CN106310259A - Multifunctional nanocomposite as well as preparation method and application thereof - Google Patents
Multifunctional nanocomposite as well as preparation method and application thereof Download PDFInfo
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- 239000002114 nanocomposite Substances 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000010931 gold Substances 0.000 claims abstract description 44
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims abstract description 34
- 229910052737 gold Inorganic materials 0.000 claims abstract description 34
- 238000005406 washing Methods 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 8
- 238000000502 dialysis Methods 0.000 claims abstract description 3
- 238000003756 stirring Methods 0.000 claims abstract description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 32
- 229910052741 iridium Inorganic materials 0.000 claims description 15
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 15
- CGUXYKPTTSTGQV-UHFFFAOYSA-N acetic acid;dysprosium Chemical compound [Dy].CC(O)=O CGUXYKPTTSTGQV-UHFFFAOYSA-N 0.000 claims description 11
- 229910004042 HAuCl4 Inorganic materials 0.000 claims description 8
- 239000002872 contrast media Substances 0.000 claims description 8
- 239000013256 coordination polymer Substances 0.000 claims description 8
- 229920001795 coordination polymer Polymers 0.000 claims description 8
- TXBFYVDRMBBEDT-UHFFFAOYSA-N N1=C(C(=C(C=C1)C(=O)O)C=1C=NC=CC1)C(=O)O.C1(=CC=CC=C1)C1=NC2=CC=CC=C2C=C1 Chemical class N1=C(C(=C(C=C1)C(=O)O)C=1C=NC=CC1)C(=O)O.C1(=CC=CC=C1)C1=NC2=CC=CC=C2C=C1 TXBFYVDRMBBEDT-UHFFFAOYSA-N 0.000 claims description 7
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 6
- 239000000376 reactant Substances 0.000 claims description 6
- 150000001991 dicarboxylic acids Chemical class 0.000 claims description 4
- 229910052979 sodium sulfide Inorganic materials 0.000 claims description 4
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims description 4
- 239000002131 composite material Substances 0.000 claims description 2
- 238000003760 magnetic stirring Methods 0.000 claims description 2
- 239000002091 nanocage Substances 0.000 abstract description 14
- 238000003384 imaging method Methods 0.000 abstract description 11
- 239000002086 nanomaterial Substances 0.000 abstract description 10
- 206010028980 Neoplasm Diseases 0.000 abstract description 5
- 238000003745 diagnosis Methods 0.000 abstract description 4
- 230000010354 integration Effects 0.000 abstract description 3
- 238000010438 heat treatment Methods 0.000 abstract description 2
- -1 iridium 2-phenylquinoline-3,3'-bipyridine dicarboxylic acid Chemical compound 0.000 abstract description 2
- 238000012634 optical imaging Methods 0.000 abstract description 2
- 238000002428 photodynamic therapy Methods 0.000 abstract description 2
- 238000007626 photothermal therapy Methods 0.000 abstract description 2
- 239000012295 chemical reaction liquid Substances 0.000 abstract 2
- WQXKGOOORHDGFP-UHFFFAOYSA-N 1,2,4,5-tetrafluoro-3,6-dimethoxybenzene Chemical compound COC1=C(F)C(F)=C(OC)C(F)=C1F WQXKGOOORHDGFP-UHFFFAOYSA-N 0.000 abstract 1
- 238000002156 mixing Methods 0.000 abstract 1
- 239000002405 nuclear magnetic resonance imaging agent Substances 0.000 abstract 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 25
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 23
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 23
- 239000000463 material Substances 0.000 description 12
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 11
- 230000003287 optical effect Effects 0.000 description 8
- 239000003814 drug Substances 0.000 description 7
- 238000002595 magnetic resonance imaging Methods 0.000 description 6
- 230000008901 benefit Effects 0.000 description 5
- 210000004027 cell Anatomy 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 201000011510 cancer Diseases 0.000 description 3
- 229940079593 drug Drugs 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- FDWREHZXQUYJFJ-UHFFFAOYSA-M gold monochloride Chemical compound [Cl-].[Au+] FDWREHZXQUYJFJ-UHFFFAOYSA-M 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 235000008429 bread Nutrition 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000001218 confocal laser scanning microscopy Methods 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 230000005291 magnetic effect Effects 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 230000035515 penetration Effects 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000011358 absorbing material Substances 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000013270 controlled release Methods 0.000 description 1
- 238000012718 coordination polymerization Methods 0.000 description 1
- 210000000805 cytoplasm Anatomy 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000002224 dissection Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000002121 endocytic effect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 210000000981 epithelium Anatomy 0.000 description 1
- 239000007850 fluorescent dye Substances 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000001631 haemodialysis Methods 0.000 description 1
- 230000000322 hemodialysis Effects 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000007777 multifunctional material Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 230000005298 paramagnetic effect Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 210000004872 soft tissue Anatomy 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000000638 stimulation Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 230000002123 temporal effect Effects 0.000 description 1
- 210000001519 tissue Anatomy 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- 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
- A61K49/228—Host-guest complexes, clathrates, chelates
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K41/00—Medicinal preparations obtained by treating materials with wave energy or particle radiation ; Therapies using these preparations
- A61K41/0052—Thermotherapy; Hyperthermia; Magnetic induction; Induction heating therapy
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K49/00—Preparations for testing in vivo
- A61K49/0002—General or multifunctional contrast agents, e.g. chelated agents
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K49/00—Preparations for testing in vivo
- 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
- A61K49/189—Host-guest complexes, e.g. cyclodextrins
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- Health & Medical Sciences (AREA)
- Epidemiology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Animal Behavior & Ethology (AREA)
- General Health & Medical Sciences (AREA)
- Public Health (AREA)
- Veterinary Medicine (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- Radiology & Medical Imaging (AREA)
- Medicinal Chemistry (AREA)
- Pharmacology & Pharmacy (AREA)
- Physics & Mathematics (AREA)
- Acoustics & Sound (AREA)
- Chemical & Material Sciences (AREA)
- Medicines Containing Antibodies Or Antigens For Use As Internal Diagnostic Agents (AREA)
- Magnetic Resonance Imaging Apparatus (AREA)
Abstract
The invention belongs to the technical field of inorganic nano materials and molecular imaging and in particular relates to a multifunctional nanocomposite as well as a preparation method and application thereof. The preparation method comprises the following steps: adding SH-PEG-NH2 into a gold nanocage wrapped by PVP on the surface, stirring for 8-20 hours, centrifuging, and washing, so that the gold nanocage wrapped by SH-PEG-NH2 on the surface is obtained; adding PVP into iridium 2-phenylquinoline-3,3'-bipyridine dicarboxylic acid solution, heating to 100-120 DEG C, and maintaining for 10-40 minutes; quickly dropwise adding dysprosium acetate solution, and reacting, so that reaction liquid is obtained; mixing the gold nanocage wrapped by SH-PEG-NH2 with the reaction liquid, carrying out dialysis reaction, centrifuging, and washing. The multifunctional nanocomposite provided by the invention can serve as a photoacoustic imaging/optical imaging/magnetic resonance imaging contrast agent and also has the function of carrying out photothermal therapy and photodynamic therapy, so that the multifunctional nanocomposite provided by the invention is a nano material which realizes integration of tumour diagnosis and treatment.
Description
Technical field
The invention belongs to inorganic nano material and molecular imaging technical field, be specifically related to a kind of multifunctional nano and be combined
Material and its preparation method and application.
Background technology
In recent years, gold nano-material shows due to its superior physics and chemical property in the Clinics and Practices of cancer
Huge potential and advantage.Gold nano-material can apply to biomedical sector, is the optical property noticeable based on it,
The specific scattering to exciting light resonant wavelength being based especially on plasma resonance and cause and absorption.Gold nano-material is many
Plant biomedical applications and provide multi-functional and multi-level platform.Recent study also demonstrate that gold nano-material is the most permissible
It is used in the Clinics of cancer.Such as, gold nano-material is used as optical instrument detection trace biology label
Substrate, it is also possible to be used as the carrier of the contrast agent of multiple optical imagery and medicament transport and control release, it is also possible to be used as
Destroy the light-heat transfer device of cancerous cell.
Gold nanometer cage (Au nanocage) represent numerous at regional area surface plasmon absorption peak the reddest
One in the adjustable gold nano-material of exterior domain.This multifunctional material has the structure of hollow and ultra-thin porous wall, and
(by silver nanoparticle cubic block Ag nanocube and gold chloride, ion exchange can occur in water by relatively simple step
Reaction) obtain in a large number.Gold nanometer cage the absorption of near infrared region can be precisely adjusted by controlling size and wall thickness to
Arbitrarily wavelength.The small size of gold nanometer cage, big absorption cross section (almost five times of conventional organic dyes) and its biology are lazy
Property and surface based on gold-mercaptan chemistry modify to become and can be applicable to biomedical absorbing material.
Gold nanometer cage is applied to the diagnosis and treatment of cancer and also has some advantages hidden: the machinery that (1) mono-crystalline structures brings is flexibly
Property, stability and even curface；(2) wall thickness gold nanometer cage in the range of 2-10nm can obtain in a large number, and can protect
Card precision is 0.5nm；(3) by controlling the addition of gold chloride, the local plasmon resonance body peak of gold nanometer cage in the reaction
Simply and accurately can be regulated and controled in the range of 600-1200nm；(4) hollow can be used for of gold nanometer cage packs (other material
Material)；(5) hole wall of gold nanometer cage can be used for medicament transport, and by multiple stimulation means Drug controlled release；(6) Jenner
Rice cage size 20-500nm in the range of change thus obtain optimum bio distribution, promote its infiltration in epithelial tissue or
Increase drug loading；(7) the local plasmon resonance body peak of gold nanometer cage is absorbed by it and scattering under different imaging patterns
Determine；(8) other noble metals (such as palladium and platinum) can be added in building-up process in wall and change the optical of gold nanometer cage
Matter.
Coordination polymer refers to by the multiple tooth organic ligands such as oxygen-containing, nitrogen (being fragrance polyacid and polybase mostly) and transition metal
The hybrid material that ion is formed by self assembly.This material can apply optics, catalysis, bio-sensing, medicine transmission,
The aspects such as bio-imaging and gas storage, have become Polymer Chemistry and Physics, physical chemistry and material science etc. many most
The Disciplinary Frontiers of door subject crossing.Paid attention to by various countries scientist owing to it is widely applied.In recent years, coordination polymer is
Through having narrowed down to nano-scale (NCPs).Compared with traditional nano-medicament carrier, NCPs has a lot of advantages, such as synthesis bar
Part is gentleer, pattern is adjustable, various structures, drug loading height, self degradable etc..Come with silicon dioxide or organic polymer
Modify NCPs, the stability of NCPs, biocompatibility can be improved.Further, since NCPs can containing substantial amounts of paramagnetic metal from
Son, so they are widely used in the contrast agent of nuclear magnetic resonance (MRI).
Optical imagery is easy and simple to handle, low cost, can combine with simple, lossless, real-time and portable operating system,
Preferably clinical service, but sensitivity is low, penetration into tissue is bad, near infrared fluorescent dye easily occurs cancellation.MRI has sky
Between temporal resolution height, good contrast, soft tissue image, the advantages such as dissection and physiologic information can be obtained simultaneously, but also have
The shortcoming that sensitivity is the highest.And although photoacoustic imaging combines high contrast features and the height of pure ultra sonic imaging of pure optical imagery
The advantage of penetration depth characteristic, but resolution is high less than MRI.So a kind of probe that can carry out multi-modality imaging becomes simultaneously
One of study hotspot for material circle and medical circle.
Summary of the invention
It is an object of the invention to provide a kind of multifunctional nanocomposites, there is good biocompatibility, have excellent
Good photo-thermal, photodynamics, magnetic property, at biological field for image-forming contrast medium, it is achieved diagnosis and treatment integration.
It is a further object to provide the preparation method of a kind of above-mentioned multifunctional nanocomposites.
The present invention is with polyhydric alcohol as reducing agent, with polyvinylpyrrolidone (PVP) as surfactant, first synthesizes shape
The Ag nanocube that looks are homogeneous, then as template, by displacement reaction, is etched into tool with gold chloride by Ag nanocube
There is the Au nanocage of cagelike structure.The Au nanocage surface protected by PVP is electronegative, with one end band sulfydryl other end
Polyethylene Glycol (SH-PEG-NH with amino2) carry out surface ligand exchange after, surface charge is just become from negative.
On the other hand, with a kind of complex of iridium, 2-phenylchinoline-3,3 '-bipyridyl dicarboxylic acids iridium and acetic acid dysprosium are raw material,
With polyvinylpyrrolidone as surfactant, in dimethyl sulfoxide, reacting by heating generates coordination polymer.Surface is wrapped up
SH-PEG-NH2Aunanocage and coordination polymer solution reaction, eventually pass dialysis and obtain surface parcel Ir-Dy and join
The Aunanocage of position polymer.
The purpose of the present invention can be realized by below scheme:
A kind of multifunctional nanocomposites, it is characterised in that: this composite is with gold nanometer cage as core, in the appearance of core
Bread wraps up in iridium coordination polymer.Preferably, the thickness of the iridium coordination polymer of this multifunctional nanocomposites is 30-40nm；
The particle diameter of multifunctional nanocomposites is 80-100nm.
The preparation method of above-mentioned multifunctional nanocomposites, its step includes:
(1) in the gold nanometer cage of surface parcel PVP, SH-PEG-NH is added2, stir 8-20 hour, obtain after centrifuge washing
Obtain surface parcel SH-PEG-NH2Gold nanometer cage；
(2) in 2-phenylchinoline-3,3 '-bipyridyl dicarboxylic acids iridium solution adds PVP, is heated to 100-120 DEG C, keep
10-40 minute；The most quickly instill acetic acid dysprosium solution reaction 4-10 hour, it is thus achieved that reactant liquor；
(3) SH-PEG-NH that will obtain in step (1)2The gold nanometer cage of parcel mixes with the reactant liquor in step (2),
Hemodialysis reaction 3-7 hour, centrifuge washing.
In described step (1), the preparation method of the gold nanometer cage of surface parcel PVP is,
(A) diethylene glycol heats under magnetic stirring, be separately added into PVP solution, Na2S solution, HCl solution and
CF3COOAg solution reaction 1-5 hour, it is thus achieved that the silver nanocubes of surface parcel PVP；
It is further preferred that in described step (A), the concentration of PVP is 0.3-0.4mmol/L, Na2The concentration of S solution is
2-4mmol/L, the concentration of HCl solution is 25-35mmol/L, CF3The concentration of COOAg solution is 2.5-3.5mol/L.
(B) in PVP solution, add the silver nanocubes of surface parcel PVP, be heated to 80-100 DEG C, the most dropwise add
Enter HAuCl4Solution, keeps 5-20 minute.Preferably, described HAuCl4Solution, control rate of addition is 45mL/h.
Preferably, in described step (B), the concentration of PVP solution is 0.05-0.15mmol/L, described HAuCl4Solution
Concentration is 0.5-1.5mmol/L.
It is further preferred that in described step (B), PVP solution, the silver nanocubes of surface parcel PVP and HAuCl4
The addition proportioning of solution is 3-7mL:1mg:1-5mL.
In described step (1), the gold nanometer cage of surface parcel PVP and SH-PEG-NH2Proportioning be 1mL:2-8mg.Preferably
, the concentration of the gold nanometer cage of described surface parcel PVP is 1-2mg/mL.
In described step (2), 2-phenylchinoline-3, the concentration of 3 '-bipyridyl dicarboxylic acids iridium solution is 0.5-1.0mg/mL；
The concentration of acetic acid dysprosium solution is 0.5-1.5mg/mL.
Preferably, in described step (2), 2-phenylchinoline-3,3 '-bipyridyl dicarboxylic acids iridium solution and acetic acid dysprosium solution
Solvent is DMSO.
Described step (2), 2-phenylchinoline-3,3 '-bipyridyl dicarboxylic acids iridium solution, PVP and the addition of acetic acid dysprosium solution
Proportioning is 1-5mL:20-30mg:1mL.
In described step (3), SH-PEG-NH2The gold nanometer cage of parcel is 1:1-3 with the volume ratio of reactant liquor.
The application in image-forming contrast medium of the described multifunctional nanocomposites.Preferably, this multifunctional nano composite wood
Expect the application in photoacoustic imaging contrast agent, optical imaging contrast agents and NMR contrast agent, and may be used for photo-thermal
In treatment and photodynamic therapy.
The invention has the beneficial effects as follows:
1, the present invention is by carrying out surface ligand exchange to Au nanocage, changes its surface charge, and utilizes electrostatic phase
Interaction, makes coordination polymer Ir-Dy-PVP be combined in Au nanocage surface, thus obtains one and have multi-modality imaging concurrently
Nano composite material with multi-mode treatment.
2, the multifunctional nanocomposites that the present invention prepares, has good T2 image contrast, temperature rise effect
Significantly, can possess again simultaneously and carry out photo-thermal therapy as photoacoustic imaging/optical imagery/magnetic resonance imaging contrast and move with light
The function of mechanics treatment, is a kind of nano material realizing tumor diagnosis and treatment integration.
3, the building-up process of the present invention is simple, with low cost.
Accompanying drawing explanation
Fig. 1 is the scanning electron microscope (SEM) photograph of the Ag nanocube prepared by embodiment 1.
Fig. 2 is the scanning electron microscope (SEM) photograph of the Aunanocage prepared by embodiment 1.
Fig. 3 is the scanning electron microscope (SEM) photograph of the multifunctional nanocomposites prepared by embodiment 2.
Fig. 4 is the transmission electron microscope picture of the multifunctional nanocomposites prepared by embodiment 2.
Fig. 5 is the solution PA figure of the multifunctional nanocomposites prepared by embodiment 2.
Fig. 6 is the solution photo-thermal intensification figure of the multifunctional nanocomposites prepared by embodiment 2.
Fig. 7 is the cell LSCM figure of the multifunctional nanocomposites prepared by embodiment 2.
Fig. 8 is the solution MRI figure of the multifunctional nanocomposites prepared by embodiment 2.
Detailed description of the invention
Below in conjunction with embodiment, the invention will be further described:
Embodiment 1
(1), the synthesis of Ag nanocube
It is formulated as follows solution respectively:
0.36mmol/L PVP solution (molecular weight 55000, takes 125mg, is dissolved in 6.25mL diethylene glycol)；
3mmol/L Na2S solution (takes 10mg, is dissolved in 1mL diethylene glycol, take out 0.1mL, be diluted to diethylene glycol
1mL)；
The HCl solution of 30mmol/L (takes the dense HCl of 25 μ L 38%, is dissolved in 10mL diethylene glycol, with taking out before
0.25mL, is diluted to 0.5mL with diethylene glycol)；The CF of 0.28mol/L3COOAg solution (takes 125mg, is dissolved in 2mL diethyl two
Alcohol).
In 100mL round-bottomed flask, add 25mL diethylene glycol, under magnetic agitation, be heated to 150 DEG C.To 150 DEG C two
Ethylene glycol adds 300 μ L Na2S solution.After 4min, add 0.5mL HCl solution and 3mL PVP solution.After 2min, add
2mL CF3COOAg solution, reacts 3h.After cooling, centrifuge washing obtains the Ag nanocube of 20-30nm, its scanning electron microscope table
Levy as it is shown in figure 1, define highly uniform Ag nanocube；
(2), surface parcel SH-PEG-NH2The preparation of Au nanocage.
The PVP solution (molecular weight 55000, takes 25mg, is dissolved in 10mL water) of preparation 0.1mmol/L.Preparation 1mmol/L's
HAuCl4Solution (takes 39.4mg HAuCl4·3H2O, is dissolved in 10mL water, takes the above-mentioned solution of 1mL and is diluted to 10mL).At round bottom
In flask, add 10mL PVP solution, be subsequently adding 1mL Ag nanocube (concentration is 2mg/mL), be heated to 90 DEG C, and protect
Hold 10min.Dropwise dropping 3mL HAuCl4Solution, control rate of addition is 45mL/h, and keeps 10min.After cooling, it is centrifuged and washes
Washing the Au nanocage obtaining 20-35nm, its scanning electron microscope characterizes as in figure 2 it is shown, its uniform particle sizes.
Take 2mLAu nanocage, add 18mLH2The SH-PEG-NH of O, 10mg2, it is stirred overnight, after centrifuge washing, obtains table
Bread wraps up in SH-PEG-NH2Au nanocage.
Embodiment 2
Weigh 2-phenylchinoline-3 of 3.5mg, 3 '-bipyridyl dicarboxylic acids iridium, be dissolved in 5mL DMSO, prepare 2-phenyl
Quinoline-3,3 '-bipyridyl dicarboxylic acids iridium solution；Weigh 2.1mg acetic acid dysprosium, be dissolved in 2mL DMSO, prepare acetic acid dysprosium solution.
In single neck flask, add 5mL 2-phenylchinoline-3,3 '-bipyridyl dicarboxylic acids iridium solution, be subsequently adding PVP
(50mg, m.w.=55000), is heated to 110 DEG C, keeps 20min.Rapidly join 2mL acetic acid dysprosium solution, react 7h.Question response
Liquid is cooled to room temperature, the SH-PEG-NH obtained in Example 12The Au nanocage 1mL of parcel, reacts liquid phase with 2mL and mixes
Closing, proceed to bag filter, dialyse 5h, and centrifuge washing obtains multifunctional nanocomposites, and its scanning electron microscope characterizes such as Fig. 3, particle diameter
For 80-100nm.
Fig. 4 is the transmission electron microscope picture of the multifunctional nanocomposites prepared by the present invention, it can be seen that coordination polymerization
Thing Ir-Dy-PVP defines effectively parcel to Au nanocage.
Fig. 5 is the solution PA figure of the multifunctional nanocomposites prepared by the present invention, it can be seen that the optoacoustic of material
Signal intensity has the strongest concentration dependent, and this also provides foundation for further cell/vivo applications.
Fig. 6 is the solution photo-thermal intensification figure of the multifunctional nanocomposites prepared by the present invention, it can be seen that along with
Concentration raises, and the temperature rise effect of material gradually strengthens.
Fig. 7 is the cell LSCM figure of the multifunctional nanocomposites prepared by the present invention, it can be seen that material has
Cytoplasm can be entered by cell endocytic and carry out the effect of optical imagery.
Fig. 8 is the solution MRI figure of the multifunctional nanocomposites prepared by the present invention, it can be seen that along with concentration
Changing, material has good T2 image contrast.
The above is presently preferred embodiments of the present invention, but the present invention should not be limited to disclosed in this embodiment
Content.So every without departing from the equivalence completed under spirit disclosed in this invention or amendment, both fall within the model of present invention protection
Enclose.
Claims (8)
1. a multifunctional nanocomposites, it is characterised in that: this composite is with gold nanometer cage as core, at the outer surface of core
Parcel iridium coordination polymer.
2. the preparation method of the multifunctional nanocomposites described in claim 1, its step includes:
(1) in the gold nanometer cage of surface parcel PVP, SH-PEG-NH is added2, stir 8-20 hour, after centrifuge washing, obtain surface
Parcel SH-PEG-NH2Gold nanometer cage；
(2) in 2-phenylchinoline-3,3 '-bipyridyl dicarboxylic acids iridium solution adds PVP, is heated to 100-120 DEG C, keep 10-
40 minutes；The most quickly instill acetic acid dysprosium solution reaction 4-10 hour, it is thus achieved that reactant liquor；
(3) SH-PEG-NH that will obtain in step (1)2The gold nanometer cage of parcel mixes with the reactant liquor in step (2), and dialysis is anti-
Answer 3-7 hour, centrifuge washing.
The preparation method of multifunctional nanocomposites the most according to claim 2, it is characterised in that: described step (1)
In, the preparation method of the gold nanometer cage of surface parcel PVP is,
(A) diethylene glycol heats under magnetic stirring, is separately added into PVP solution, Na2S solution, HCl solution and CF3COOAg solution
React 1-5 hour, it is thus achieved that the silver nanocubes of surface parcel PVP；
(B) in PVP solution, add the silver nanocubes of surface parcel PVP, be heated to 80-100 DEG C, be then added dropwise over
HAuCl4Solution, keeps 5-20 minute.
The preparation method of multifunctional nanocomposites the most according to claim 2, it is characterised in that: described step (1)
In, the gold nanometer cage of surface parcel PVP and SH-PEG-NH2Proportioning be 1mg:2-8mg.
The preparation method of multifunctional nanocomposites the most according to claim 2, it is characterised in that: described step (2)
In, 2-phenylchinoline-3, the concentration of 3 '-bipyridyl dicarboxylic acids iridium solution is 0.5-1.0mg/mL；The concentration of acetic acid dysprosium solution is
0.5-1.5mg/mL。
6. according to the preparation method of the multifunctional nanocomposites described in claim 2 or 5, it is characterised in that: described step
(2), 2-phenylchinoline-3, the proportioning that adds of 3 '-bipyridyl dicarboxylic acids iridium solution, PVP and acetic acid dysprosium solution is 1-5mL:20-
30mg:1mL.
The preparation method of multifunctional nanocomposites the most according to claim 2, it is characterised in that: described step (3)
In, SH-PEG-NH2The gold nanometer cage of parcel is 1:1-3 with the volume ratio of reactant liquor.
8. the application in image-forming contrast medium of the multifunctional nanocomposites in claim 1.
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| CN107670040A (en) * | 2017-10-25 | 2018-02-09 | 深圳先进技术研究院 | Gold nanometer cage manganese dioxide composite nanometer particle and its preparation method and application |
| CN110125434A (en) * | 2019-05-14 | 2019-08-16 | 东南大学 | A kind of preparation method of photo-thermal gold nano-material |
| CN111154115A (en) * | 2020-01-03 | 2020-05-15 | 大连理工大学 | Preparation method and application of binuclear Ir (III) metal-organic supermolecular cage-like compound |
| CN112338199A (en) * | 2020-10-20 | 2021-02-09 | 华中科技大学同济医学院附属协和医院 | Preparation method and application of gold nanocages |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107670040A (en) * | 2017-10-25 | 2018-02-09 | 深圳先进技术研究院 | Gold nanometer cage manganese dioxide composite nanometer particle and its preparation method and application |
| CN107670040B (en) * | 2017-10-25 | 2020-10-27 | 深圳先进技术研究院 | Gold nanocage-manganese dioxide composite nanoparticle and preparation method and application thereof |
| CN110125434A (en) * | 2019-05-14 | 2019-08-16 | 东南大学 | A kind of preparation method of photo-thermal gold nano-material |
| CN111154115A (en) * | 2020-01-03 | 2020-05-15 | 大连理工大学 | Preparation method and application of binuclear Ir (III) metal-organic supermolecular cage-like compound |
| CN112338199A (en) * | 2020-10-20 | 2021-02-09 | 华中科技大学同济医学院附属协和医院 | Preparation method and application of gold nanocages |
| CN112338199B (en) * | 2020-10-20 | 2022-05-31 | 华中科技大学同济医学院附属协和医院 | Preparation method and application of gold nanocages |
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