch
Shape silica@carbon dots composite nanometer particle alleviates CDs high concentration fluorescent quenching effect.
Comparative example 1
First with the condition preparation dendroid silica and carbon dots in embodiment 1.
The dendroid silica 0.3g that centrifuge separation obtains is distributed in the toluene of 30mL, the N- ammonia of 1.2mL is added
Ethyl-γ-aminopropyltrimethoxysilane (DAPS) stirs for 24 hours at 60 DEG C, under nitrogen protection after toluene and ethanol washing
60 DEG C of dendroid silica being dried in vacuo after being modified；By the hydride modified dendroid nano SiO 2 particle of gained point
It dissipates in aqueous solution, the aqueous dispersions of carbon dots is added, the concentration of dendroid nano SiO 2 particle is 3.0 × 10-2Mol/L,
The concentration of CDs is 1.0 × 10-1mol/L.With 1.0 × 10-1The pH value that mol/L ammonium hydroxide adjusts solution is 14, adds 3- amino
Propyl trimethoxy silicane.Gained reaction mixture reacts 24 hours at 30 DEG C；It is finally centrifuged, separates, washing, gained precipitating
It is dry, composite nanometer particle is obtained, transmission electron microscope and fluorescence spectrum are shown in Fig. 5, Fig. 6.
Fig. 5 is the transmission electron microscope photo of 1 gained composite nanometer particle of comparative example, the results showed that the shape of dendroid silica
Looks have been totally disrupted, and are unable to get dendroid silica@carbon dots composite nanometer particle；
Fig. 6 is the comparative diagram of embodiment 1 and 1 gained composite nanometer particle fluorescence pattern of comparative example, the results showed that, embodiment
The fluorescence intensity of 1 gained composite nanometer particle is apparently higher than comparative example 1.
Embodiment 5
1 gained dendroid nano SiO 2 particle of embodiment and HepG2 cell are incubated for altogether carries out MTT test, as a result table
Bright, HepG2 cell relative viability and control group are almost similar in dendroid nano SiO 2 particle group, without significantly raw
Object toxicity has good biocompatibility (Fig. 7).
1 gained dendroid silica@carbon dots composite nanometer particle of embodiment is applied to HepG2 cell, can be eliminated
Active oxygen radical；Various concentration H2O2It is incubated for altogether with cell, H2O2Simulate extraneous oxidative stress pressure, MTT test result table
It is bright, compared with the control group, 2mM H2O2Reduce cell viability by nearly half, H2O2Concentration increases to 20mM from 2mM, and cell is living
Force gradient reduces.Have the function of elimination activity oxygen radical in the cell to verify dendroid nano SiO 2 particle,
By the way that 20mM H is added2O2It is incubated for altogether 3 hours with cell, dendroid silica@carbon dots composite nanometer particle, then carries out MTT
Test, as a result as shown in figure 8, in H2O2Oxidative stress environment under, with dendroid silica@carbon dots composite nanometer particle
Concentration is increased to 125 μ g/mL from 0, and cell relative viability is stepped up to 42% from 29%, illustrates dendroid silica@carbon
Point composite nanometer particle concentration is higher, stronger to the ability of anti-oxidation stress, has and eliminates Free Radical.
The foregoing is merely presently preferred embodiments of the present invention, is not intended to limit the invention, it is all in spirit of the invention and
Within principle, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.
Claims (7)
1. a kind of preparation method of dendroid silica@carbon dots composite nanometer particle, which is characterized in that
Carbon dots are added into the aqueous dispersions of dendroid nano SiO 2 particle, adjusting to be added after pH is 7.5~14 has ammonia
The silane coupling agent of base functional group, gained reaction mixture react 3~24 hours at 25~40 DEG C, obtain the dendroid two
Silica@carbon dots composite nanometer particle,
In the reaction mixture, the concentration of the dendroid nano SiO 2 particle is 3.0 × 10-4~5.5mol/L, carbon
The concentration of point is 1.0 × 10-3~10mol/L, the concentration of the 3- TSL 8330 are 8.0 × 10-7~2.0
×104mol/L。
2. preparation method as described in claim 1, which is characterized in that the carbon dots are the carbon dots that surface has carboxyl, described
Silane coupling agent with amido functional group is 3- TSL 8330 or aminopropyl triethoxysilane.
3. preparation method as claimed in claim 1 or 2, which is characterized in that
The carbon dots aqueous dispersions that hydrothermal synthesis method obtains are added into the aqueous dispersions of dendroid nano SiO 2 particle, adjust
PH is added the silane coupling agent with amido functional group after being 7.5~14, and gained reaction mixture reacts 3 at 25~40 DEG C~
24 hours, obtain the dendroid silica@carbon dots composite nanometer particle.
4. preparation method as claimed in claim 3, which is characterized in that
The carbon dots dispersion liquid that the hydrothermal synthesis method obtains obtains in accordance with the following steps: by 670 μ L of citric acid 1.05g and ethylenediamine
It is added in 10mL water, hydro-thermal reaction 1-12h at 180-240 DEG C obtains carbon dots aqueous dispersions.
5. preparation method as claimed in claim 1 or 2, which is characterized in that the dendroid nano SiO 2 particle utilizes
Ethyl orthosilicate is silica precursor, with cationic surfactant cetyl trimethylammonium bromide and anionic surface
Both activating agent sodium salicylates are mixed templates synthesis.
6. preparation method as claimed in claim 5, which is characterized in that triethanolamine 68mg is added in 25mL water, 80 DEG C are held
Continuous stirring 30min；Cetyl trimethylammonium bromide 380mg and sodium salicylate 168mg is added, stirs 1h；Positive silicic acid second is added
Ester 4mL, 80 DEG C of stirring 2h；Purification, obtains the dendroid nano SiO 2 particle.
7. the resulting dendroid silica@carbon dots composite nanometer particle of any one of claim 1-6 preparation method.
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