CN106692994A - Flexible metamaterial composed of spiral gold nanoparticles, and preparation method and application thereof - Google Patents

Flexible metamaterial composed of spiral gold nanoparticles, and preparation method and application thereof Download PDF

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Publication number
CN106692994A
CN106692994A CN201710045236.0A CN201710045236A CN106692994A CN 106692994 A CN106692994 A CN 106692994A CN 201710045236 A CN201710045236 A CN 201710045236A CN 106692994 A CN106692994 A CN 106692994A
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gold nano
substrate
nano grain
flexible
meta materials
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CN106692994B (en
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孙剑飞
王鹏
顾宁
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Southeast University
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Southeast University
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    • 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
    • A61K49/1896—Nuclear magnetic resonance [NMR] contrast preparations; Magnetic resonance imaging [MRI] contrast preparations characterised by a special physical form, e.g. emulsions, microcapsules, liposomes not provided for elsewhere, e.g. cells, viruses, ghosts, red blood cells, virus capsides
    • 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
    • A61K49/08—Nuclear magnetic resonance [NMR] contrast preparations; Magnetic resonance imaging [MRI] contrast preparations characterised by the carrier
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/28—Materials for coating prostheses
    • A61L27/30—Inorganic materials
    • A61L27/306—Other specific inorganic materials not covered by A61L27/303 - A61L27/32
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2400/00—Materials characterised by their function or physical properties
    • A61L2400/12—Nanosized materials, e.g. nanofibres, nanoparticles, nanowires, nanotubes; Nanostructured surfaces
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2430/00—Materials or treatment for tissue regeneration
    • A61L2430/02—Materials or treatment for tissue regeneration for reconstruction of bones; weight-bearing implants

Abstract

The invention discloses a flexible metamaterial composed of spiral gold nanoparticles, and a preparation method and an application thereof, wherein the flexible metamaterial adopts a flexible spiral metamaterial as a substrate and gold nanometer particles are formed on the substrate. The flexible metamaterial takes the spiral metamaterial ITO membrane as the substrate, and is formed by assembling the gold nanoparticles by a layer-by-layer self-assembly method; the flexible metamaterial has the resonance characteristics at microwave frequency bands, and an obvious resonance peak can be detected in a specific frequency band, so a feasible way is provided for in vivo biological detection by an electromagnetic field.

Description

A kind of flexible Meta Materials of helical form gold nano grain composition and preparation method thereof and Using
Technical field
The invention belongs to technical field of biological, more particularly to a kind of helical form gold nano grain meta-material thin film and its Preparation method and application.
Background technology
Biomaterial plays the role of important for tissue repair.For hard tissue repairing material, current people are Many bone renovating materials are developed, and is clinically widely used, good effect is generated to Bone Defect Repari.Nanometer Material has many unique and excellent property, and discovered in recent years has important influence for organism activity, therefore increasingly Obtain the attention of biomaterial researcher.It is desirable that traditional biological material can be assigned except promoting by the conversion of structure The function of surrounding tissue growing state can also be perceived outside cell growth.The Meta Materials of currently reported helical structure are in microwave There is the characteristic of resonance under frequency range, an obvious formant can be detected in special frequency channel, this is entered for us using electromagnetic field The detection of row vivo biodistribution provides a feasible path, and has found that nanoparticle assemblies have before us and promote marrow Cell differentiation is Gegenbaur's cell, and promotes the property of Oesteoblast growth, therefore research gold nano grain assembles the spiral to be formed The microwave resonance property of shape superstructure has important Research Significance to exploitation multifunctional novel biological tissue repair materials.
The content of the invention
To solve the problems, such as above-mentioned prior art, it is an object of the invention to provide a kind of helical form gold nano grain group Into flexible Meta Materials and preparation method thereof.
To achieve the above object, the technical solution adopted by the present invention is：
A kind of flexible Meta Materials of helical form gold nano grain composition, the flexible Meta Materials are with flexible screw shape Meta Materials As substrate, there is gold nano grain thereon.
The substrate is ito films, and resistivity is 6 Ω/cm2。
The particle diameter of the gold nano grain is 18nm.
A kind of preparation method of the flexible Meta Materials of helical form gold nano grain composition, comprises the following steps：
(1) substrate surface corona treatment 5 minutes；
(2) substrate is put into polyelectrolyte solution and is soaked 10 minutes, it is ensured that polyelectrolyte solution all submerges substrate；
(3) substrate is taken out from polyelectrolyte solution, is first rinsed 3 minutes with running water, then with 3 points of ultrapure water Clock, is dried up with liquid nitrogen afterwards；
(4) substrate is put into gold nano-particle colloid solution and is soaked 15 minutes, it is ensured that gold nano-particle colloid solution will Substrate is all submerged；
(5) operation of repeat step (3), substrate is cleaned and is dried up with liquid nitrogen；Such 1 layer of gold nanoparticle film is just made It is standby to finish；
(6) repeat step (2)-(5), prepare multi-layer spiral gold nano grain meta-material thin film.
In step (2), the polyelectrolyte is diallyl dimethyl ammoniumchloride (PDDA), and it is in polyelectrolyte solution In volume fraction be 2%.
In step (4), the concentration of the gold nano-particle colloid solution is 0.5mg/ml.
In step (3) and (5), during flushing, it is rinsed along same direction.
Flexible Meta Materials it is a further object to provide above-mentioned helical form gold nano grain composition are examined in biology Application in survey, specifically includes following steps：
(1) the flexible Meta Materials constituted with the helical form gold nano grain for preparing are repaiied on bone renovating material surface Decorations；
(2) bone renovating material is implanted into human body, with the flexible Meta Materials of helical form gold nano grain composition to electromagnetism The response of ripple, carries out external Non-invasive detection.
Beneficial effect：The flexible Meta Materials of the helical form gold nano grain composition that the present invention is provided have altogether under microwave frequency band The characteristic shaken, can detect an obvious formant in special frequency channel, and this is to carry out vivo biodistribution detection using electromagnetic field There is provided a feasible path, it can be modified bone renovating material surface, and then bone renovating material is implanted into people In vivo, the response with helical structure nanometer particle film to electromagnetic wave, can carry out internal Non-invasive detection.
Brief description of the drawings
Fig. 1 is the structural representation of the flexible Meta Materials film of the helical form gold nano grain composition that the present invention is provided；
Fig. 2 is the preparation method schematic diagram of the flexible Meta Materials of helical form gold nano grain composition of the present invention；
Fig. 3 is microwave resonance measurement result, and it has an obvious resonance peak at 1.6GHz.
Specific embodiment
The present invention is further described below in conjunction with the accompanying drawings.
It is as shown in Figure 1 a kind of helical form gold nano grain meta-material thin film of the invention, it is super with flexible screw shape Material ito films are substrate, there is helical form gold nano grain in substrate.With the method for LBL self-assembly, using polyelectrolyte as Adhesive, the superstructure film of helical form gold nano grain is formed by electrostatic adsorption in substrate.
Wherein, silicon materials substrate is High Resistivity Si, and resistivity is 6 Ω * cm2.The particle diameter of gold nano grain is 18nm.
With reference to specific embodiment, the present invention will be further described：
Embodiment
As shown in Fig. 2 helical form gold nano grain meta-material thin film of the invention is comprised the following steps：
(1) substrate surface corona treatment 5 minutes；
(2) 10 points of immersion in diallyl dimethyl ammoniumchloride (PDDA) solution that volume fraction is 2% is put it into Clock, it is ensured that diallyl dimethyl ammoniumchloride (PDDA) solution all submerges substrate；
(3) substrate is taken out from diallyl dimethyl ammoniumchloride (PDDA) solution, first rinses 3 points with running water Clock, then with ultrapure water 3 minutes, note being rinsed along same direction, dried up with liquid nitrogen afterwards；
(4) concentration is put it into be soaked 15 minutes in the gold nano-particle colloid solution of 0.5mg/ml, it is ensured that gold nano Particle colloid solution all submerges substrate；
(5) (3) operation is repeated, substrate is cleaned and is dried up with liquid nitrogen；Such 1 layer of golden nanometer particle film has just been prepared Finish；
(6) (2)-(5) step is repeated, 2,3,4 ... helical layer shape gold nano grain meta-material thin films are prepared.
Such as Fig. 3, according to 50 helical layer shape gold nano grain meta-material thin film obtained in aforesaid operations, it is in 1.6GHz frequency ranges There is an obvious resonance peak at place, and this provides a feasible road to carry out vivo biodistribution detection using electromagnetic field, by it Bone renovating material surface is modified, and then bone renovating material is implanted into human body, with the super material of helical form gold nano grain Response of the material film to electromagnetic wave, carries out the best results of internal Non-invasive detection.
The above is only the preferred embodiment of the present invention, it should be pointed out that：For the ordinary skill people of the art For member, under the premise without departing from the principles of the invention, some improvements and modifications can also be made, these improvements and modifications also should It is considered as protection scope of the present invention.

Claims (9)

1. the flexible Meta Materials that a kind of helical form gold nano grain is constituted, it is characterised in that：The flexible Meta Materials are with flexible spiral shell Rotation shape Meta Materials have gold nano grain thereon as substrate.
2. the flexible Meta Materials that helical form gold nano grain according to claim 1 is constituted, it is characterised in that：The substrate It is ito films, resistivity is 6 Ω/cm2。
3. the flexible Meta Materials that helical form gold nano grain according to claim 1 is constituted, it is characterised in that：The Jenner The particle diameter of rice grain is 18nm.
4. the preparation method of the flexible Meta Materials of a kind of helical form gold nano grain composition, it is characterised in that：Comprise the following steps：
(1) substrate surface corona treatment 5 minutes；
(2) substrate is put into polyelectrolyte solution and is soaked 10 minutes, it is ensured that polyelectrolyte solution all submerges substrate；
(3) substrate is taken out from polyelectrolyte solution, is first rinsed 3 minutes with running water, then with ultrapure water 3 minutes, it Dried up with liquid nitrogen afterwards；
(4) substrate is put into gold nano-particle colloid solution and is soaked 15 minutes, it is ensured that gold nano-particle colloid solution is by substrate All submergences；
(5) operation of repeat step (3), substrate is cleaned and is dried up with liquid nitrogen；Such 1 layer of gold nanoparticle film has just been prepared Finish；
(6) repeat step (2)-(5), prepare multi-layer spiral gold nano grain meta-material thin film.
5. the preparation method of the flexible Meta Materials of helical form gold nano grain according to claim 4 composition, its feature exists In：In step (2), the polyelectrolyte is diallyl dimethyl ammoniumchloride, its volume integral in polyelectrolyte solution Number is 2%.
6. the preparation method of the flexible Meta Materials of helical form gold nano grain according to claim 4 composition, its feature exists In：In step (4), the concentration of the gold nano-particle colloid solution is 0.5mg/ml.
7. the preparation method of the flexible Meta Materials of helical form gold nano grain according to claim 4 composition, its feature exists In：In step (3) and (5), during flushing, it is rinsed along same direction.
8. application of the flexible Meta Materials of the helical form gold nano grain composition described in claim 1 in biological detection.
9. application according to claim 8, it is characterised in that：Comprise the following steps：
(1) the flexible Meta Materials constituted with the helical form gold nano grain for preparing are modified on bone renovating material surface；
(2) bone renovating material is implanted into human body, with the flexible Meta Materials of helical form gold nano grain composition to electromagnetic wave Response, carries out external Non-invasive detection.
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CN110186574A (en) * 2017-09-30 2019-08-30 烟台睿创微纳技术股份有限公司 A kind of non refrigerating infrared imaging sensor based on super surface
CN110416740A (en) * 2019-08-09 2019-11-05 北京航空航天大学 A kind of Meta Materials and its manufacturing method based on micro- helical structure

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CN110186574A (en) * 2017-09-30 2019-08-30 烟台睿创微纳技术股份有限公司 A kind of non refrigerating infrared imaging sensor based on super surface
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CN110416740A (en) * 2019-08-09 2019-11-05 北京航空航天大学 A kind of Meta Materials and its manufacturing method based on micro- helical structure

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