CN105880631B - A kind of golden cluster-carbon dots nano particle of nucleocapsid structure and its preparation method and application - Google Patents
A kind of golden cluster-carbon dots nano particle of nucleocapsid structure and its preparation method and application Download PDFInfo
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- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
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- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/05—Metallic powder characterised by the size or surface area of the particles
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- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
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- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/07—Metallic powder characterised by particles having a nanoscale microstructure
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Abstract
The present invention provides a kind of golden cluster carbon dots nano particle of nucleocapsid and its preparation method and application, the gold cluster carbon dots nano particle is using carbon dots as template, there is nanogold cluster inside it, the nanogold cluster is connected with carbon dots by Au N coordinate bonds, and the particle size of the gold cluster carbon dots nano particle is 3 5nm.The preparation method of the gold cluster carbon dots nano particle is：Gold chloride is added as template in the carbon dots synthesized using polyamines polyene and citric acid, and the golden cluster carbon dots nano particle is obtained by the reaction in the presence of a reducing agent.The golden cluster carbon dots nano particle diameter that the present invention obtains is uniform, favorable dispersibility, and nanogold cluster is connected with carbon dots by Au N coordinate bonds, golden cluster is maintained to stablize, it is not easy to reunite, gold cluster carbon dots nano particle of the present invention, which can be applied to Cellular Oxidation, to be amplified, and oncotherapy is used for.
Description
Technical field
The invention belongs to field of nanometer material technology, it is related to a kind of golden cluster-carbon dots nano particle and preparation method thereof and with use, especially
It is related to extra small golden cluster-carbon dots nano particle of a kind of nucleocapsid structure and its preparation method and application.
Background technology
Tumour cell has highly reactive form of oxygen (Reactive oxygen species, ROS) level, and compares normal cell
It is more sensitive to ROS.But simultaneously tumour cell have high oxidation stress, and with reduced glutathione (glutathione,
GSH characteristic feature is adjusted on).GSH is intracellular most important, and the most abundant small molecule antioxidant of content, GSH passes through its mercapto
Base provides anti oxidative damage, inhibits apoptosis of tumor cells, the ROS of high concentration that can promote division and the proliferation of tumour cell,
Increase Oncogenome unstability and induces the generation and development of tumour.Balance influence between ROS and GSH cancer cell
Existence and death.Therefore, the oxidative stress for adjusting tumour cell is the key that oncotherapy.
Carbon dots are as a kind of novel nano-material, since its preparation is simple, high-fluorescence quantum yield, and spectrum is adjustable Deng spies
Property, in fluorescence imaging, detection etc. is many-sided to have huge potential using value.Carbon dots nano particle size is usually in 1-
5nm size uniformities, pattern rule.And it has usually from organic molecule high temperature cabonization than more loose structure.Carbon dots
Due to preparing the difference of raw material and preparation method, ingredient is different.
The catalytic performance of noble metal nano cluster is a up-and-coming application.For example, gold is initially considered to have
Catalytically inactive, but the gold of Nano grade has been proved in an extensive chemical reaction there is good catalysis to live at present
Property.Metal nanometre cluster possesses intrinsic activity similar with native enzyme, because the small volume of its ultra micro, low toxicity the advantages that molecule at
Picture, bio-sensing, medicine and catalytic field have potential application value.
CN 103981531A disclose a kind of preparation method of fluorescent carbon point, and the method includes pretreatment and liquid phases etc.
Plasma discharge step, although fluorescent carbon point is successfully prepared in it, the ingredient of fluorescent carbon point prepared by this method is single, and its
It needs to use liquid phase plasma electric discharge in preparation process, process is relative complex.For another example CN104071769A discloses a kind ofization
The method that oxidizing process prepares fluorescent carbon point is learned, the method heats the coke mass obtained after charing process with coal or by coal
For carbon source material, specifically includes oxide etch, dialysis desalination and drying steps, the fluorescent carbon point that this method is prepared and be also only
Coal base fluorescent carbon point.
Therefore, in the art, it is expected that obtaining a kind of fluorescent carbon point system being combined carbon dots with noble metal nano cluster
Preparation Method.
Invention content
In view of the deficiencies of the prior art, the purpose of the present invention is to provide a kind of golden cluster-carbon dots nano particle and its preparations
Methods and applications are especially to provide extra small golden cluster-carbon dots nano particle of a kind of nucleocapsid structure and its preparation method and application.
To reach the invention purpose, the present invention uses following technical scheme：
On the one hand, the present invention provides a kind of golden cluster-carbon dots nano particle (golden cluster@carbon dots nano particle), the gold cluster-carbon
Point nano particle using carbon dots as template there is nanogold cluster, the nanogold cluster to pass through Au-N coordinate bonds with carbon dots inside it
It is connected, the particle size of the gold cluster-carbon dots nano particle is 3-5nm.
In the present invention the particle size of the cluster-carbon dots nano particle can be 3nm, 3.2nm, 3.5nm, 3.8nm,
4nm, 4.3nm, 4.5nm, 4.8nm or 5nm.Golden cluster-carbon dots nano particle of the present invention has extra small nanometer particle size size, and
Uniform particle diameter is in monodispersity.
Inside carbon dots, golden cluster is connected with carbon dots by Au-N coordinate bonds the golden cluster of the present invention, maintains the steady of golden cluster
It is unlikely to reunite calmly.Since the bond energy of Au-S keys is 40kcal/mol, the bond energy of Au-N keys is 8kcal/mol, the bond energy of Au-S
Bond energy much larger than Au-N, therefore the golden cluster@carbon dots nano particles of the present invention enter after inside tumor cells, intracellular
GSH can replace the amino in carbon dots to form coordinate bond with Au, to which the GSH for consuming cell interior is horizontal, to reach characteristic killing
The purpose of tumour cell, due to the presence of GSH-ROS balances, the reduction of GSH levels necessarily leads to the increasing of intracellular ROS level
Height, to the oxidative stress in magnocell, apoptosis occurs for induction tumour cell.
On the other hand, the present invention provides a kind of preparation method of golden cluster-carbon dots nano particle as described above, and the method is
Gold chloride is added as template in the carbon dots synthesized using polyamines polyene and citric acid, and the golden cluster-is obtained by the reaction in the presence of a reducing agent
Carbon dots nano particle.
The preparation method of gold cluster-carbon dots nano particle of the present invention includes the following steps：
(1) polyamines polyene and citric acid are mixed, carbon dots solution is obtained by the reaction；
(2) chlorauric acid solution is added in the carbon dots solution obtained to step (1), reducing agent is then added and carries out reduction reaction
Obtain the golden cluster-carbon dots nano particle.
The present invention adsorbs gold chloride with carbon dots, and carbon dots have than more loose structure, utilize a large amount of amino-functionals of carbon dots
Group is combined with gold chloride brings gold chloride in the open structure of carbon dots into, then reducing agent is used to restore, in carbon dots internal in-situ
The golden cluster of synthesis, to obtain extra small golden cluster-carbon dots nano particle (being indicated with golden cluster@carbon dots) of uniform particle diameter, nanogold cluster and
Carbon dots are connected by Au-N coordinate bonds, are maintained golden cluster to stablize, are not easy to reunite.
Preferably, the mass ratio of step (1) polyamines polyene and citric acid is 1:1-50:1, such as 1:1、2:1、3:1、
4:1、5:1、6:1、7:1、8:1、9:1、10:1、12:1、15:1、18:1、20:1、23:1、25:1、28:1、30:1、35:1、40:
1、45:1 or 50:1.
Preferably, the temperature of step (1) described reaction be 130-190 DEG C, such as 130 DEG C, 135 DEG C, 140 DEG C, 145 DEG C,
150 DEG C, 155 DEG C, 160 DEG C, 165 DEG C, 170 DEG C, 175 DEG C, 180 DEG C, 185 DEG C or 190 DEG C, preferably 170 DEG C.
Preferably, the time of step (1) described reaction be 1-8h, such as 1h, 1.5h, 2h, 2.5h, 3h, 3.5h, 4h,
4.5h, 5h, 5.5h, 6h, 6.5h, 7h, 7.5h or 8h.
Preferably, the carbon dots obtained to step (1) using dialysis are purified.
Preferably, the mass concentration of step (2) described carbon dots solution is 1-30mg/mL, such as 0.2mg/mL, 0.5mg/
mL、0.8mg/mL、1mg/mL、1.5mg/mL、2mg/mL、3mg/mL、5mg/mL、8mg/mL、10mg/mL、12mg/mL、15mg/
ML, 18mg/mL, 20mg/mL, 23mg/mL, 25mg/mL, 28mg/mL or 30mg/mL.
Preferably, step (2) described chlorauric acid solution is aqueous solution of chloraurate.
Preferably, the molar concentration of step (2) described chlorauric acid solution be 2-15mM, such as 2mM, 3mM, 4mM, 5mM,
7mM, 9mM, 10mM, 12mM, 14mM or 15mM, preferably 10mM.
Preferably, the mole of the gold chloride of step (2) described addition is 1-10 μm of ol, such as 1 μm of ol, 2 μm of ol, 3 μ
Mol, 4 μm of ol, 5 μm of ol, 6 μm of ol, 7 μm of ol, 8 μm of ol, 9 μm of ol or 10 μm of ol.
Preferably, step (2) carbon dots solution and the volume ratio of chlorauric acid solution are 1:1-1:8, such as 1:1、1:
1.5、1:2、1:2.5、1:3、1:3,5、1:4、1:4.5、1:5、1:5.5、1:6、1:6.5、1:7、1:7.5 or 1:8.
Preferably, step (2) it is described be added into carbon dots solution chlorauric acid solution 5-20min (such as 5min, 6min,
7min, 8min, 9min, 10min, 12min, 14min, 15min, 17min, 19min or 20min) after add reducing agent progress
Reduction reaction.After the time described in chlorauric acid solution is added in carbon dots solution in the present invention, it can make gold chloride radical ion more
Good is combined by coordinate bond with the amino in carbon dots, ensures sufficient incubation time so that saturation adsorbs chlorine inside and outside carbon dots
Auric acid radical ion.
Preferably, step (2) described reducing agent is sodium borohydride.
Preferably, the addition of step (2) described reducing agent is 3-20 times of gold chloride mole, for example, 3 times, 5 times, 7
Again, 9 times, 10 times, 12 times, 15 times, 18 times or 20 times.
Preferably, step (2) described reduction reaction carries out in the presence of alkaline reagent.
Preferably, the alkaline reagent is sodium hydroxide and/or potassium hydroxide.
Preferably, the mass ratio of the alkaline reagent and reducing agent is 2:1-8:1, such as 2:1、3:1、4:1、5:1、6:1、
7:1 or 8:1.
Preferably, step (2) described reduction reaction carries out under stiring.
Preferably, the speed of agitator be 1000rpm or more, such as 1000rpm, 2000rpm, 2500rpm, 3000rpm,
3800rpm, 4000rpm, 5000rpm, 6000rpm, 7500rpm, 8000rpm, 10000rpm etc., preferably 1000-5000rpm.
Preferably, the temperature of step (2) described reduction reaction be 20-30 DEG C, such as 20 DEG C, 22 DEG C, 24 DEG C, 25 DEG C, 26
DEG C, 28 DEG C or 30 DEG C.
Preferably, the time of step (2) described reduction reaction be 2-8h, such as 2h, 2.5h, 3h, 3.5h, 4h, 4.5h,
5h, 5.5h, 6h, 6.5h, 7h, 7.5h or 8h.
Preferably, the product of step (2) described reduction reaction is centrifuged, ultrafiltration or dialysis is carried out to supernatant, removed
Decontamination obtains the golden cluster-carbon dots nano particle.
Preferably, the ultrafiltration is carried out using super filter tube or ultrafiltration membrane, the molecular cut off of the super filter tube or ultrafiltration membrane
For 10-30kDa, such as 10kDa, 12kDa, 14kDa, 16kDa, 18kDa, 20kDa, 23kDa, 25kDa, 28kDa or 30kDa.
Preferably, the molecular cut off of bag filter used of dialysing is 10-30kDa, such as 10kDa, 12kDa,
14kDa, 16kDa, 18kDa, 20kDa, 23kDa, 25kDa, 28kDa or 30kDa.
On the other hand, the present invention provides the golden cluster-carbon dots nano particles in preparing the drug for treating tumour
Application.
The drug that golden cluster-carbon dots nano particle of the present invention can be used as treating tumour is used in the medicine for preparing treatment tumour
Object, can be applied to Cellular Oxidation stress amplify, and be conducive to the treatment of tumour.
Compared with the existing technology, the invention has the advantages that：
The method that the present invention prepares golden cluster-carbon dots nano particle has the characteristics that simple for process, yield is high, environmental-friendly.
The grain size of extra small golden cluster-carbon dots nano particle of nucleocapsid structure provided by the invention is 3-5nm, and uniform particle diameter is dispersed good
Good, the nanogold cluster is connected with carbon dots by Au-N coordinate bonds, is maintained golden cluster to stablize, is not easy to reunite, gold of the present invention
Carbon dots nano particle can be applied to Cellular Oxidation to cluster-to amplify, cell viability experiment display, the gold cluster@carbon dots nanometers
IC of the particle to human hepatoma cell strain50Value is 32 μ g/mL, has preferable tumor cell killing potential, can be used for oncotherapy.
Description of the drawings
The preparation method schematic diagram of golden cluster@carbon dots nano particles prepared by Fig. 1 present invention.
Fig. 2 is the transmission electron microscope picture of golden cluster@carbon dots nano particles prepared by the present invention, and wherein B figures are in A figures inside box
The enlarged drawing in region.
Fig. 3 is the dynamic light scattering characterization result figure of golden cluster@carbon dots nano particles prepared by the present invention.
Fig. 4 is the uv-visible absorption spectra characterization result figure of golden cluster@carbon dots nano particles prepared by the present invention.
Fig. 5 is paddy Guang in cell after handling HepG-2 cells using the golden cluster@carbon dots nano particles that the present invention is prepared
Sweet peptide content test result figure.
Fig. 6 is the cytotoxicity experiment result figure of the golden cluster@carbon dots nano particles prepared by the present invention.
Specific implementation mode
The technical solution further illustrated the present invention below by specific implementation mode.Those skilled in the art should be bright
, the embodiment, which is only to aid in, understands the present invention, should not be regarded as a specific limitation of the invention.
Embodiment 1
In the present embodiment, golden cluster@carbon dots core-shell nanoparticles are prepared by the following method, following steps are specifically included
(preparation method schematic diagram is as shown in Figure 1)：
(1) by polyamines polyene and citric acid with 1:1 mass ratio mixing reacts 2h at 170 DEG C and obtains carbon dots solution, dialyses
The carbon dots of method purifying synthesis, obtain the carbon dots solution of a concentration of 12mg/mL；
(2) carbon dots solution for taking 1mL steps (1) to obtain after 10mM chlorauric acid solutions 1mL, 10min is added, turns in stirring
Under fast 1000rpm stirrings, addition is added dropwise 1mL and contains 12mg NaOH and 2mg NaBH4Ice water solution, stirred at 25 DEG C
Reaction 4h is mixed, after reaction centrifuges the super filter tube that reaction product is 10kDa with molecular cut off under 5000rpm rotating speeds,
With water washing three times it is multiple after obtain the golden cluster-carbon dots nano particle.
It is (golden to the golden cluster-carbon dots nano particle being prepared using transmission electron microscope (Tecnai G2 20S-TWIN, FEI)
Cluster@carbon dots nano particle) it is characterized, the results are shown in Figure 2, and as seen from Figure 2, the size of carbon dots shell is 4-5nm, gold
Cluster is distributed in the core position of carbon dots, and the size of golden cluster is 1-2nm, the nano particle favorable dispersibility.
Using dynamic light scattering (Zetasizer Nano ZS, Malvern) to golden cluster-carbon dots nanometer for being prepared
Particle (golden cluster@carbon dots nano particle) is characterized, and the results are shown in Figure 3, as seen from Figure 3, nano particle dispersibility
Well, uniform particle diameter, size is in 4.7 ± 0.38nm.
In addition, having carried out ultraviolet-visible to the golden cluster-carbon dots nano particle (golden cluster@carbon dots nano particle) being prepared
Absorption spectrum characterizes, and the results are shown in Figure 4, and as shown in Figure 4, simple carbon dots are absorbed in 500nm or so without apparent, but golden cluster@carbon
Point has apparent UV absorption 500nm at, it was demonstrated that the successful synthesis of gold cluster in carbon dots.
Embodiment 2
In the present embodiment, golden cluster@carbon dots core-shell nanoparticles are prepared by the following method, following steps are specifically included
(preparation method schematic diagram is as shown in Figure 1)：
(1) by polyamines polyene and citric acid with 5:1 mass ratio mixing reacts 1h at 190 DEG C and obtains carbon dots solution, dialyses
The carbon dots of method purifying synthesis, obtain the carbon dots solution of a concentration of 30mg/mL；
(2) carbon dots solution for taking 1mL steps (1) to obtain, after 5mM chlorauric acid solutions 5mL, 5min is added, in speed of agitator
Under 5000rpm stirrings, addition is added dropwise 1mL and contains 8mg NaOH and 2mg NaBH4Ice water solution, stirred at 20 DEG C anti-
4h is answered, is after reaction centrifuged the super filter tube that reaction product is 10kDa with molecular cut off under 5000rpm rotating speeds, with three
Golden cluster-carbon dots the nano particle is obtained after secondary water washing is multiple.
Characterization is carried out using transmission electron microscope it can be seen that the size of carbon dots shell is 4-5nm, and golden cluster is distributed in the core of carbon dots
The size of heart position, golden cluster is 1-2nm, the nano particle favorable dispersibility.Dynamic light scattering characterization result also indicates that the gold
Cluster-carbon dots nano particle favorable dispersibility, uniform particle diameter, size is in 4.5 ± 0.4nm.Uv-visible absorption spectra characterization result
Demonstrate the successful synthesis of golden cluster@carbon dots nano particles.
Embodiment 3
In the present embodiment, golden cluster@carbon dots core-shell nanoparticles are prepared by the following method, following steps are specifically included
(preparation method schematic diagram is as shown in Figure 1)：
(1) by polyamines polyene and citric acid with 15:1 mass ratio mixing reacts 8h at 130 DEG C and obtains carbon dots solution, thoroughly
The carbon dots of analysis method purifying synthesis, obtain the carbon dots solution of a concentration of 1mg/mL；
(2) carbon dots solution for taking 1mL steps (1) to obtain after 15mM chlorauric acid solutions 1mL, 15min is added, turns in stirring
Under fast 5000rpm stirrings, addition is added dropwise 1mL and contains 4mg NaOH and 2mg NaBH4Ice water solution, stirred at 30 DEG C
2h is reacted, after reaction centrifuges the super filter tube that reaction product is 10kDa with molecular cut off under 5000rpm rotating speeds, with
Golden cluster-carbon dots the nano particle is obtained after water washing is multiple three times.
Characterization is carried out using transmission electron microscope it can be seen that the size of carbon dots shell is 3-5nm, and golden cluster is distributed in the core of carbon dots
The size of heart position, golden cluster is 1-2nm, the nano particle favorable dispersibility.Dynamic light scattering characterization result also indicates that the gold
Cluster-carbon dots nano particle favorable dispersibility, uniform particle diameter, size is in 4.3 ± 0.8nm.Uv-visible absorption spectra characterization result
Demonstrate the successful synthesis of golden cluster@carbon dots nano particles.
Embodiment 4
In the present embodiment, golden cluster@carbon dots core-shell nanoparticles are prepared by the following method, following steps are specifically included
(preparation method schematic diagram is as shown in Figure 1)：
(1) by polyamines polyene and citric acid with 50:1 mass ratio mixing reacts 5h at 150 DEG C and obtains carbon dots solution, thoroughly
The carbon dots of analysis method purifying synthesis, obtain the carbon dots solution of a concentration of 15mg/mL；
(2) carbon dots solution for taking 1mL steps (1) to obtain, after 2mM chlorauric acid solutions 8mL, 20min is added, in speed of agitator
Under 5000rpm stirrings, addition is added dropwise 1mL and contains 12mg NaOH and 1.9mg NaBH4Ice water solution, stirred at 25 DEG C
Reaction 8h is mixed, after reaction centrifuges the super filter tube that reaction product is 10kDa with molecular cut off under 5000rpm rotating speeds,
With water washing three times it is multiple after obtain the golden cluster-carbon dots nano particle.
Characterization is carried out using transmission electron microscope it can be seen that the size of carbon dots shell is 3-5nm, and golden cluster is distributed in the core of carbon dots
The size of heart position, golden cluster is 1-2nm, the nano particle favorable dispersibility.Dynamic light scattering characterization result also indicates that the gold
Cluster-carbon dots nano particle favorable dispersibility, uniform particle diameter, size is in 4.7 ± 0.32nm.Uv-visible absorption spectra characterization knot
Fruit demonstrates the successful synthesis of golden cluster@carbon dots nano particles.
Embodiment 5
Influence of the golden cluster carbon dots nano particle to tumour cell Glutathione peptide content, method are investigated in the present embodiment
It is as follows：
HepG-2 cells are inoculated in 50000 density per hole in 6 orifice plates, after cell is adherent, embodiment 1 is made
Standby obtained golden cluster@carbon dots nano particle handles cell 2h with 0,2,4,8,16,32,64 μ g/mL, discards culture solution, to each
Each 200 μ L of the efficient lysates of RIPA are added in hole, with cell scraper by under cell scraper, 4 DEG C crack 30min, using glutathione
Detection kit detects the glutathione content in lysate, and as a contrast with carbon dots, the results are shown in Figure 5, can be obtained by Fig. 5
Intracellular GSH levels can effectively be consumed by going out golden cluster@carbon dots nano particle.
Embodiment 6
Influence of the golden cluster@carbon dots nano particle to tumor cell vigor is investigated in the present embodiment, and method is as follows：
HepG-2 cells are inoculated in 8000 density per hole in 96 orifice plates, after cell is adherent, embodiment 1 is made
Standby obtained golden cluster@carbon dots for 24 hours, are discarded supernatant liquid, are added and are tried containing cck-8 with 2,4,8,16,32,64 μ g/mL processing cells
The culture medium of liquid after being incubated 2h, detects 450nm absorbances, as a contrast with carbon dots under microplate reader.Gold is shown in FIG. 6
The comparison of cluster@carbon dots and carbon dots cell viability, Fig. 6 show that simple carbon dots are safe and non-toxic, at 64 μ g/mL of concentration also
100% cell viability is maintained, and corresponding carbon dots gold particle processing group shows good toxic effect, half
Lethal dose (IC50In 32 μ g/mL).
Applicant states that the present invention illustrates golden cluster-carbon dots nanometer of the nucleocapsid structure of the present invention by above-described embodiment
Particle and its preparation method and application, but the invention is not limited in above-described embodiments, that is, do not mean that the present invention has to rely on
Above-described embodiment could be implemented.Person of ordinary skill in the field is it will be clearly understood that any improvement in the present invention, to the present invention
The equivalence replacement of selected raw material and the addition of auxiliary element, the selection of concrete mode etc., all fall within protection scope of the present invention
Within the open scope.
Claims (27)
1. a kind of preparation method of gold cluster-carbon dots nano particle, which is characterized in that the gold cluster-carbon dots nano particle is with carbon dots
For template, there is nanogold cluster, the nanogold cluster to be connected by Au-N coordinate bonds with carbon dots inside it, the gold cluster-
The particle size of carbon dots nano particle is 3-5nm；
The method is：As template gold chloride is added, in the presence of a reducing agent instead in the carbon dots synthesized using polyamines polyene and citric acid
It should obtain the golden cluster-carbon dots nano particle.
2. preparation method according to claim 1, which is characterized in that the described method comprises the following steps：
(1) polyamines polyene and citric acid are mixed, carbon dots solution is obtained by the reaction；
(2) chlorauric acid solution is added in the carbon dots solution obtained to step (1), reducing agent progress reduction reaction is then added and obtains
Gold cluster-carbon dots the nano particle.
3. preparation method according to claim 2, which is characterized in that the matter of step (1) polyamines polyene and citric acid
Amount is than being 1:1-50:1.
4. preparation method according to claim 2, which is characterized in that the temperature of step (1) described reaction is 130-190
℃。
5. preparation method according to claim 4, which is characterized in that the temperature of step (1) described reaction is 170 DEG C.
6. preparation method according to claim 2, which is characterized in that the time of step (1) described reaction is 1-8h.
7. preparation method according to claim 2, which is characterized in that the carbon dots that step (1) is obtained using dialysis into
Row purifying.
8. preparation method according to claim 2, which is characterized in that the mass concentration of step (2) described carbon dots solution is
1-30mg/mL。
9. preparation method according to claim 2, which is characterized in that step (2) described chlorauric acid solution is gold chloride water
Solution.
10. preparation method according to claim 2, which is characterized in that the molar concentration of step (2) described chlorauric acid solution
For 2-15mM.
11. preparation method according to claim 10, which is characterized in that step (2) described chlorauric acid solution it is mole dense
Degree is 10mM.
12. preparation method according to claim 2, which is characterized in that the mole of the gold chloride of step (2) described addition
For 1-10 μm of ol.
13. preparation method according to claim 2, which is characterized in that step (2) carbon dots solution and chlorauric acid solution
Volume ratio be 1:1-1:8.
14. preparation method according to claim 2, which is characterized in that step (2) is described, and chlorine gold is added into carbon dots solution
Reducing agent is added after acid solution 5-20min carries out reduction reaction.
15. preparation method according to claim 2, which is characterized in that step (2) described reducing agent is sodium borohydride.
16. preparation method according to claim 2, which is characterized in that the addition of step (2) described reducing agent is chlorine gold
3-20 times of sour mole.
17. preparation method according to claim 2, which is characterized in that step (2) described reduction reaction is deposited in alkaline reagent
In lower progress.
18. preparation method according to claim 17, which is characterized in that the alkaline reagent is sodium hydroxide and/or hydrogen
Potassium oxide.
19. preparation method according to claim 17, which is characterized in that the mass ratio of the alkaline reagent and reducing agent is
2:1-8:1。
20. preparation method according to claim 2, which is characterized in that step (2) described reduction reaction under stiring into
Row.
21. preparation method according to claim 20, which is characterized in that the speed of agitator is 1000rpm or more.
22. preparation method according to claim 21, which is characterized in that the speed of agitator is 1000-5000rpm.
23. preparation method according to claim 2, which is characterized in that the temperature of step (2) described reduction reaction is 20-
30℃。
24. preparation method according to claim 2, which is characterized in that the time of step (2) described reduction reaction is 2-
8h。
25. preparation method according to claim 2, which is characterized in that carry out the product of step (2) described reduction reaction
Centrifugation carries out ultrafiltration or dialysis to supernatant, removes impurity and obtains the golden cluster-carbon dots nano particle.
26. preparation method according to claim 25, which is characterized in that the ultrafiltration using super filter tube or ultrafiltration membrane into
The molecular cut off of row, the super filter tube or ultrafiltration membrane is 10-30kDa.
27. preparation method according to claim 25, which is characterized in that the retention molecule of the bag filter used of dialysing
Amount is 10-30kDa.
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