CN108465114A - A kind of poly-dopamine-polypyrrole nanocomposite and its preparation method and application - Google Patents
A kind of poly-dopamine-polypyrrole nanocomposite and its preparation method and application Download PDFInfo
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- 229920000128 polypyrrole Polymers 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000002114 nanocomposite Substances 0.000 title claims abstract description 12
- 239000002105 nanoparticle Substances 0.000 claims abstract description 29
- 238000003384 imaging method Methods 0.000 claims abstract description 20
- 238000001069 Raman spectroscopy Methods 0.000 claims abstract description 15
- 239000000463 material Substances 0.000 claims abstract description 14
- 229920001690 polydopamine Polymers 0.000 claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 10
- 239000002270 dispersing agent Substances 0.000 claims abstract description 6
- 238000007626 photothermal therapy Methods 0.000 claims abstract description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000000377 silicon dioxide Substances 0.000 claims description 8
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 239000007800 oxidant agent Substances 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- 229960003638 dopamine Drugs 0.000 claims description 5
- 235000019441 ethanol Nutrition 0.000 claims description 5
- 229910021389 graphene Inorganic materials 0.000 claims description 5
- 150000003233 pyrroles Chemical class 0.000 claims description 5
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 4
- 229920002385 Sodium hyaluronate Polymers 0.000 claims description 4
- 230000001590 oxidative effect Effects 0.000 claims description 4
- 229920000642 polymer Polymers 0.000 claims description 4
- 229940010747 sodium hyaluronate Drugs 0.000 claims description 4
- YWIVKILSMZOHHF-QJZPQSOGSA-N sodium;(2s,3s,4s,5r,6r)-6-[(2s,3r,4r,5s,6r)-3-acetamido-2-[(2s,3s,4r,5r,6r)-6-[(2r,3r,4r,5s,6r)-3-acetamido-2,5-dihydroxy-6-(hydroxymethyl)oxan-4-yl]oxy-2-carboxy-4,5-dihydroxyoxan-3-yl]oxy-5-hydroxy-6-(hydroxymethyl)oxan-4-yl]oxy-3,4,5-trihydroxyoxane-2- Chemical group [Na+].CC(=O)N[C@H]1[C@H](O)O[C@H](CO)[C@@H](O)[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@H](O[C@H]2[C@@H]([C@@H](O[C@H]3[C@@H]([C@@H](O)[C@H](O)[C@H](O3)C(O)=O)O)[C@H](O)[C@@H](CO)O2)NC(C)=O)[C@@H](C(O)=O)O1 YWIVKILSMZOHHF-QJZPQSOGSA-N 0.000 claims description 4
- CTENFNNZBMHDDG-UHFFFAOYSA-N Dopamine hydrochloride Chemical compound Cl.NCCC1=CC=C(O)C(O)=C1 CTENFNNZBMHDDG-UHFFFAOYSA-N 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 238000005119 centrifugation Methods 0.000 claims description 2
- 229960001149 dopamine hydrochloride Drugs 0.000 claims description 2
- 150000004676 glycans Chemical class 0.000 claims description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052737 gold Inorganic materials 0.000 claims description 2
- 239000010931 gold Substances 0.000 claims description 2
- 238000002595 magnetic resonance imaging Methods 0.000 claims description 2
- 239000000178 monomer Substances 0.000 claims description 2
- 229920001282 polysaccharide Polymers 0.000 claims description 2
- 239000005017 polysaccharide Substances 0.000 claims description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 2
- 238000003786 synthesis reaction Methods 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims 2
- 229920002567 Chondroitin Polymers 0.000 claims 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims 1
- DLGJWSVWTWEWBJ-HGGSSLSASA-N chondroitin Chemical compound CC(O)=N[C@@H]1[C@H](O)O[C@H](CO)[C@H](O)[C@@H]1OC1[C@H](O)[C@H](O)C=C(C(O)=O)O1 DLGJWSVWTWEWBJ-HGGSSLSASA-N 0.000 claims 1
- 239000002131 composite material Substances 0.000 abstract description 16
- 238000003745 diagnosis Methods 0.000 abstract description 9
- 239000002086 nanomaterial Substances 0.000 abstract description 7
- 238000005253 cladding Methods 0.000 abstract description 4
- 235000007164 Oryza sativa Nutrition 0.000 abstract description 3
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 3
- 239000002872 contrast media Substances 0.000 abstract description 3
- 238000001514 detection method Methods 0.000 abstract description 3
- 235000009566 rice Nutrition 0.000 abstract description 3
- 229920002521 macromolecule Polymers 0.000 abstract description 2
- 240000007594 Oryza sativa Species 0.000 abstract 1
- 239000008346 aqueous phase Substances 0.000 abstract 1
- 238000007385 chemical modification Methods 0.000 abstract 1
- 239000003814 drug Substances 0.000 abstract 1
- 229910052709 silver Inorganic materials 0.000 abstract 1
- 239000004332 silver Substances 0.000 abstract 1
- 206010028980 Neoplasm Diseases 0.000 description 10
- 235000012239 silicon dioxide Nutrition 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 201000011510 cancer Diseases 0.000 description 4
- 238000002601 radiography Methods 0.000 description 4
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 3
- 239000002322 conducting polymer Substances 0.000 description 3
- 229920001940 conductive polymer Polymers 0.000 description 3
- -1 dopamine hydrochlorides Chemical class 0.000 description 3
- 229910001447 ferric ion Inorganic materials 0.000 description 3
- 239000001963 growth medium Substances 0.000 description 3
- 239000005457 ice water Substances 0.000 description 3
- 238000001727 in vivo Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- SQDAZGGFXASXDW-UHFFFAOYSA-N 5-bromo-2-(trifluoromethoxy)pyridine Chemical compound FC(F)(F)OC1=CC=C(Br)C=N1 SQDAZGGFXASXDW-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- 229920001287 Chondroitin sulfate Polymers 0.000 description 2
- 241000209094 Oryza Species 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 229940059329 chondroitin sulfate Drugs 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000000799 fluorescence microscopy Methods 0.000 description 2
- 239000003574 free electron Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000002082 metal nanoparticle Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000012544 monitoring process Methods 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 238000012634 optical imaging Methods 0.000 description 2
- 230000008520 organization Effects 0.000 description 2
- 150000004968 peroxymonosulfuric acids Chemical class 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- 241000790917 Dioxys <bee> Species 0.000 description 1
- 239000006144 Dulbecco’s modified Eagle's medium Substances 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- WTDRDQBEARUVNC-UHFFFAOYSA-N L-Dopa Natural products OC(=O)C(N)CC1=CC=C(O)C(O)=C1 WTDRDQBEARUVNC-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 229910003978 SiClx Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- 239000002775 capsule Substances 0.000 description 1
- 230000001413 cellular effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 229920000547 conjugated polymer Polymers 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000013399 early diagnosis Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000005669 field effect Effects 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 231100000734 genotoxic potential Toxicity 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000011534 incubation Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 229960004502 levodopa Drugs 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 231100001252 long-term toxicity Toxicity 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- 238000003541 multi-stage reaction Methods 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 210000000056 organ Anatomy 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 230000005622 photoelectricity Effects 0.000 description 1
- 230000003389 potentiating effect Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000002198 surface plasmon resonance spectroscopy Methods 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 230000008685 targeting Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K49/00—Preparations for testing in vivo
- A61K49/22—Echographic preparations; Ultrasound imaging preparations ; Optoacoustic imaging preparations
- A61K49/222—Echographic preparations; Ultrasound imaging preparations ; Optoacoustic imaging preparations characterised by a special physical form, e.g. emulsions, liposomes
- A61K49/223—Microbubbles, hollow microspheres, free gas bubbles, gas microspheres
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- A61K41/00—Medicinal preparations obtained by treating materials with wave energy or particle radiation ; Therapies using these preparations
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- A61K49/06—Nuclear magnetic resonance [NMR] contrast preparations; Magnetic resonance imaging [MRI] contrast preparations
- A61K49/18—Nuclear magnetic resonance [NMR] contrast preparations; Magnetic resonance imaging [MRI] contrast preparations characterised by a special physical form, e.g. emulsions, microcapsules, liposomes
- A61K49/1818—Nuclear magnetic resonance [NMR] contrast preparations; Magnetic resonance imaging [MRI] contrast preparations characterised by a special physical form, e.g. emulsions, microcapsules, liposomes particles, e.g. uncoated or non-functionalised microparticles or nanoparticles
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Abstract
The invention belongs to technical field of biomedical materials, specially the poly-dopamine polypyrrole nanocomposite and its preparation method and application with a variety of diagnosis and treatment functions.The present invention uses simple one kettle way, and poly-dopamine silver/poly pyrrole composite nano material is synthesized on nano template surface using macromolecule dispersing agent in aqueous phase system.Poly-dopamine material and the contrast agent that polypyrrole material is common photo-thermal therapy reagent and photoacoustic imaging.Compared with single poly-dopamine and polypyrrole, there are two kinds of detection signals of high Raman and high photoacoustic imaging and high photothermal conversion efficiency in the poly-dopamine Pt/Polypyrrole composite material of nanoparticle surface cladding, three kinds of medicine, multi-modal imaging and treatment functions are carried without can be achieved at the same time by further chemical modification, becoming a kind of novel diagnosis and treatment Integral rice corpuscles.
Description
Technical field
The invention belongs to technical field of biomedical materials, and in particular to a kind of nanocomposite and preparation method thereof and
Using.
Background technology
The World Health Organization points out that cancer has become whole world morbidity and death at present in cancer report in 2015
The early detection of main cause, tumour helps to improve the survival rate of patient.The early detection of tumour be unable to do without accurate effective
Imaging in sensitivity, spatial resolution, specificity and penetrates depth at present clinically and some emerging imaging means
All respectively there is certain limitation on degree.Therefore, the advantage in conjunction with a variety of imaging patterns respectively is conducive to obtain comprehensive group
Information is knitted, effective position tumour realizes the early diagnosis of cancer.
In recent years, with the development of nanotechnology, people gradually turn one's attention to nano material answering in tumour diagnosis and treatment
With, on imaging angle for, the function of nano-particle itself is utilized on single nano-particle, or passes through physical chemistry
Used load contrast agent can realize a variety of imaging functions on the same vector, be conducive to positioning tumor, monitoring curative effect.However
The current nano material with a variety of radiography functions, typically carries out the combination of radiography function by the method subsequently modified
, multi step modification can seriously affect the characteristic in the dispersibility and pharmacokinetics of nano material；In addition, multistep reaction can not
Toxic reagent is used in the meeting avoided, also can be unfavorable for its further application to the genotoxic potential of raising nano-particle.These are asked
One of solution of topic is the novel nano material itself with a variety of imaging functions of exploitation, at present to this aspect
Investigation of materials mainly also focuses in inorganic material, has there is a series of document surfaces, inorganic to receive in subsequent metabolism
Rice can be trapped in vivo for a long time, and can bring toxicity to other organs.Therefore, itself is developed with the poly- of multiple functions imaging
Close the new direction that object material is multi-modal imaging material future.
Semi-conducting polymer is a kind of common conductive material, is often used in and prepares photoelectricity composite material, field-effect
Transistor and biosensor etc..In recent years, excellent photothermal conversion performance makes it in exploitation New Generation Optical acoustic imaging radiography
It is received significant attention in agent or the exploitation of photo-thermal therapy reagent.And it due to the conjugated structure of its main polymer chain, makes it have
Stronger Raman image signal.Wherein photoacoustic imaging is a kind of deep penetration for the highly selective and ultrasonic imaging having both optical imagery
The Optical Imaging Modes of the advantages of characteristic can be obtained the organization chart picture of high-resolution and high contrast, light avoided from principle
The influence of scattering breaches high resolution optical imaging depth " soft limiting ".And Raman image is as pure optical imagery means,
Can realize can effectively evade the bleaching of fluorescence imaging while high sensitivity, the high-resolution of fluorescence imaging, background is made an uproar
Problem caused by the effect of sound and fluorescence probe and tissue.And due to the simple feature of its fast imaging, device, in hand
There is in art in imaging good application value.However the main problem of Raman image is difference in signal strength, needs to pass through increasing
It is potent to carry out promotion signal intensity.The common Raman enhancements of biomedicine field are broadly divided into two kinds at present, one is sharp
With the surface plasmon resonance effect of noble metal nano particles；The second is the light absorpting ability and Raman using material itself dissipate
Capable resonance is injected, the amplification of Raman signal is realized with this.The former introduces noble metal nano particles difficult to degrade so that nanoparticle
Son can have long term toxicity in vivo；The problem of the latter is primarily present is that amplified signal level number is limited, it is difficult to which realization is answered in vivo
With.And existing theory shows the signal strength of both imaging patterns, all related with the free electron movement in system.
In this system, we have selected a kind of common semi-conducting polymer -- polypyrrole, by itself and poly- DOPA
Amine forms composite material, and reinforces locomitivity of the free electron in semi-conducting polymer by specific method, substantially
While the photo-thermal curative effect of raising, photoacoustic signal and Raman signal, the problem of significantly improving the modification of polypyrrole difficulty, not only carry
Its high biocompatibility, and further expanded its application in biomedicine field.In addition, being obtained with prepared before
To amorphous or micron level capsule compare, this material is integrated in nanoscale by us, makes it as cancer
Diagnosis and treatment material preferably can be enriched with and permeate in tumor locus.Multifunctional composite nanometer material in the present invention, prepared
A variety of nano templates, stabilizer can be used in journey, there is certain universality, therefore in structure diagnosis and treatment integration of new generation
Nano platform plays an important role.
Invention content
The purpose of the present invention is to provide a kind of poly-dopamine-polypyrrole nanocomposites with a variety of diagnosis and treatment functions
And preparation method thereof, and the application of this composite material is provided.
The preparation method of poly-dopamine provided by the invention-polypyrrole nanocomposite, is as follows：
（1）Nano-particle is dispersed in the deionized water of certain pH value；
（2）Dispersant is added, is stirred at room temperature 16-28 hours；
（3）Step is added in dopamine hydrochloride and pyrrole monomer（2）In the solution of gained, it is uniformly dispersed；
（4）Oxidant is dissolved in deionized water, and the pH value and step of the deionized water（1）In solution ph it is identical,
To step（3）Configured oxidizing agent solution is added dropwise in the solution of gained；
（5）Low-temp reaction is kept to stay overnight, centrifugation is washed for several times with water and ethyl alcohol, is dried in vacuo to get nano-particle has been coated
Poly-dopamine-polypyrrole（That is nucleocapsid）Nanocomposite.
In the present invention, the nano-particle can be a series of common organic/inorganic nano-particles, for example, dioxy
SiClx, mesoporous silicon oxide, gold nanoparticle, polymer nano-particle, graphene etc..
In the present invention, the dispersant can be natural polysaccharide, such as Sodium Hyaluronate, chondroitin sulfate etc., also may be used
To be synthesis macromolecule, such as polyvinylpyrrolidone etc..
In the present invention, the oxidant is persulfate.
In the present invention, for the pH value of reaction system between 1 ~ 8.5, preferably pH is 6 ~ 7.5.
In the present invention, the molar ratio of pyrroles and dopamine is 10:1~1:Between 5.Preferred molar ratio is 6:1~1:3.
In the present invention, when solution centrifuges, 9000 ~ 11000 r/min of rotating speed, 20 ~ 30 min of time.
The poly-dopamine of nucleocapsid prepared by the present invention-polypyrrole nanocomposite, itself has Raman and optoacoustic
Radiography function, photo-thermal therapy functions of two kinds of imagings, and this composite material is for single polymers, treatment and at
The effect of picture has been greatly improved.
The nanometer kind composite material of the present invention, raw material are easy to get, and can be anti-by " one kettle way " in water solution system
It should be made, for the synthetic method of other conjugated polymers, effectively avoid and use organic solvent and multistep
It the problem of bio distribution and toxicity that reaction zone comes, has a good application prospect.
The composite material that the present invention obtains is coated on a series of nano-material surfaces, has good modifiability energy.Energy
It is enough in load chemotherapeutics, targeting ligand, Fe3+Or Gd3+A series of equal contrast agent etc. functional moleculars；Can to its into
The further functions expanding of row, is used to prepare Raman image, photoacoustic imaging, Magnetic resonance imaging and photo-thermal therapy material etc.,
And it can be used as a nano platform, be combined with other functionalization components, it is further to build multifunctional nano diagnosis and treatment one
Body system.
Description of the drawings
Fig. 1 is that poly-dopamine-Pt/Polypyrrole composite material of 1 gained of embodiment is coated on Nano particles of silicon dioxide surface
Transmission electron microscope photo.
Fig. 2 is the UV-visible-near infrared absorption of poly-dopamine-Pt/Polypyrrole composite material of 1 gained of embodiment
Figure.
Fig. 3 is the Raman spectrogram of poly-dopamine-Pt/Polypyrrole composite material of 1 gained of embodiment
Fig. 4 is the Raman image photo on cellular level in embodiment 1（Under）.
Fig. 5 is the photoacoustic signal optoacoustic picture of poly-dopamine-Pt/Polypyrrole composite material of 1 gained of embodiment.
Fig. 6 is that the poly-dopamine Pt/Polypyrrole composite material for having loaded ferric ion external 1/ of 6 gained of embodiment is longitudinal
Relaxation time ~ concentration curve.
Fig. 7 is that the heating that poly-dopamine-Pt/Polypyrrole composite material of 5 gained of embodiment receives after near-infrared laser irradiation is bent
Line chart.
Fig. 8 is that poly-dopamine-Pt/Polypyrrole composite material of 3 gained of embodiment is coated on the transmission electricity of surface of graphene oxide
Sub- microscope photo.
Specific implementation mode
The present invention is further described in detail below in conjunction with specific embodiments and the drawings, example is served only for solving
The present invention is released, is not intended to limit the scope of the present invention：
Embodiment 1：
The mass concentration for preparing pH=1 is 0.2% Nano particles of silicon dioxide solution, 25 mL, and the chondroitin sulfate of 200 mg is added,
It stirs 24 hours at room temperature；189 mg dopamine hydrochlorides are added, 70 μ L pyrroles, stirring is until dissolving；0.456 g persulfuric acid
Ammonium is dissolved in Nano particles of silicon dioxide solution mixed liquor being added dropwise after dissolving in 5 mL water in ice-water bath, keeps low temperature,
Reaction is overnight.It is washed for several times with water and ethyl alcohol, vacuum drying, obtains the silica dioxide nano particle of polypyrrole-poly-dopamine cladding
Son（See Fig. 1）.
Embodiment 2：
The mass concentration for preparing pH=1 is 0.2% Nano particles of silicon dioxide solution, 25 mL, and the Sodium Hyaluronate of 200 mg is added,
It stirs 24 hours at room temperature；189 mg dopamine hydrochlorides are added, 70 μ L pyrroles, stirring is until dissolving；0.456 g persulfuric acid
Ammonium is dissolved in Nano particles of silicon dioxide solution mixed liquor being added dropwise after dissolving in 5 mL water in ice-water bath, keeps low temperature,
Reaction is overnight.It is washed for several times with water and ethyl alcohol, vacuum drying, obtains the silica dioxide nano particle of polypyrrole-poly-dopamine cladding
Son.
Embodiment 3：
The mass concentration for preparing pH=1 is 0.2% graphene oxide solution, 25 mL, the Sodium Hyaluronate of 200 mg is added, at room temperature
Stirring 24 hours；189 mg dopamine hydrochlorides are added, 70 μ L pyrroles, stirring is until dissolving；0.456 g ammonium persulfates are dissolved in 5
The Nano particles of silicon dioxide solution in ice-water bath is added dropwise in mixed liquor after being dissolved in ml water, keeps low temperature, reaction is overnight.
It is washed for several times with water and ethyl alcohol, vacuum drying, obtains the stannic oxide/graphene nano material of polypyrrole-poly-dopamine cladding（See figure
2）.
The diagnosis and treatment Integral rice corpuscles with nucleocapsid for preparing embodiment 1 is tested in detail below to examine
It surveys：
Embodiment 4：
Enter the process of cell, nuclear shell structure nano prepared by monitoring embodiment 1 with laser Raman spectrometer characterization nano-particle
Particle enters the case where cell.HeLa cells cultivate 24 h in DMEM culture mediums, and culture medium is sucked out, and addition is prepared with culture medium
100 μ g/mL embodiments 1 in prepared nano-particle co-incubation, the culture medium containing material is inhaled in different time
Go out, cleaned three times with PBS, cell fixation is placed on laser Raman spectrometer（With dark field microscope）Lower test（See Fig. 3,4）.
Embodiment 5：
Using 1 preparation-obtained nano-particle of embodiment, the PBS dispersion liquids of a concentration of 50 μ g/mL are respectively configured, use wave
A length of 808 nm, energy density are 2 W/cm2Each dispersion liquid of laser irradiation and control group, and measure temperature in different time periods and become
Change（See Fig. 7）.
Embodiment 6：
Using 1 preparation-obtained nano-particle of embodiment, six water and ferric chloride solution of 1 M are dispersed in, are stirred overnight at room temperature.
It is dry after centrifuge washing.It is the mM solution of 2 mM, 1.5 mM, 1.0 mM, 0.5 that ferric ion concentration, which is respectively configured, and with
Solution without the diagnosis and treatment nano-particle as a control group, is positioned under the magnetic field of 0.5 T and obtains T1The nuclear magnetic resonance of weighting
Images（See Fig. 8）.
Claims (10)
1. a kind of preparation method of poly-dopamine-polypyrrole nanocomposite, which is characterized in that be as follows：
（1）Nano-particle is dispersed in the deionized water of certain pH value；
（2）Dispersant is added, is stirred at room temperature 16-28 hours；
（3）Step is added in dopamine hydrochloride and pyrrole monomer（2）In the solution of gained, it is uniformly dispersed；
（4）Oxidant is dissolved in deionized water, and the pH value and step of the deionized water（1）In solution ph it is identical,
To step（3）Configured oxidizing agent solution is added dropwise in the solution of gained；
（5）Low-temp reaction is kept to stay overnight, centrifugation is washed for several times with water and ethyl alcohol, is dried in vacuo to get nano-particle has been coated
Poly-dopamine-polypyrrole nanocomposite.
2. preparation method according to claim 1, which is characterized in that the nano-particle is silica, mesoporous two
Silica, gold nanoparticle, polymer nano-particle or graphene.
3. preparation method according to claim 1, which is characterized in that the dispersant is natural polysaccharide or synthesis high score
Son.
4. preparation method according to claim 3, which is characterized in that the dispersant is selected from Sodium Hyaluronate, sulfuric acid
Chondroitin, polyvinylpyrrolidone.
5. according to the preparation method described in one of claim 1-4, which is characterized in that oxidant used is ammonium persulfate.
6. preparation method according to claim 5, which is characterized in that the pH value of reaction system is between 1-8.5.
7. according to the preparation method described in claim 1-4, one of 6, which is characterized in that the molar ratio of pyrroles and dopamine is
10:1—1:5。
8. preparation method according to claim 7, which is characterized in that when solution centrifuges, 9000-11000 r/ of rotating speed
Min, 20-30 min of time.
9. a kind of poly-dopamine obtained by one of the claim 1-8 preparation methods-polypyrrole nanocomposite.
10. poly-dopamine as claimed in claim 9-polypyrrole nanocomposite, prepare Raman image, photoacoustic imaging,
Application in terms of Magnetic resonance imaging and photo-thermal therapy material.
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