CN106421785A - Polydopamine-coated nanometer composite photothermal reagent and preparation method thereof - Google Patents
Polydopamine-coated nanometer composite photothermal reagent and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a polydopamine-coated nanometer composite photothermal reagent and a preparation method thereof and belongs to the technical field of function materials. The method is simple to operate and two coating methods are provided: firstly, inorganic nanometer particles or the surface of an assembly of the inorganic nanometer particles are directly coated with a polydopamine shell layer through the oxidative polymerization character of a dopamine monomer; and secondly, nanometer particles are synthesized and coated by one step by utilizing the reducibility and the oxidative polymerization character of dopamine, so that the trouble of synthesizing the nanometer particles in advance is prevented, operation is more simple, and a synthesis method has better green environmental protection character. Proved by experiments, after the nanometer particles are coated with the polydopamine shell layer, the biocompatibility, the physiological environment stability and the photothermal stability of the nanometer particles are greatly improved; by introducing a hydroxyl functional group and an amino functional group, the condition of further modifying a biological targeting matter or a loaded medicine is supplied for the nanometer particles; and in addition, as the polydopamine has the photothermal character, the photothermal conversion efficiency of a material coated with the polydopamine shell layer is improved.
Description
Technical field
The invention belongs to technical field of function materials and in particular to a kind of poly-dopamine cladding nano combined photothermal reagent
And preparation method thereof.
Background technology
In order to avoid traditional therapy is for the side effect of cancer patient, photo-thermal therapy method enjoys researchers to close
Note.Photo-thermal therapy refers to, photothermal reagent absorbs near infrared light, is rapidly converted into heat, so that system is heated up, leads to protein denaturation,
Finally kill the tumor therapeuticing method of the new high specificity of cancer cell.The species of photothermal reagent is various, is broadly divided into inorganic
Nano-particle or its assembly and organic polymer nano-particle, wherein inorganic nano-particle or its assembly are due to its preparation side
Method is simple, morphology controllable, and has the hot coefficient of high light and photothermal conversion efficiency at near-infrared and be widely studied, such as your gold
Belong to nano-particle and its assembly, ferromagnetism nanometer particle and its assembly, semi-conductor nano particles and graphene carbon base material
Material etc..But inorganic nano-particle or its assembly are readily incorporated virose part in preparation process and make its biocompatibility
Reduce and limit application；And inorganic nano-particle or its assembly are easy to due to having higher specific surface area occur to gather
" melting effect " is occurred to lose original pattern and optical property after collection, and heating, its photo and thermal stability has much room for improvement；Remove
Outside this, in order to increase the specificity of photo-thermal therapy, nano material needs to modify some biological target tropism molecules or medicine, therefore
Increase nanoparticle surface functional groups very necessary.
In order to solve problem above, we are using in inorganic nano-particle and its assembly Surface coating poly-dopamine shell
Method, so that biocompatibility, physiological environment stability and the photo and thermal stability of material is improved, and be nanoparticle sublist
Face is successfully introduced into functional groups.This method is simple to operate, just can in high volume coat nano-particle at room temperature, therefore, be
A kind of effective ways being applied to industrialized production.
Content of the invention
The purpose of the present invention is large batch of in aqueous to prepare a kind of poly- DOPA using the synthetic method of colloid chemistry
The nano combined photothermal reagent of amine cladding.
The present invention is to modify the reason shell prepares nano combined photothermal reagent to be using poly-dopamine, is initially used for synthesizing
The DOPA amine monomers of poly-dopamine are a kind of materials that human body produces, and cytotoxicity is low, and biocompatibility is good；Secondly poly- DOPA
Amine has the structure similar with bivalves biological super-strong adhesion protein, thus has superpower adhesive attraction, can be used for
Cladding nano-particle strengthens its photo and thermal stability；And, poly-dopamine surface has rich functionality group, can be by entering one
Step is modified and to be expanded the multifunctionality of nano-particle；In addition, because poly-dopamine has photo-thermal effect in itself, make cladding
The nano combined photothermal reagent of poly-dopamine shell has higher photothermal conversion efficiency.
Method of the present invention is simple to operate, and the method for cladding is divided into two kinds：One is the oxidation by DOPA amine monomers
Aggregation property is directly in inorganic nano-particle or its assembly Surface coating poly-dopamine shell；Two is the reduction using dopamine
Property and oxidation polymerization property, one-step synthesis and cladding nano-particle, it is to avoid the trouble of prior synthesizing nano-particle, make operation more
Plus simple, the more standby environmental protection property of synthetic method.It is verified by experiments, coated the life of nano-particle after poly-dopamine shell
Thing compatibility, physiological environment stability and photo and thermal stability increase substantially；And introduce hydroxyl and amino functional group, it is
Nano-particle further modified biological targeting substance or carrying medicament provide condition；In addition, because poly-dopamine has
Light thermal property, makes the material photothermal conversion efficiency having coated poly-dopamine shell be improved.
Employing colloid chemistry synthetic method of the present invention, using receiving that the poly-dopamine of DOPA amine monomers synthesis coats
The preparation method of rice composite optothermal reagent, its step is as follows：
(1) method one：First will be soluble in water to inorganic nano-particle to be covered or its assembly, adjust pH value of solution to alkali
Property (pH=7.5～9.0)；It is subsequently adding DOPA amine monomers；Inorganic nano-particle or its assembly and DOPA amine monomers in solution
Concentration ratio scope be 0.1mg/mL:0.045～0.45mg/mL, is stirred at room temperature 1～6 hour, solution becomes brownish black；So
Afterwards by above-mentioned solution centrifugal, isolate inorganic nano-particle or its assembly of poly-dopamine cladding, that is, obtain of the present invention
Poly-dopamine cladding nano combined photothermal reagent；By changing consumption, solution ph and the oxidation polymerization of DOPA amine monomers
Time change the thickness of shell.
(2) method two：Prepare the stable silver nano-particle solution of sodium citrate first, preparation method is as follows：In 100mL water
The silver nitrate of middle addition 17mg, is heated to seething with excitement, is subsequently adding the sodium citrate aqueous solution of 2mL, 1w/v%, keeps solution boiling
1 hour, after being cooled to room temperature, be settled to 100mL, obtain a size of 50～60nm, silver atomic concentration be 1mM sodium citrate steady
Fixed silver nano-particle solution.
Gold chloride is mixed with silver nano-particle solution 2～5 minutes and carries out potential difference substitution reaction, be subsequently adding dopamine
Monomer is by Au remaining in solutionIIIThe Ag generating with potential difference substitution reactionIAll it is deposited on potential difference substitution reaction generation
On golden core, the concentration ratio scope of Chlorine in Solution auric acid, Nano silver grain and DOPA amine monomers is 0.1mM:0.011～
0.032mM:0.12～0.72mM；After 5～15 minutes, adjust pH value of solution to alkaline (pH=7.5～9.0), continue room temperature reaction 1
～6 hours, solution became brownish black；Then by above-mentioned solution centrifugal, separate the nano combined photo-thermal obtaining poly-dopamine cladding
Reagent, as uses the dendritic nano combined photothermal reagent of gold and silver of the reduction of DOPA amine monomers one step and cladding.By adjusting silver nanoparticle
The usage ratio of particle, gold chloride and dopamine and reaction time and pH value of solution, adjust particle size, shell thickness and table
Face plasma resonance peak.
Method one can obtain the different-shape various sizes of poly-dopamine cladding of inorganic nano-particle or its assembly
Nano combined photothermal reagent；Method two can obtain the dendritic nano combined photothermal reagent of gold and silver of poly-dopamine cladding.Two kinds
The nano combined photothermal reagent that method obtains all has good stability and light thermal property.
In method one, inorganic nano-particle or its assembly can be receive micro-dimension various patterns noble metal nano
Particle or its assembly, ferromagnetism nanometer particle or its assembly, semi-conductor nano particles.Alkalescence in method one and method two
Environment can be with trishydroxymethylaminomethane (Tris) cushioning liquid, sodium hydroxide solution, borax buffer solution or ammonia spirit
Cooperation hydrochloric acid solution auxiliary adjustment, commercially can directly buy.
In method two, Nano silver grain synthesis is simple.With gold chloride as presoma, dopamine is reducing agent and covering
The dendritic nano combined photothermal reagent of gold and silver using potential difference substitution reaction one-step synthesis poly-dopamine cladding.The method operation letter
Single, and synthetic method is using noxious materials such as surfactants, more for environmental protection property.
Both approaches all can obtain good biocompatibility, physiological environment good stability and high poly- many of photo and thermal stability
The nano combined photothermal reagent of bar amine cladding, and because poly-dopamine shell has certain photo-thermal effect, make compound particle whole
The photothermal conversion efficiency of body is improved, and under the laser of 808nm irradiates, can be rapidly heated more than 43 degree by local temperature,
There is provided adequate heat for killing cancer cell, and avoid the damage for normal structure organ.In addition, due to particle surface
There is amino, the targeting of photo-thermal therapy with biological active matter qualitative response or carrying medicaments such as folic acid, can be strengthened or increase material
The Chemotherapy of material, greatly strengthen its application in photo-thermal therapy field.
Brief description
Fig. 1：The dendritic nano-particle of gold and silver described in 1mg embodiment 1 to be covered is dissolved in 5mL water, addition 5mL,
The Tris cushioning liquid of 0.02M simultaneously assists hydrochloric acid solution so that reaction system pH is adjusted to 8.5, adds the DOPA of 100 μ L, 0.03M
Amine aqueous solution, is stirred at room temperature 3 hours, then by above-mentioned solution centrifugal, separates the nano compound light heat examination obtaining poly-dopamine cladding
Agent.Poly-dopamine shell thickness is 6nm, and surface plasma resonance peak is 811nm.(a) transmission electron microscope photo, (b) ultraviolet spectra
Figure.Corresponding embodiment 1.
Fig. 2：The dendritic nano-particle of gold and silver described in 1mg embodiment 1 to be covered is dissolved in 5mL water, addition 5mL,
The Tris cushioning liquid of 0.02M simultaneously assists hydrochloric acid solution so that reaction system pH is adjusted to 8.5, adds the DOPA of 200 μ L, 0.03M
Amine aqueous solution, is stirred at room temperature 3 hours, then by above-mentioned solution centrifugal, separates the nano compound light heat examination obtaining poly-dopamine cladding
Agent.Poly-dopamine shell thickness is 10nm, and surface plasma resonance peak is 817nm.(a) transmission electron microscope photo, (b) ultraviolet spectra
Figure.Corresponding embodiment 2.
Fig. 3：The dendritic nano-particle of gold and silver described in 1mg embodiment 1 to be covered is dissolved in 5mL water, addition 5mL,
The Tris cushioning liquid of 0.02M simultaneously assists hydrochloric acid solution so that reaction system pH is adjusted to 8.5, adds the DOPA of 600 μ L, 0.03M
Amine aqueous solution, is stirred at room temperature 3 hours, then by above-mentioned solution centrifugal, separates the nano compound light heat examination obtaining poly-dopamine cladding
Agent.Poly-dopamine shell thickness is 34nm, and surface plasma resonance peak is 917nm.(a) transmission electron microscope photo, (b) ultraviolet spectra
Figure.Corresponding embodiment 3.
Fig. 1～Fig. 3 explanation be：Using first method in the dendritic poly- DOPA of inorganic nano-particle Surface coating of gold and silver
Amine shell, and control the thickness of poly-dopamine shell by adjusting the consumption of DOPA amine monomers.
Fig. 4：First the 1mg ferroso-ferric oxide superparticle to be covered described in embodiment 6 is dissolved in 5mL water, adds
The Tris cushioning liquid of 5mL, 0.02M simultaneously assists hydrochloric acid solution so that reaction system pH is adjusted to 8.5, adds 200 μ L, 0.03M's
Dopamine solution, is stirred at room temperature 3 hours, then by above-mentioned solution centrifugal, separates the nano compound light obtaining poly-dopamine cladding
Thermal agent.Poly-dopamine shell thickness is 11nm.Figure is transmission electron microscope photo.Corresponding embodiment 6.
Fig. 4 explanation be：Gathered in the assembly Surface coating of ferroso-ferric oxide inorganic nano-particle using first method
Dopamine shell.
Fig. 5：The gold and silver of the poly-dopamine cladding that the dendritic nano-particle of gold and silver that describe embodiment 1 and embodiment 1 obtain
Dendritic nano-particle be respectively dissolved in water, 0.9w/v% sodium chloride solution, phosphate buffer solution (pH=7.4), serum-free thin
Born of the same parents' culture medium (has serum cell culture medium with having in the cell culture medium of serum：10% hyclone concentration；The dendritic nanometer of gold and silver
The dendritic nanoparticle concentration of gold and silver of particle and poly-dopamine cladding is 100mg/mL), after placing 48 hours, measure its ultraviolet
Spectrogram.It is found that there being the gold and silver branch compared to uncoated poly-dopamine for the dendritic nano-particle of gold and silver of poly-dopamine cladding
Shape nanoparticle surface plasma resonance peak is not moved, with more physiological environment stability.The dendritic nano-particle of (a) gold and silver
Ultraviolet spectrogram, (b) poly-dopamine cladding the dendritic nano-particle of gold and silver ultraviolet spectrogram.Corresponding embodiment 7.
Fig. 5 explanation be：The nano combined photothermal reagent of poly-dopamine cladding is compared to the nanometer of uncoated poly-dopamine
Particle, has more preferable physiological stability.
Fig. 6：Under conditions of room temperature is 20 DEG C, the gold and silver branch of the different poly-dopamine shell thicknesses that embodiment 1-3 obtains
Shape nano-particle was through 30 minutes 808nm, 3W/cm2Under laser irradiates, measure the temperature change of solution.Three solution to be measured
The quality of photothermal reagent be identical.Corresponding embodiment 8.
Fig. 6 explanation be：The nano combined photothermal reagent of poly-dopamine cladding has higher photo-thermal intensification ability, and its
Photo-thermal intensification ability increases with poly-dopamine shell thickness and strengthens.
Fig. 7：Add 50 μ L, 0.1M chlorauric acid solutions in 25mL water, add 800 μ L silver nano-particle solution to react 3 points
Clock, adds the dopamine solution of 200 μ L, 0.03M to react 10 minutes, is subsequently added the Tris cushioning liquid of 25mL, 0.01M, auxiliary
Helping hydrochloric acid solution to adjust pH value of solution is 8.5, continues room temperature reaction 3 hours, then by above-mentioned solution centrifugal, separates and obtain poly- DOPA
The nano combined photothermal reagent of amine cladding, as uses the dendritic nano combined photo-thermal of gold and silver of the reduction of DOPA amine monomers one step and cladding
Reagent.Scantling is 60nm, and poly-dopamine shell thickness is 3nm, and surface plasma resonance peak is 650nm.(a) transmission electron microscope
Photo, (b) ultraviolet spectrogram.Corresponding embodiment 9.
Fig. 8：Add 50 μ L, 0.1M chlorauric acid solutions in 25mL water, add 800 μ L silver nano-particle solution to react 3 points
Clock, adds the dopamine solution of 400 μ L, 0.03M to react 10 minutes, is subsequently added the Tris cushioning liquid of 25mL, 0.01M, auxiliary
Helping hydrochloric acid solution to adjust pH value of solution is 8.5, continues room temperature reaction 3 hours, then by above-mentioned solution centrifugal, separates and obtain poly- DOPA
The nano combined photothermal reagent of amine cladding, as uses the dendritic nano combined photo-thermal of gold and silver of the reduction of DOPA amine monomers one step and cladding
Reagent.Scantling is 100nm, and poly-dopamine shell thickness is 15nm, and surface plasma resonance peak is 760nm.(a) transmission electricity
Mirror photo, (b) ultraviolet spectrogram.Corresponding embodiment 10.
Fig. 9：Add 50 μ L, 0.1M chlorauric acid solutions in 25mL water, add 800 μ L silver nano-particle solution to react 3 points
Clock, adds the dopamine solution of 600 μ L, 0.03M to react 10 minutes, is subsequently added the Tris cushioning liquid of 25mL, 0.01M, auxiliary
Helping hydrochloric acid solution to adjust pH value of solution is 8.5, continues room temperature reaction 3 hours, then by above-mentioned solution centrifugal, separates and obtain poly- DOPA
The nano combined photothermal reagent of amine cladding, as uses the dendritic nano combined photo-thermal of gold and silver of the reduction of DOPA amine monomers one step and cladding
Reagent.Scantling is 110nm, and poly-dopamine shell thickness is 20nm, and surface plasma resonance peak is 800nm.(a) transmission electricity
Mirror photo, (b) ultraviolet spectrogram.Corresponding embodiment 11.
Fig. 7～Fig. 9 explanation adopts second method with DOPA amine monomers as reducing agent and the poly- DOPA of covering one-step synthesis
The dendritic nano combined photothermal reagent of gold and silver of amine cladding.By change DOPA amine monomers consumption can change material size and
The thickness of poly-dopamine shell.
Figure 10：Add 35 μ L, 0.1M chlorauric acid solutions in 25mL water, add 800 μ L silver nano-particle solution to react 3 points
Clock, adds the dopamine solution of 600 μ L, 0.03M to react 10 minutes, is subsequently added the Tris cushioning liquid of 25mL, 0.01M, auxiliary
Helping hydrochloric acid solution to adjust pH value of solution is 8.5, continues room temperature reaction 3 hours, then by above-mentioned solution centrifugal, separates and obtain poly- DOPA
The nano combined photothermal reagent of amine cladding, as uses the dendritic nano combined photo-thermal of gold and silver of the reduction of DOPA amine monomers one step and cladding
Reagent.Scantling is 90nm, and poly-dopamine shell thickness is 14nm, and surface plasma resonance peak is 760nm.(a) transmission electricity
Mirror photo, (b) ultraviolet spectrogram.Corresponding embodiment 13.
Figure 11：Add 75 μ L, 0.1M chlorauric acid solutions in 25mL water, add 800 μ L silver nano-particle solution to react 3 points
Clock, adds the dopamine solution of 600 μ L, 0.03M to react 10 minutes, is subsequently added the Tris cushioning liquid of 25mL, 0.01M, auxiliary
Helping hydrochloric acid solution to adjust pH value of solution is 8.5, continues room temperature reaction 3 hours, then by above-mentioned solution centrifugal, separates and obtain poly- DOPA
The nano combined photothermal reagent of amine cladding, as uses the dendritic nano combined photo-thermal of gold and silver of the reduction of DOPA amine monomers one step and cladding
Reagent.Scantling is 140nm, and poly-dopamine shell thickness is 25nm, and surface plasma resonance peak is 860nm.(a) transmission electricity
Mirror photo, (b) ultraviolet spectrogram.Corresponding embodiment 14.
Figure 10～Figure 11 explanation adopts second method with DOPA amine monomers as reducing agent and covering one-step synthesis is poly- many
The dendritic nano combined photothermal reagent of gold and silver of bar amine cladding.The size of material can be changed by changing the consumption of gold chloride.
Specific embodiment
With reference to embodiment, the present invention is further elaborated, rather than will be limited the invention with this.
Embodiment 1
Poly-dopamine shell is coated to inorganic nano-particle using first method：First by 1mg gold and silver branch to be covered
Shape nano-particle is dissolved in 5mL water, adds the Tris cushioning liquid of 5mL, 0.02M and assists hydrochloric acid solution so that reaction system pH is adjusted
Save to 8.5, be subsequently adding the dopamine solution (nano-particle of 100 μ L, 0.03M：Dopamine monomer concentration=0.1mg/mL：
0.045mg/mL), it is stirred at room temperature 3 hours, then by above-mentioned solution centrifugal, separate the nano compound light obtaining poly-dopamine cladding
Thermal agent；Poly-dopamine shell thickness is 6nm, and after cladding poly-dopamine shell, surface plasma resonance peak (is coated on for 811nm
The dopamine of nanoparticle surface only account for put into dopamine sub-fraction, quality very little, permissible compared to inorganic nano-particle
Ignore).
This gold and silver dendritic nano-particles size is 135nm, and plasma resonance peak is 800nm.This gold and silver is dendritic
The preparation method of nano-particle is：The first step prepares silver nano-particle solution：The silver nitrate of 17mg is added in 100mL water, plus
Hot extremely boiling, is subsequently adding the sodium citrate aqueous solution of 2mL, 1w/v%, keeps solution to seethe with excitement 1 hour, determines after being cooled to room temperature
Hold to 100mL, obtain a size of 50～60nm, silver atomic concentration be 1mM the stable silver nano-particle solution of sodium citrate.The
The dendritic particle of two step gold and silver synthesizes：Take 100 μ L, 0.1HAuCl4The aqueous solution adds in 10mL water, and stirring is lower to add 1mL silver nanoparticle
Particle solution, after reacting 2 minutes, adds the quinol solution of 1mL, 0.03mM, and solution is changed into black-and-blue, stirs 10 minutes
Afterwards, stop reaction, then by above-mentioned solution centrifugal, the gold and silver in the bottom nano-particle as embodiment 1 isolated is dendritic to be received
Rice corpuscles, this nano-particle quality is about 2mg.
Embodiment 2
Poly-dopamine shell is coated to inorganic nano-particle using first method：First by 1mg embodiment 1 to be covered
Described in the dendritic nano-particle of gold and silver be dissolved in 5mL water, add the Tris cushioning liquid of 5mL, 0.02M simultaneously to assist hydrochloric acid solution
So that reaction system pH is adjusted to 8.5 (cushioning liquid only provides alkaline environment, is not involved in reacting), be subsequently adding 200 μ L, 0.03M
Dopamine solution (nano-particle：Dopamine monomer concentration=0.1mg/mL：0.090mg/mL), it is stirred at room temperature 3 hours, then
By above-mentioned solution centrifugal, separate the nano combined photothermal reagent obtaining poly-dopamine cladding；Poly-dopamine shell thickness is 10nm,
After cladding poly-dopamine shell, surface plasma resonance peak is 817nm.
Embodiment 3
Poly-dopamine shell is coated to inorganic nano-particle using first method：First by 1mg embodiment 1 to be covered
Described in the dendritic nano-particle of gold and silver be dissolved in 5mL water, add the Tris cushioning liquid of 5mL, 0.02M simultaneously to assist hydrochloric acid solution
So that reaction system pH is adjusted to 8.5 (cushioning liquid only provides alkaline environment, is not involved in reacting), be subsequently adding 600 μ L, 0.03M
Dopamine solution (nano-particle：Dopamine monomer concentration=0.1mg/mL：0.260mg/mL), it is stirred at room temperature 3 hours, then
By above-mentioned solution centrifugal, separate the nano combined photothermal reagent obtaining poly-dopamine cladding；Poly-dopamine shell thickness is 34nm,
After cladding poly-dopamine shell, surface plasma resonance peak is 917nm.
Embodiment 1～3 illustrate be：Using first method in the poly- DOPA of gold and silver dendritic inorganic nano-particle Surface coating
Amine shell, and control the thickness of poly-dopamine shell by adjusting the consumption of DOPA amine monomers.As embodiment 1～3, with many
Bar amine monomers consumption increases, and shell thickness increases to 34nm by 6nm, and surface plasma resonance peak is by 811nm red shift to 917nm.
The phagocytosis amount that the regulation of shell thickness swallows nano-particle for cell in Bioexperiment is significant, the regulation of peak position for
The wavelength of the LASER Light Source matching with peak position used in Bioexperiment has material impact.
Embodiment 4
Poly-dopamine shell is coated to inorganic nano-particle using first method：First by 1mg sea urchin shape to be covered
Golden nanometer particle is dissolved in 5mL water, adds the Tris cushioning liquid of 5mL, 0.02M and assists hydrochloric acid solution so that reaction system pH is adjusted
Save to 8.5, be subsequently adding the dopamine solution (nano-particle of 200 μ L, 0.03M：Dopamine monomer concentration=0.1mg/mL：
0.090mg/mL), it is stirred at room temperature 3 hours, then by above-mentioned solution centrifugal, separate the nano compound light obtaining poly-dopamine cladding
Thermal agent；Poly-dopamine shell thickness is 12nm, and after cladding poly-dopamine shell, surface plasma resonance peak is 702nm.
The size of sea urchin shape golden nanometer particle is 120nm, and plasma resonance peak is 680nm, and this sea urchin shape receives
The preparation method of rice corpuscles is：The first step prepares solution of gold nanoparticles：By 75 μ L, 0.1M HAuCl4The aqueous solution be added to
In 30mL water, add the sodium citrate aqueous solution of 900 μ L, 1w/v%, solution after being stirred and heated to seethe with excitement immediately in solution
Gradually it is changed into purple from colourless, stop heating after eventually becoming claret, be settled to 30mL after being cooled to room temperature, obtain a size of
The stable solution of gold nanoparticles of 20nm, the gold atom concentration sodium citrate for 0.25mM.Second step sea urchin shape nano-particle
Synthesis：Take 25 μ L, 0.1M HAuCl4The aqueous solution be added in 9.6mL water, be added thereto under agitation 50 the μ L first steps close
The solution of gold nanoparticles becoming, after mixing, adds the sodium citrate aqueous solution 22 μ L of 1w/v%, adds 1mL 30mM immediately
Quinol solution, stirring stopped reaction after 30 minutes, and then by above-mentioned solution centrifugal, the bottom nano-particle isolated is
Sea urchin shape golden nanometer particle in embodiment 4, this nano-particle quality is about 0.5mg.
Embodiment 5
Poly-dopamine shell is coated to inorganic nano-particle using first method：First by 1mg gold nano to be covered
Rod is dissolved in 5mL water, adds the Tris cushioning liquid of 5mL, 0.02M and assists hydrochloric acid solution so that reaction system pH is adjusted to 8.5,
It is subsequently adding the dopamine solution (nano-particle of 200 μ L, 0.03M：Dopamine monomer concentration=0.1mg/mL：0.090mg/
ML), it is stirred at room temperature 3 hours, then by above-mentioned solution centrifugal, separate the nano combined photothermal reagent obtaining poly-dopamine cladding；
Poly-dopamine shell thickness is 10nm, and after cladding poly-dopamine shell, surface plasma resonance peak is 848nm.
This gold nanorods a size of 47 × 11nm, plasma resonance peak is 830nm, the preparation of this gold nanorods
Method is：Containing 50mM CTAB, 0.5mM HAuCl4Growth solution in add 110 μ L, 10mM AgNO3Afterwards, add no
500 μ L, 0.1M resveratrols of water-ethanol dissolving, after standing 10min under room temperature, add 15 μ L, 10mM of ice-water bath cooling
NaBH4, put into standing heating in 70 degree of water-baths after rocking 1min manually, the volume of whole reaction solution is 10mL.Reaction 6 is little
When after, by above-mentioned solution centrifugal, the bottom nano-particle isolated is the gold nanorods in embodiment 5, this nano-particle
Quality is about 1mg.
Embodiment 4～5 illustrate be：Using first method in inorganic nano-particle such as sea urchin shape golden nanometer particle and gold
Nanorod surfaces coat poly-dopamine shell.
Embodiment 6
Poly-dopamine shell is coated to the assembly of inorganic nano-particle using first method：First will be to be covered
1mg ferroso-ferric oxide superparticle is dissolved in 5mL water, adds the Tris cushioning liquid of 5mL, 0.02M and assists hydrochloric acid solution to make instead
The system pH of answering is adjusted to 8.5, is subsequently adding the dopamine solution (nano-particle of 200 μ L, 0.03M：Dopamine monomer concentration=
0.1mg/mL：0.090mg/mL), it is stirred at room temperature 3 hours, then by above-mentioned solution centrifugal, separate and obtain poly-dopamine cladding
Nano combined photothermal reagent；Poly-dopamine shell thickness is 8nm, and the assembly after cladding poly-dopamine shell is at near-infrared
Influx and translocation.
This ferroso-ferric oxide superparticle assembly a size of 55～65nm about, its preparation method is：The first step four aoxidizes
The synthesis of three Fe nanometer particles：By 2mmol Fe (acac) 3,10mmol 1,2- hexadecane diol, 6mmol octadecenic acid,
6mmol octadecenyl amine, 20mL benzyl ether is added sequentially in three neck round bottom, stirs 15 minutes under nitrogen protection.To mix
Close solution to be to slowly warm up to 200 DEG C (3 DEG C/min of programming rate), after backflow 30min, reaction solution is warming up to 265 DEG C and (heats up
3 DEG C/min of speed), continue heating stirring 30min.Solution is cooled to room temperature, adds the mixing of 40mL absolute ethyl alcohol, will with magnet
Product is separated, and is dissolved in chloroform, obtains the stable ferriferrous oxide nano-particle of octadecenic acid.Second step is four oxidations
The preparation of three-iron superparticle：During room temperature, under mechanical stirring lauryl sodium sulfate aqueous solution (28mg/mL, 5mL) is led to nitrogen
After 15 minutes, it is added dropwise over the toluene solution (10mg/mL) of 0.6mL ferriferrous oxide nano-particle, 60 DEG C of water-baths, ultrasonic agitation
Evaporation toluene, obtains 50-60nm ferroso-ferric oxide superparticle.
Embodiment 6 illustrate be：Wrapped on the assembly surface of ferroso-ferric oxide inorganic nano-particle using first method
Cover poly-dopamine shell.
Embodiment 7
The gold and silver of the poly-dopamine cladding that the dendritic nano-particle of gold and silver that describe embodiment 1 and embodiment 1 obtain is dendritic
Nano-particle is respectively dissolved in the cell training of water, 0.9w/v% sodium chloride solution, phosphate buffer solution (pH=7.4), serum-free
Foster base (has serum cell culture medium with having in the cell culture medium of serum：10% hyclone concentration；The dendritic nano-particle of gold and silver
It is 100mg/mL with the dendritic nanoparticle concentration of gold and silver of poly-dopamine cladding), after placing 48 hours, measure its ultraviolet spectra
Figure.It is found that having, the dendritic nano-particle of gold and silver that poly-dopamine coats is dendritic compared to the gold and silver of uncoated poly-dopamine to be received
Rice corpuscles surface plasma resonance peak is not moved, with more physiological environment stability.
Embodiment 7 illustrates the nanoparticle compared to uncoated poly-dopamine for the nano combined photothermal reagent of poly-dopamine cladding
Son, has more preferable physiological stability.
Embodiment 8
Under conditions of room temperature is 20 DEG C, the gold and silver of the different poly-dopamine shell thicknesses that embodiment 1-3 obtains is dendritic to be received
Rice corpuscles was through 30 minutes 808nm, 3W/cm2Under laser irradiates, measure the temperature change of solution.The light of three solution to be measured
The quality of thermal agent is identical.
Embodiment 8 illustrates that the nano combined photothermal reagent of poly-dopamine cladding has higher photo-thermal intensification ability, and its
Photo-thermal intensification ability increases with poly-dopamine shell thickness and strengthens.
Embodiment 9
Adopt second method with DOPA amine monomers as reducing agent and covering one-step synthesis poly-dopamine cladding gold and silver
Dendritic nano combined photothermal reagent：Add 50 μ L, 0.1M chlorauric acid solutions in 25mL water, add 800 μ L Nano silver grains molten
Liquid reacts 3 minutes, adds the dopamine solution of 200 μ L, 0.03M to react 10 minutes, the Tris being subsequently added 25mL, 0.01M delays
Rush solution, it is 8.5 that auxiliary hydrochloric acid solution adjusts pH value of solution, (the concentration of Chlorine in Solution auric acid, Nano silver grain and DOPA amine monomers
Ratio is 0.1mM:0.016mM:0.12mM) continue room temperature reaction 3 hours；Then by above-mentioned solution centrifugal, separation obtains poly- many
The nano combined photothermal reagent of bar amine cladding, as uses the dendritic nano compound light of gold and silver of the reduction of DOPA amine monomers one step and cladding
Thermal agent, the size of this particle is 60nm, and shell thickness is 3nm, and surface plasma resonance peak is 650nm.
Embodiment 10
Adopt second method with DOPA amine monomers as reducing agent and covering one-step synthesis poly-dopamine cladding gold and silver
Dendritic nano combined photothermal reagent：Add 50 μ L, 0.1M chlorauric acid solutions in 25mL water, add 800 μ L Nano silver grains molten
Liquid reacts 3 minutes, adds the dopamine solution of 400 μ L, 0.03M to react 10 minutes, the Tris being subsequently added 25mL, 0.01M delays
Rush solution, it is 8.5 that auxiliary hydrochloric acid solution adjusts pH value of solution, (the concentration of Chlorine in Solution auric acid, Nano silver grain and DOPA amine monomers
Ratio is 0.1mM:0.016mM:0.23mM) continue room temperature reaction 3 hours；Then by above-mentioned solution centrifugal, separation obtains poly- many
The nano combined photothermal reagent of bar amine cladding, as uses the dendritic nano compound light of gold and silver of the reduction of DOPA amine monomers one step and cladding
Thermal agent, the size of this particle is 100nm, and shell thickness is 15nm, and surface plasma resonance peak is 760nm.
Embodiment 11
Adopt second method with DOPA amine monomers as reducing agent and covering one-step synthesis poly-dopamine cladding gold and silver
Dendritic nano combined photothermal reagent：Add 50 μ L, 0.1M chlorauric acid solutions in 25mL water, add 800 μ L Nano silver grains molten
Liquid reacts 3 minutes, adds the dopamine solution of 600 μ L, 0.03M to react 10 minutes, the Tris being subsequently added 25mL, 0.01M delays
Rush solution, it is 8.5 that auxiliary hydrochloric acid solution adjusts pH value of solution, (the concentration of Chlorine in Solution auric acid, Nano silver grain and DOPA amine monomers
Ratio is 0.1mM:0.016mM:0.35mM) continue room temperature reaction 3 hours；Then by above-mentioned solution centrifugal, separation obtains poly- many
The nano combined photothermal reagent of bar amine cladding, as uses the dendritic nano compound light of gold and silver of the reduction of DOPA amine monomers one step and cladding
Thermal agent, the size of this particle is 110nm, and shell thickness is 20nm, and surface plasma resonance peak is 800nm.
Embodiment 12
Adopt second method with DOPA amine monomers as reducing agent and covering one-step synthesis poly-dopamine cladding gold and silver
Dendritic nano combined photothermal reagent：Add 50 μ L, 0.1M chlorauric acid solutions in 25mL water, add 800 μ L Nano silver grains molten
Liquid reacts 3 minutes, adds the dopamine solution of 800 μ L, 0.03M to react 10 minutes, the Tris being subsequently added 25mL, 0.01M delays
Rush solution, it is 8.5 that auxiliary hydrochloric acid solution adjusts pH value of solution, (the concentration of Chlorine in Solution auric acid, Nano silver grain and DOPA amine monomers
Ratio is 0.1mM:0.015mM:0.46mM) continue room temperature reaction 3 hours；Then by above-mentioned solution centrifugal, separation obtains poly- many
The nano combined photothermal reagent of bar amine cladding, as uses the dendritic nano compound light of gold and silver of the reduction of DOPA amine monomers one step and cladding
Thermal agent, the size of this particle is 110nm, and shell thickness is 30nm, and surface plasma resonance peak is 920nm.
What embodiment 9～12 illustrated is to adopt second method with DOPA amine monomers as reducing agent and covering one-step synthesis
The dendritic nano combined photothermal reagent of gold and silver of poly-dopamine cladding.Can by change dopamine consumption adjust particle size and
Shell thickness, changes surface plasma resonance peak shift.Such as embodiment 9～12, increases with DOPA amine monomers consumption, particle chi
Very little 110nm is increased to by 60nm, shell thickness increases to 30nm by 3nm, and surface plasma resonance peak is by 650nm red shift extremely
920nm.The phagocytosis amount that the regulation of shell thickness swallows nano-particle for cell in Bioexperiment is significant, the tune of peak position
Section has material impact for the wavelength of the LASER Light Source matching with peak position used in Bioexperiment.
Embodiment 13
Adopt second method with DOPA amine monomers as reducing agent and covering one-step synthesis poly-dopamine cladding gold and silver
Dendritic nano combined photothermal reagent：Add 35 μ L, 0.1M chlorauric acid solutions in 25mL water, add 800 μ L Nano silver grains molten
Liquid reacts 3 minutes, adds the dopamine solution of 600 μ L, 0.03M to react 10 minutes, the Tris being subsequently added 25mL, 0.01M delays
Rush solution, it is 8.5 that auxiliary hydrochloric acid solution adjusts pH value of solution, (the concentration of Chlorine in Solution auric acid, Nano silver grain and DOPA amine monomers
Ratio is 0.1mM:0.024mM:0.51mM) continue room temperature reaction 3 hours；Then by above-mentioned solution centrifugal, separation obtains poly- many
The nano combined photothermal reagent of bar amine cladding, as uses the dendritic nano compound light of gold and silver of the reduction of DOPA amine monomers one step and cladding
Thermal agent, the size of this particle is 90nm, and shell thickness is 14nm, and surface plasma resonance peak is 760nm.
Embodiment 14
Adopt second method with DOPA amine monomers as reducing agent and covering one-step synthesis poly-dopamine cladding gold and silver
Dendritic nano combined photothermal reagent：Add 75 μ L, 0.1M chlorauric acid solutions in 25mL water, add 800 μ L Nano silver grains molten
Liquid reacts 3 minutes, adds the dopamine solution of 600 μ L, 0.03M to react 10 minutes, the Tris being subsequently added 25mL, 0.01M delays
Rush solution, it is 8.5 that auxiliary hydrochloric acid solution adjusts pH value of solution, (the concentration of Chlorine in Solution auric acid, Nano silver grain and DOPA amine monomers
Ratio is 0.1mM:0.011mM:0.24mM) continue room temperature reaction 3 hours；Then by above-mentioned solution centrifugal, separation obtains poly- many
The nano combined photothermal reagent of bar amine cladding, as uses the dendritic nano compound light of gold and silver of the reduction of DOPA amine monomers one step and cladding
Thermal agent, the size of this particle is 140nm, and shell thickness is 25nm, and surface plasma resonance peak is 860nm.
What embodiment 13～14 illustrated is to adopt second method with DOPA amine monomers as reducing agent and the conjunction of covering one step
Become the dendritic nano combined photothermal reagent of gold and silver of poly-dopamine cladding.Particle chi can be adjusted by changing the consumption of gold chloride
Very little, shell thickness, change surface plasma resonance peak shift.Such as embodiment 13～14, increases with gold chloride consumption, particle chi
Very little 140nm is increased to by 90nm, shell thickness increases to 25nm by 14nm, and surface plasma resonance peak is by 760nm red shift extremely
860nm.
Embodiment 15
Adopt second method with DOPA amine monomers as reducing agent and covering one-step synthesis poly-dopamine cladding gold and silver
Dendritic nano combined photothermal reagent：Add 50 μ L, 0.1M chlorauric acid solutions in 25mL water, add 600 μ L Nano silver grains molten
Liquid reacts 3 minutes, adds the dopamine solution of 600 μ L, 0.03M to react 10 minutes, the Tris being subsequently added 25mL, 0.01M delays
Rush solution, it is 8.5 that auxiliary hydrochloric acid solution adjusts pH value of solution, (the concentration of Chlorine in Solution auric acid, Nano silver grain and DOPA amine monomers
Ratio is 0.1mM:0.012mM:0.35mM) continue room temperature reaction 3 hours；Then by above-mentioned solution centrifugal, separation obtains poly- many
The nano combined photothermal reagent of bar amine cladding, as uses the dendritic nano compound light of gold and silver of the reduction of DOPA amine monomers one step and cladding
Thermal agent, the size of this particle is 120nm, and shell thickness is 20nm, and surface plasma resonance peak is 870nm.
Embodiment 16
Adopt second method with DOPA amine monomers as reducing agent and covering one-step synthesis poly-dopamine cladding gold and silver
Dendritic nano combined photothermal reagent：Add 50 μ L, 0.1M chlorauric acid solutions in 25mL water, add 1200 μ L Nano silver grains molten
Liquid reacts 3 minutes, adds the dopamine solution of 600 μ L, 0.03M to react 10 minutes, the Tris being subsequently added 25mL, 0.01M delays
Rush solution, it is 8.5 that auxiliary hydrochloric acid solution adjusts pH value of solution, (the concentration of Chlorine in Solution auric acid, Nano silver grain and DOPA amine monomers
Ratio is 0.1mM:0.023mM:0.35mM) continue room temperature reaction 3 hours；Then by above-mentioned solution centrifugal, separation obtains poly- many
The nano combined photothermal reagent of bar amine cladding, as uses the dendritic nano compound light of gold and silver of the reduction of DOPA amine monomers one step and cladding
Thermal agent, the size of this particle is 85nm, and shell thickness is 18nm, and surface plasma resonance peak is 770nm.
What embodiment 15～16 illustrated is to adopt second method with DOPA amine monomers as reducing agent and the conjunction of covering one step
Become the dendritic nano combined photothermal reagent of gold and silver of poly-dopamine cladding.Particle can be adjusted by changing the consumption of Nano silver grain
Size, shell thickness, change surface plasma resonance peak shift.Such as embodiment 15～16, increases with Nano silver grain consumption,
Particle size is decreased to 85nm by 120nm, and shell thickness is reduced to 18nm by 20nm, and surface plasma resonance peak is blue by 870nm
Move to 770nm.
Embodiment 17
Adopt second method with DOPA amine monomers as reducing agent and covering one-step synthesis poly-dopamine cladding gold and silver
Dendritic nano combined photothermal reagent：Add 50 μ L, 0.1M chlorauric acid solutions in 25mL water, add 800 μ L Nano silver grains molten
Liquid reacts 3 minutes, adds the dopamine solution of 600 μ L, 0.03M to react 10 minutes, the Tris being subsequently added 25mL, 0.01M delays
Rush solution, it is 7.5 that auxiliary hydrochloric acid solution adjusts pH value of solution, (the concentration of Chlorine in Solution auric acid, Nano silver grain and DOPA amine monomers
Ratio is 0.1mM:0.016mM:0.35mM) continue room temperature reaction 3 hours；Then by above-mentioned solution centrifugal, separation obtains poly- many
The nano combined photothermal reagent of bar amine cladding, as uses the dendritic nano compound light of gold and silver of the reduction of DOPA amine monomers one step and cladding
Thermal agent, the size of this particle is 110nm, and shell thickness is 35nm, and surface plasma resonance peak is 930nm.
Embodiment 18
Adopt second method with DOPA amine monomers as reducing agent and covering one-step synthesis poly-dopamine cladding gold and silver
Dendritic nano combined photothermal reagent：Add 50 μ L, 0.1M chlorauric acid solutions in 25mL water, add 800 μ L Nano silver grains molten
Liquid reacts 3 minutes, adds the dopamine solution of 600 μ L, 0.03M to react 10 minutes, the Tris being subsequently added 25mL, 0.01M delays
Rush solution, it is 9.0 that auxiliary hydrochloric acid solution adjusts pH value of solution, (the concentration of Chlorine in Solution auric acid, Nano silver grain and DOPA amine monomers
Ratio is 0.1mM:0.016mM:0.35mM) continue room temperature reaction 3 hours；Then by above-mentioned solution centrifugal, separation obtains poly- many
The nano combined photothermal reagent of bar amine cladding, as uses the dendritic nano compound light of gold and silver of the reduction of DOPA amine monomers one step and cladding
Thermal agent, the size of this particle is 110nm, and shell thickness is 9nm, and surface plasma resonance peak is 780nm.
What embodiment 17～18 illustrated is to adopt second method with DOPA amine monomers as reducing agent and the conjunction of covering one step
Become the dendritic nano combined photothermal reagent of gold and silver of poly-dopamine cladding.Shell thickness can be adjusted by changing the pH value of solution,
Change surface plasma resonance peak shift.Such as embodiment 17～18, with the increase of pH value of solution, particle shell thickness is dropped by 35nm
As little as 9nm, surface plasma resonance peak is blue shifted to 780nm by 930nm.
Embodiment 19
Adopt second method with DOPA amine monomers as reducing agent and covering one-step synthesis poly-dopamine cladding gold and silver
Dendritic nano combined photothermal reagent：Add 50 μ L, 0.1M chlorauric acid solutions in 25mL water, add 800 μ L Nano silver grains molten
Liquid reacts 3 minutes, adds the dopamine solution of 600 μ L, 0.03M to react 10 minutes, the Tris being subsequently added 25mL, 0.01M delays
Rush solution, it is 8.5 that auxiliary hydrochloric acid solution adjusts pH value of solution, (the concentration of Chlorine in Solution auric acid, Nano silver grain and DOPA amine monomers
Ratio is 0.1mM:0.016mM:0.35mM) continue room temperature reaction 1 hour；Then by above-mentioned solution centrifugal, separation obtains poly- many
The nano combined photothermal reagent of bar amine cladding, as uses the dendritic nano compound light of gold and silver of the reduction of DOPA amine monomers one step and cladding
Thermal agent, the size of this particle is 110nm, and shell thickness is 18nm, and surface plasma resonance peak is 790nm.
Embodiment 20
Adopt second method with DOPA amine monomers as reducing agent and covering one-step synthesis poly-dopamine cladding gold and silver
Dendritic nano combined photothermal reagent：Add 50 μ L, 0.1M chlorauric acid solutions in 25mL water, add 800 μ L Nano silver grains molten
Liquid reacts 3 minutes, adds the dopamine solution of 600 μ L, 0.03M to react 10 minutes, the Tris being subsequently added 25mL, 0.01M delays
Rush solution, it is 8.5 that auxiliary hydrochloric acid solution adjusts pH value of solution, (the concentration of Chlorine in Solution auric acid, Nano silver grain and DOPA amine monomers
Ratio is 0.1mM:0.016mM:0.35mM) continue room temperature reaction 6 hours；Then by above-mentioned solution centrifugal, separation obtains poly- many
The nano combined photothermal reagent of bar amine cladding, as uses the dendritic nano compound light of gold and silver of the reduction of DOPA amine monomers one step and cladding
Thermal agent, the size of this particle is 110nm, and shell thickness is 30nm, and surface plasma resonance peak is 900nm.
What embodiment 19～20 illustrated is to adopt second method with DOPA amine monomers as reducing agent and the conjunction of covering one step
Become the dendritic nano combined photothermal reagent of gold and silver of poly-dopamine cladding.Shell thickness can be adjusted by adjusting reaction time, change
Become surface plasma resonance peak shift.Such as embodiment 19～20, increased with the reaction time, and particle shell thickness is increased by 18nm
To 30nm, surface plasma resonance peak is by 790nm red shift to 900nm.
Claims (6)
1. a kind of nano combined photothermal reagent of poly-dopamine cladding preparation method it is characterised in that：It is first will be to be covered
Inorganic nano-particle or its assembly soluble in water, adjust pH value of solution to alkaline, be subsequently adding DOPA amine monomers；In solution no
Machine nano-particle or its assembly are 0.1mg/mL with the concentration ratio scope of DOPA amine monomers:0.045～0.45mg/mL；Room
Temperature stirring 1～6 hour, solution becomes brownish black, then by above-mentioned solution centrifugal, isolates the inorganic nano of poly-dopamine cladding
Particle or its assembly, that is, obtain the nano combined photothermal reagent of poly-dopamine cladding.
2. the preparation method of the nano combined photothermal reagent of a kind of poly-dopamine cladding as claimed in claim 1, its feature exists
In：Inorganic nano-particle or its assembly are to receive the noble metal nano particles of various patterns of micro-dimension or its assembly, ferromagnetic
Property one of nano-particle or its assembly, semi-conductor nano particles.
3. the preparation method of the nano combined photothermal reagent of a kind of poly-dopamine cladding as claimed in claim 1, its feature exists
In：It is molten with trishydroxymethylaminomethane cushioning liquid, sodium hydroxide solution, borax buffer solution or ammonia spirit cooperation hydrochloric acid
Liquid adjusts pH value of solution to alkalescence, pH=7.5～9.0.
4. a kind of nano combined photothermal reagent of poly-dopamine cladding preparation method it is characterised in that：Prepare first a size of
The stable silver nano-particle solution of 50～60nm, the silver atomic concentration sodium citrate for 1mM；Again by gold chloride and this nano grain of silver
The mixing of sub- solution carries out potential difference substitution reaction in 2～5 minutes, is subsequently adding DOPA amine monomers by Au remaining in solutionIIIAnd electricity
The Ag that potential difference substitution reaction generatesIAll it is deposited on the Jin Heshang of potential difference substitution reaction generation, Chlorine in Solution auric acid, silver nanoparticle
The concentration ratio scope of particle and DOPA amine monomers is 0.1mM:0.011～0.032mM:0.12～0.72mM；5～15 minutes
Afterwards, adjust pH value of solution to alkalescence, continue room temperature reaction 1～6 hour, solution becomes brownish black；Then by above-mentioned solution centrifugal, point
From the nano combined photothermal reagent obtaining poly-dopamine cladding.
5. the preparation method of the nano combined photothermal reagent of a kind of poly-dopamine cladding as claimed in claim 4, its feature exists
In：It is molten with trishydroxymethylaminomethane cushioning liquid, sodium hydroxide solution, borax buffer solution or ammonia spirit cooperation hydrochloric acid
Liquid adjusts pH value of solution to alkalescence, pH=7.5～9.0.
6. a kind of poly-dopamine cladding nano combined photothermal reagent it is characterised in that：It is by Claims 1 to 5 any one
Methods described prepares.
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