CN105880631A - Core-shell structured gold cluster-carbon dot nano-particles as well as preparation method and application thereof - Google Patents
Core-shell structured gold cluster-carbon dot nano-particles as well as preparation method and application thereof Download PDFInfo
- Publication number
- CN105880631A CN105880631A CN201610416821.2A CN201610416821A CN105880631A CN 105880631 A CN105880631 A CN 105880631A CN 201610416821 A CN201610416821 A CN 201610416821A CN 105880631 A CN105880631 A CN 105880631A
- Authority
- CN
- China
- Prior art keywords
- carbon point
- nano
- gold
- particle
- preparation
- 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
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- 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
- B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- 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
- B22F1/054—Nanosized particles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/06—Metallic powder characterised by the shape of the particles
- B22F1/065—Spherical particles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- 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
-
- 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
Abstract
The invention provides core-shell structured gold cluster-carbon dot nano-particles as well as a preparation method and application thereof. According to the gold cluster-carbon dot nano-particles, carbon dots are taken as a template, a nano gold cluster exists inside the template, the nano gold cluster and the carbon dots are connected by virtue of Au-N coordinate bonds, and the particle size of the gold cluster-carbon dot nano-particles is 3-5nm. The preparation method of the gold cluster-carbon dot nano-particles comprises the following steps: by taking carbon dots synthesized from polyethylene-polyamine and citric acid as a template, adding chloroauric acid, enabling the components to react in the presence of a reducing agent, so as to obtain the gold cluster-carbon dot nano-particles. The gold cluster-carbon dot nano-particles provided by the invention are uniform in particle size and good in dispersity, the nano gold cluster and the carbon dots are connected by virtue of the Au-N coordinate bonds, and the gold cluster is kept stable and is difficult to aggregate. The gold cluster-carbon dot nano-particles provided by the invention can be applied to intracellular oxidative stress amplification for tumor treatment.
Description
Technical field
The invention belongs to field of nanometer material technology, relate to a kind of gold bunch-carbon point nano-particle and preparation method thereof and use
With, extra small gold bunch-carbon point nano-particle particularly relating to a kind of nucleocapsid structure and its preparation method and application.
Background technology
Tumor cell has highly reactive form of oxygen (Reactive oxygen species, ROS) level, and compares normal
Cell is more sensitive to ROS.But simultaneously tumor cell have high oxidation stress, and with reduced glutathion
It is adjusted to typical characteristic on (glutathione, GSH).GSH is intracellular most important, and content is the abundantest
Small molecule antioxidant, GSH provides anti oxidative damage by its sulfydryl, suppresses apoptosis of tumor cells,
The ROS of high concentration can promote division and the propagation of tumor cell, increases Oncogenome unstability and induces
The generation of tumor and development.Balance influence between ROS and GSH existence and the death of cancerous cell.Therefore,
The oxidative stress level of regulation tumor cell is the key of oncotherapy.
Carbon point is as a kind of novel nano-material, and owing to its preparation is simple, high-fluorescence quantum yield, spectrum can
The characteristics such as tune, it is at fluorescence imaging, and detection etc. is many-sided has huge potential using value.Carbon point nanometer
Granular size is generally in 1-5nm size uniformity, pattern rule.And it is generally by organic molecule high temperature cabonization
Coming, it has than more loose structure.Carbon point is owing to preparing the difference of raw material and preparation method, and composition is different.
The catalytic performance of noble metal nano cluster is a up-and-coming application.Such as, gold is initially considered
There is catalytically inactive, but the gold of Nano grade has been proved in one widely chemical reaction at present
There is good catalysis activity.Metal nanometre cluster has the intrinsic activity similar to native enzyme, because of its ultra micro
The advantages such as little volume, low toxicity have potential at molecular imaging, bio-sensing, medicine and catalytic field
Using value.
CN 103981531A discloses the preparation method of a kind of fluorescent carbon point, described method include pretreatment and
Liquid phase plasma discharge step, although it successfully prepares fluorescent carbon point, fluorescent carbon prepared by the method
The composition of point is single, and needs in its preparation process to use liquid phase plasma electric discharge, and process is relative complex.
And for example CN104071769A discloses a kind of method that chemical oxidization method prepares fluorescent carbon point, described method with
Coal or coal heats the coke mass that obtains after carbonization processes is carbon source material, specifically include oxide etch,
Dialysis desalination and drying steps, the fluorescent carbon point that the method prepares is also only coal base fluorescent carbon point.
Therefore, in the art, it is desirable to obtain a kind of fluorescence combined by carbon point with noble metal nano cluster
Carbon point preparation method.
Summary of the invention
For the deficiencies in the prior art, it is an object of the invention to provide a kind of gold bunch-carbon point nano-particle and
Preparation method and application, particularly provide extra small gold bunch-carbon point nano-particle and the system thereof of a kind of nucleocapsid structure
Preparation Method and application.
For reaching this goal of the invention, the present invention by the following technical solutions:
On the one hand, the present invention provides a kind of gold bunch-carbon point nano-particle (gold bunch@carbon point nano-particle), institute
State gold bunch-carbon point nano-particle with carbon point as template, there is nanometer gold bunch therein, described nanometer gold bunch with
Carbon point is connected by Au-N coordinate bond, and the size of described gold bunch-carbon point nano-particle is 3-5nm.
In the present invention the size of described bunch-carbon point nano-particle can be 3nm, 3.2nm, 3.5
Nm, 3.8nm, 4nm, 4.3nm, 4.5nm, 4.8nm or 5nm.The gold bunch of the present invention-carbon point nanometer
Granule has extra small nanometer particle size size, and uniform particle diameter, in monodispersity.
The gold bunch of the present invention is inside carbon point, and gold bunch is connected by Au-N coordinate bond with carbon point, maintains
Stablizing of gold bunch is unlikely to reunite.Owing to the bond energy that the bond energy of Au-S key is 40kcal/mol, Au-N key is 8
The bond energy of kcal/mol, the Au-S bond energy much larger than Au-N, the therefore gold bunch@carbon point nano-particle of the present invention
After entering inside tumor cells, the amino that intracellular GSH can replace on carbon point is coordinated with Au is formed
Key, thus consume the GSH level of cell interior, to reach the purpose of characteristic killing tumor cell, due to
The existence of GSH-ROS balance, the reduction of GSH level necessarily causes increasing of intracellular ROS level, from
And the oxidative stress level in magnocell, inducing tumor cell generation apoptosis.
On the other hand, the present invention provides the preparation method of a kind of gold bunch described above-carbon point nano-particle, described
Method be the carbon point synthesized with polyamines polyene and citric acid as template, add gold chloride, in the presence of a reducing agent
Reaction obtains described gold bunch-carbon point nano-particle.
The preparation method of gold bunch of the present invention-carbon point nano-particle comprises the following steps:
(1) polyamines polyene and citric acid being mixed, reaction obtains carbon point solution；
(2) in the carbon point solution that step (1) obtains, add chlorauric acid solution, then add reducing agent and enter
Row reduction reaction obtains described gold bunch-carbon point nano-particle.
The present invention adsorbs gold chloride with carbon point, and carbon point has the more loose structure of ratio, utilizes a large amount of ammonia of carbon point
Base functional group is combined in the open structure that gold chloride is brought into carbon point with gold chloride, then uses reducing agent also
Former, at carbon point internal in-situ synthesis gold bunch, thus obtain the extra small gold bunch-carbon point nano-particle of uniform particle diameter
(representing with a gold bunch@carbon point), nanometer gold bunch is connected by Au-N coordinate bond with carbon point, maintains gold bunch steady
Fixed, it is difficult to reunite.
Preferably, the mass ratio of step (1) described 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 is 130-190 DEG C, such as 130 DEG C, 135 DEG C,
140℃、145℃、150℃、155℃、160℃、165℃、170℃、175℃、180℃、185℃
Or 190 DEG C, preferably 170 DEG C.
Preferably, the time of step (1) described reaction is 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 point utilizing dialysis to obtain step (1) is purified.
Preferably, the mass concentration of step (2) described carbon point solution is 1-30mg/mL, such as 0.2
mg/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、20
Mg/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 is 2-15mM, such as 2mM, 3
MM, 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 ol, such as 1 μm ol,
2 μm ol, 3 μm ol, 4 μm ol, 5 μm ol, 6 μm ol, 7 μm ol, 8 μm ol, 9 μm ol or 10
μmol。
Preferably, step (2) described carbon point solution is 1:1-1:8 with the volume ratio of chlorauric acid solution, 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) described in carbon point solution add chlorauric acid solution 5-20min (such as 5min,
6min、7min、8min、9min、10min、12min、14min、15min、17min、19
Min or 20min) after add reducing agent and carry out reduction reaction.Carbon point solution adds chlorine gold in the present invention
After time described in acid solution, so that gold chloride radical ion is preferably by coordinate bond and the amino on carbon point
In conjunction with, it is ensured that sufficient incubation time so that the most saturated absorption gold chloride radical ion inside and outside carbon point.
Preferably, step (2) described reducing agent is sodium borohydride.
Preferably, 3-20 times that addition is gold chloride mole of step (2) described reducing agent, such as 3
Again, 5 times, 7 times, 9 times, 10 times, 12 times, 15 times, 18 times or 20 times.
Preferably, step (2) described reduction reaction is carried out in the presence of alkaline reagent.
Preferably, described alkaline reagent is sodium hydroxide and/or potassium hydroxide.
Preferably, the mass ratio of described 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 is under agitation carried out.
Preferably, described speed of agitator is more than 1000rpm, such as 1000rpm, 2000rpm, 2500
rpm、3000rpm、3800rpm、4000rpm、5000rpm、6000rpm、7500rpm、8000
Rpm, 10000rpm etc., preferably 1000-5000rpm.
Preferably, the temperature of step (2) described reduction reaction is 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 is 2-8h, such as 2h, 2.5h, 3h, 3.5
H, 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, supernatant is carried out ultrafiltration or
Dialysis, removes impurity and obtains described gold bunch-carbon point nano-particle.
Preferably, described ultrafiltration utilizes super filter tube or ultrafilter membrane to carry out, retaining of described super filter tube or ultrafilter membrane
Molecular weight is 10-30kDa, such as 10kDa, 12kDa, 14kDa, 16kDa, 18kDa, 20
KDa, 23kDa, 25kDa, 28kDa or 30kDa.
Preferably, the molecular cut off of the bag filter that described dialysis uses is 10-30kDa, such as 10kDa,
12kDa, 14kDa, 16kDa, 18kDa, 20kDa, 23kDa, 25kDa, 28kDa or 30
kDa。
On the other hand, the invention provides described gold bunch-carbon point nano-particle in preparation for the medicine treating tumor
Application in thing.
The gold bunch of the present invention-carbon point nano-particle can be used as treating the medicine of tumor and is used in preparation treatment tumor
Medicine, it can be applicable to Cellular Oxidation and stress amplify, the beneficially treatment of tumor.
Relative to prior art, the method have the advantages that
The present invention prepares the gold bunch-method of carbon point nano-particle and has that technique is simple, productivity is high, environmental friendliness etc.
Feature.The particle diameter of the extra small gold bunch-carbon point nano-particle of the nucleocapsid structure that the present invention provides is 3-5nm, grain
Footpath is homogeneous, favorable dispersibility, and described nanometer gold bunch is connected by Au-N coordinate bond with carbon point, maintains gold
Bunch stable, it is difficult to reunite, gold bunch of the present invention-carbon point nano-particle can apply to Cellular Oxidation stress
Amplify, cell viability experiment display, this gold bunch@carbon point nano-particle IC to human hepatoma cell strain50Value is
32 μ g/mL, have preferable tumor cell killing potential, may be used for oncotherapy.
Accompanying drawing explanation
The preparation method schematic diagram of gold bunch@carbon point nano-particle prepared by Fig. 1 present invention.
Fig. 2 is the transmission electron microscope picture of gold bunch@carbon point nano-particle prepared by the present invention, and wherein B figure is A figure
The enlarged drawing of middle square frame interior zone.
Fig. 3 is the dynamic light scattering characterization result figure of gold bunch@carbon point nano-particle prepared by the present invention.
Fig. 4 is the uv-visible absorption spectra characterization result of gold bunch@carbon point nano-particle prepared by the present invention
Figure.
Fig. 5 is after the gold bunch@carbon point nano-particle utilizing the present invention to prepare processes HepG-2 cell, carefully
Born of the same parents' GSH-PX activity content measuring result figure.
Fig. 6 is the cytotoxicity experiment result figure of the gold bunch@carbon point nano-particle prepared by the present invention.
Detailed description of the invention
Technical scheme is further illustrated below by detailed description of the invention.Those skilled in the art
It will be clearly understood that the only help of described embodiment understands the present invention, it is not construed as the concrete limit to the present invention
System.
Embodiment 1
In the present embodiment, be prepared by the following method gold bunch@carbon point core-shell nanoparticles, specifically include with
Lower step (preparation method schematic diagram is as shown in Figure 1):
(1) polyamines polyene and citric acid are mixed with the mass ratio of 1:1, obtain carbon point at 170 DEG C of reaction 2h
Solution, the carbon point of dialysis purification synthesis, obtain the carbon point solution that concentration is 12mg/mL；
(2) take the carbon point solution that 1mL step (1) obtains, add 10mM chlorauric acid solution 1mL,
After 10min, under speed of agitator 1000rpm stirs, addition is added dropwise over 1mL and contains 12mg NaOH
With 2mg NaBH4Ice water solution, at 25 DEG C stirring reaction 4h, reaction terminate after by product use
Molecular cut off is that the super filter tube of 10kDa is centrifugal under 5000rpm rotating speed, obtains the most afterwards with three water washings
To described gold bunch-carbon point nano-particle.
Utilize transmission electron microscope (Tecnai G2 20S-TWIN, FEI) to the gold bunch prepared-carbon point nanometer
Granule (gold bunch@carbon point nano-particle) characterizes, result as in figure 2 it is shown, as seen from Figure 2,
The size of carbon point shell is 4-5nm, and gold bunch is distributed in the core position of carbon point, and the size of gold bunch is 1-2nm,
This nano-particle favorable dispersibility.
Utilize dynamic light scattering (Zetasizer Nano ZS, Malvern) that the gold bunch prepared-carbon point is received
Rice grain (gold bunch@carbon point nano-particle) characterizes, result as it is shown on figure 3, as seen from Figure 3,
This nano-particle favorable dispersibility, uniform particle diameter, size is at 4.7 ± 0.38nm.
Additionally, the gold bunch prepared-carbon point nano-particle (gold bunch@carbon point nano-particle) has been carried out purple
Outward-visible absorption spectra characterizes, and as shown in Figure 4, as shown in Figure 4, simple carbon point is at about 500nm for result
Without substantially absorbing, but a gold bunch@carbon point has obvious uv absorption at 500nm, it was demonstrated that carbon point Endothelium corneum
Bunch successful synthesis.
Embodiment 2
In the present embodiment, be prepared by the following method gold bunch@carbon point core-shell nanoparticles, specifically include with
Lower step (preparation method schematic diagram is as shown in Figure 1):
(1) polyamines polyene and citric acid are mixed with the mass ratio of 5:1, obtain carbon point at 190 DEG C of reaction 1h
Solution, the carbon point of dialysis purification synthesis, obtain the carbon point solution that concentration is 30mg/mL；
(2) take the carbon point solution that 1mL step (1) obtains, add 5mM chlorauric acid solution 5mL, 5
After min, speed of agitator 5000rpm stir under, add be added dropwise over 1mL contain 8mg NaOH with
2mg NaBH4Ice water solution, at 20 DEG C stirring reaction 4h, reaction terminate after by product with cut
The super filter tube staying molecular weight to be 10kDa is centrifugal under 5000rpm rotating speed, obtains the most afterwards with three water washings
Described gold bunch-carbon point nano-particle.
Utilizing transmission electron microscope to carry out characterizing it can be seen that the size of carbon point shell is 4-5nm, gold bunch is distributed in carbon
The core position of point, the size of gold bunch is 1-2nm, this nano-particle favorable dispersibility.Dynamic light scattering table
Levying result and also indicate that described gold bunch-carbon point nano-particle favorable dispersibility, uniform particle diameter, size is 4.5 ± 0.4
nm.Uv-visible absorption spectra characterization result demonstrates the successful synthesis of gold bunch@carbon point nano-particle.
Embodiment 3
In the present embodiment, be prepared by the following method gold bunch@carbon point core-shell nanoparticles, specifically include with
Lower step (preparation method schematic diagram is as shown in Figure 1):
(1) polyamines polyene and citric acid are mixed with the mass ratio of 15:1, obtain carbon at 130 DEG C of reaction 8h
Point solution, the carbon point of dialysis purification synthesis, obtain the carbon point solution that concentration is 1mg/mL；
(2) take the carbon point solution that 1mL step (1) obtains, add 15mM chlorauric acid solution 1mL,
After 15min, under speed of agitator 5000rpm stirs, addition is added dropwise over 1mL and contains 4mg NaOH
With 2mg NaBH4Ice water solution, at 30 DEG C stirring reaction 2h, reaction terminate after by product use
Molecular cut off is that the super filter tube of 10kDa is centrifugal under 5000rpm rotating speed, obtains the most afterwards with three water washings
To described gold bunch-carbon point nano-particle.
Utilizing transmission electron microscope to carry out characterizing it can be seen that the size of carbon point shell is 3-5nm, gold bunch is distributed in carbon
The core position of point, the size of gold bunch is 1-2nm, this nano-particle favorable dispersibility.Dynamic light scattering table
Levying result and also indicate that described gold bunch-carbon point nano-particle favorable dispersibility, uniform particle diameter, size is 4.3 ± 0.8
nm.Uv-visible absorption spectra characterization result demonstrates the successful synthesis of gold bunch@carbon point nano-particle.
Embodiment 4
In the present embodiment, be prepared by the following method gold bunch@carbon point core-shell nanoparticles, specifically include with
Lower step (preparation method schematic diagram is as shown in Figure 1):
(1) polyamines polyene and citric acid are mixed with the mass ratio of 50:1, obtain carbon at 150 DEG C of reaction 5h
Point solution, the carbon point of dialysis purification synthesis, obtain the carbon point solution that concentration is 15mg/mL；
(2) take the carbon point solution that 1mL step (1) obtains, add 2mM chlorauric acid solution 8mL,
After 20min, under speed of agitator 5000rpm stirs, addition is added dropwise over 1mL and contains 12mg NaOH
With 1.9mg NaBH4Ice water solution, at 25 DEG C stirring reaction 8h, reaction terminate after by product
It is centrifuged under 5000rpm rotating speed with the super filter tube that molecular cut off is 10kDa, after three water washings repeatedly
Obtain described gold bunch-carbon point nano-particle.
Utilizing transmission electron microscope to carry out characterizing it can be seen that the size of carbon point shell is 3-5nm, gold bunch is distributed in carbon
The core position of point, the size of gold bunch is 1-2nm, this nano-particle favorable dispersibility.Dynamic light scattering table
Levying result and also indicate that described gold bunch-carbon point nano-particle favorable dispersibility, uniform particle diameter, size is 4.7 ± 0.32
nm.Uv-visible absorption spectra characterization result demonstrates the successful synthesis of gold bunch@carbon point nano-particle.
Embodiment 5
Investigate the gold bunch carbon point nano-particle shadow to tumor cell Glutathione peptide content in the present embodiment
Ringing, method is as follows:
HepG-2 cell is inoculated in 6 orifice plates with the density in 50000 every holes, after cell attachment, will
The gold bunch@carbon point nano-particle that embodiment 1 prepares with 0,2,4,8,16,32,64 μ g/mL at
Reason cell 2h, discards culture fluid, adds each 200 μ L of the efficient lysate of RIPA, use cell in each hole
Cell is scraped by scraper, 4 DEG C of cracking 30min, uses the paddy in glutathion detection kit detection lysate
The sweet peptide content of Guang, using carbon point as comparison, result is as it is shown in figure 5, can be drawn gold bunch@carbon point by Fig. 5
Nano-particle can effectively consume intracellular GSH level.
Embodiment 6
Investigate the gold bunch@carbon point nano-particle impact on tumor cell vigor, method in the present embodiment
As follows:
HepG-2 cell is inoculated in 96 orifice plates with the density in 8000 every holes, after cell attachment, will
The gold bunch@carbon o'clock that embodiment 1 prepares processes cell 24h with 2,4,8,16,32,64 μ g/mL,
Abandoning supernatant, adds the culture medium containing cck-8 test solution, after hatching 2h, detects 450nm under microplate reader
Absorbance, using carbon point as comparison.Figure 6 illustrates gold bunch@carbon point and the contrast of carbon point cell viability,
Fig. 6 shows, simple carbon point is safety non-toxic, also maintain under concentration 64 μ g/mL 100% thin
Born of the same parents' vigor, and the carbon of correspondence point gold grain process group shows good toxic effect, its median lethal
Amount (IC50At 32 μ g/mL).
Applicant states, the present invention illustrates the gold bunch-carbon point of the nucleocapsid structure of the present invention by above-described embodiment
Nano-particle and its preparation method and application, but the invention is not limited in above-described embodiment, i.e. do not mean that
The present invention has to rely on above-described embodiment and could implement.Person of ordinary skill in the field is it will be clearly understood that right
Any improvement of the present invention, the equivalence to raw material selected by the present invention is replaced and the interpolation of auxiliary element, concrete
Way choice etc., within the scope of all falling within protection scope of the present invention and disclosure.
Claims (10)
1. gold bunch-carbon point nano-particle, it is characterised in that described gold bunch-carbon point nano-particle is with carbon point
For template, having nanometer gold bunch therein, described nanometer gold bunch is connected by Au-N coordinate bond with carbon point
Connecing, the size of described gold bunch-carbon point nano-particle is 3-5nm.
The preparation method of gold bunch the most according to claim 1-carbon point nano-particle, it is characterised in that
Described method is: the carbon point synthesized with polyamines polyene and citric acid, as template, adds gold chloride, at reducing agent
In the presence of reaction obtain described gold bunch-carbon point nano-particle.
Preparation method the most according to claim 2, it is characterised in that described method includes following step
Rapid:
(1) polyamines polyene and citric acid being mixed, reaction obtains carbon point solution；
(2) in the carbon point solution that step (1) obtains, add chlorauric acid solution, then add reducing agent and enter
Row reduction reaction obtains described gold bunch-carbon point nano-particle.
Preparation method the most according to claim 3, it is characterised in that step (1) described polyenoid is many
The mass ratio of amine and citric acid is 1:1-50:1；
Preferably, the temperature of step (1) described reaction is 130-190 DEG C, preferably 170 DEG C；
Preferably, the time of step (1) described reaction is 1-8h；
Preferably, the carbon point utilizing dialysis to obtain step (1) is purified.
5. according to the preparation method described in claim 3 or 4, it is characterised in that step (2) described carbon
The mass concentration of some solution is 1-30mg/mL；
Preferably, step (2) described chlorauric acid solution is aqueous solution of chloraurate；
Preferably, the molar concentration of step (2) described chlorauric acid solution is 2-15mM, preferably 10mM；
Preferably, the mole of the gold chloride of step (2) described addition is 1-10 μm ol.
6. according to the preparation method according to any one of claim 3-5, it is characterised in that step (2)
Described carbon point solution is 1:1-1:8 with the volume ratio of chlorauric acid solution.
7. according to the preparation method according to any one of claim 3-6, it is characterised in that step (2)
Described addition in carbon point solution adds reducing agent after chlorauric acid solution 5-20min and carries out reduction reaction；
Preferably, step (2) described reducing agent is sodium borohydride；
Preferably, 3-20 times that addition is gold chloride mole of step (2) described reducing agent；
Preferably, step (2) described reduction reaction is carried out in the presence of alkaline reagent；
Preferably, described alkaline reagent is sodium hydroxide and/or potassium hydroxide；
Preferably, described alkaline reagent is 2:1-8:1 with the mass ratio of reducing agent.
8. according to the preparation method according to any one of claim 3-7, it is characterised in that step (2)
Described reduction reaction is under agitation carried out；
Preferably, described speed of agitator is more than 1000rpm, preferably 1000-5000rpm；
Preferably, the temperature of step (2) described reduction reaction is 20-30 DEG C；
Preferably, the time of step (2) described reduction reaction is 2-8h.
9. according to the preparation method according to any one of claim 3-8, it is characterised in that by step (2)
The product of described reduction reaction is centrifuged, and supernatant carries out ultrafiltration or dialysis, removes impurity and obtains described
Gold bunch-carbon point nano-particle；
Preferably, described ultrafiltration utilizes super filter tube or ultrafilter membrane to carry out, retaining of described super filter tube or ultrafilter membrane
Molecular weight is 10-30kDa；
Preferably, the molecular cut off of the bag filter that described dialysis uses is 10-30kDa.
Gold bunch the most according to claim 1-carbon point nano-particle is used for treating the medicine of tumor in preparation
In application.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610416821.2A CN105880631B (en) | 2016-06-14 | 2016-06-14 | A kind of golden cluster-carbon dots nano particle of nucleocapsid structure and its preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610416821.2A CN105880631B (en) | 2016-06-14 | 2016-06-14 | A kind of golden cluster-carbon dots nano particle of nucleocapsid structure and its preparation method and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105880631A true CN105880631A (en) | 2016-08-24 |
| CN105880631B CN105880631B (en) | 2018-09-04 |
Family
ID=56730503
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610416821.2A Active CN105880631B (en) | 2016-06-14 | 2016-06-14 | A kind of golden cluster-carbon dots nano particle of nucleocapsid structure and its preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105880631B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109351963A (en) * | 2018-10-26 | 2019-02-19 | 中南大学 | A kind of blacker-than-black material and its preparation method and application |
| CN110157421A (en) * | 2019-04-22 | 2019-08-23 | 山西大学 | A kind of gold nanoclusters/carbon dots composite fluorescent nano particle and preparation method thereof and the application in tetracycline detection |
| CN110251684A (en) * | 2019-07-05 | 2019-09-20 | 中国药科大学 | Have nano-complex of the oxidative stress from enlarging function, preparation method and application |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008259993A (en) * | 2007-04-13 | 2008-10-30 | Tokyo Metropolitan Univ | Method for dispersing and fixing gold fine particle to carrier, gold fine particle-deposited carrier obtained thereby, catalyst and colorant |
| JP2009213993A (en) * | 2008-03-10 | 2009-09-24 | Japan Science & Technology Agency | Polymer supported gold cluster catalyst for oxidation reaction and manufacturing method of carbonyl compound using it |
| WO2014068163A1 (en) * | 2012-10-30 | 2014-05-08 | Consejo Superior De Investigaciones Científicas (Csic) | Production of atomic aggregates of gold in an acid medium and the application thereof in catalysis |
| CN105067577A (en) * | 2015-07-14 | 2015-11-18 | 天津大学 | Dual emission rate type fluorescent probe for visually detecting carbon dots-Au nanoclusters of mercury ions and preparation method |
-
2016
- 2016-06-14 CN CN201610416821.2A patent/CN105880631B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008259993A (en) * | 2007-04-13 | 2008-10-30 | Tokyo Metropolitan Univ | Method for dispersing and fixing gold fine particle to carrier, gold fine particle-deposited carrier obtained thereby, catalyst and colorant |
| JP2009213993A (en) * | 2008-03-10 | 2009-09-24 | Japan Science & Technology Agency | Polymer supported gold cluster catalyst for oxidation reaction and manufacturing method of carbonyl compound using it |
| WO2014068163A1 (en) * | 2012-10-30 | 2014-05-08 | Consejo Superior De Investigaciones Científicas (Csic) | Production of atomic aggregates of gold in an acid medium and the application thereof in catalysis |
| CN105067577A (en) * | 2015-07-14 | 2015-11-18 | 天津大学 | Dual emission rate type fluorescent probe for visually detecting carbon dots-Au nanoclusters of mercury ions and preparation method |
Non-Patent Citations (2)
| Title |
|---|
| L.CALLIARI ET AL.,: "Core-level photoemission from nanocluster-matrix composites:Au clusters in amorphous carbon", 《APPLIED SURFACE SCIENCE》 * |
| LINGYANG ZHANG ET AL.，: "Preparation of Gold−Carbon Dots and Ratiometric Fluorescence Cellular Imaging", 《ACS APPL.MATER.INTERFACES》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109351963A (en) * | 2018-10-26 | 2019-02-19 | 中南大学 | A kind of blacker-than-black material and its preparation method and application |
| CN110157421A (en) * | 2019-04-22 | 2019-08-23 | 山西大学 | A kind of gold nanoclusters/carbon dots composite fluorescent nano particle and preparation method thereof and the application in tetracycline detection |
| CN110251684A (en) * | 2019-07-05 | 2019-09-20 | 中国药科大学 | Have nano-complex of the oxidative stress from enlarging function, preparation method and application |
| CN110251684B (en) * | 2019-07-05 | 2021-10-29 | 中国药科大学 | Nano compound with oxidative stress self-amplification function, preparation method and application |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105880631B (en) | 2018-09-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Zhou et al. | Carbon nitride nanotubes with in situ grafted hydroxyl groups for highly efficient spontaneous H2O2 production | |
| Liu et al. | A titanium nitride nanozyme for pH‐responsive and irradiation‐enhanced cascade‐catalytic tumor therapy | |
| Dong et al. | Fabrication of highly dispersed Pd nanoparticles supported on reduced graphene oxide for catalytic reduction of 4-nitrophenol | |
| CN105880631A (en) | Core-shell structured gold cluster-carbon dot nano-particles as well as preparation method and application thereof | |
| Geng et al. | Cu2-xO@ TiO2-y Z-scheme heterojunctions for sonodynamic-chemodynamic combined tumor eradication | |
| CN106377770A (en) | Nanocomposite of black phosphorus nanosheet/copper sulfide nanoparticles as well as preparation method and application thereof | |
| Bonardd et al. | A novel environmentally friendly method in solid phase for in situ synthesis of chitosan-gold bionanocomposites with catalytic applications | |
| CN107802835A (en) | A kind of black phosphorus nanometer sheet/nano platinum particle composite and its preparation method and application | |
| Jin et al. | Enhanced performance of Ag3PO4/Fe3O4/GO bifunctional catalysts on p-chlorophenol degradation in advanced catalytic oxidation systems | |
| Duan et al. | Enhanced photocatalytic activity of bismuth molybdate via hybridization with carbon | |
| CN106040307B (en) | One step hydro thermal method synthesizes Fe3O4(PAA) preparation method of@C-Au core-shell structure microballoon | |
| Sharma et al. | Constructing a novel all-solid-state Z-scheme BiVO4/CQDs/FeVO4 photocatalyst and its enhancement to the photocatalytic activity | |
| Palanisamy et al. | Novel biomolecule-capped CdTe nanoparticles for highly efficient photodegradation of methyl orange dye under visible-light irradiation | |
| Atta-Eyison et al. | Photocatalysis using zinc oxide-zinc phthalocyanine composite for effective mineralization of organic pollutants | |
| Mafukidze et al. | Spectroscopic characterization and photodynamic antimicrobial chemotherapy of phthalocyanine-silver triangular nanoprism conjugates when supported on asymmetric polymer membranes | |
| He et al. | Recent developments of inorganic nanosensitizers for sonodynamic therapy | |
| Fu et al. | Versatile BP/Pd-FPEI-CpG nanocomposite for" three-in-one" multimodal tumor therapy | |
| Liu et al. | Ag/black phosphorus composite based on multilayer black phosphorus: Its preparation and photocatalytic methyl orange degradation performance | |
| Kongor et al. | Calix [4] pyrrole stabilized PdNPs as an efficient heterogeneous catalyst for enhanced degradation of water-soluble carcinogenic Azo dyes | |
| Liu et al. | N-doped three-dimensional graphene aerogel with a high loading of Ag particles as an efficient catalyst and antibacterial agent | |
| Bhattacharya et al. | Evaluation of N doped rGO-ZnO-CoPc (COOH) 8 nanocomposite in cyanide degradation and its bactericidal activities | |
| Beaton et al. | Al2O3 anchored silver and gold nanoparticles as accessible, stable, and re-usable catalysts | |
| Li et al. | Laccase-assisted rapid synthesis of colloidal gold nanoparticles for the catalytic reduction of 4-Nitrophenol | |
| Tian et al. | Revealing Mn doping effect in transition metal phosphides to trigger active centers for highly efficient Chemodynamic and NIR-II Photothermal therapy | |
| CN104368338B (en) | A kind of have amido modified Pd/TiO2The preparation method of photocatalyst |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |