CN106692994B - A kind of flexible Meta Materials and its preparation method and application of helical form gold nano grain composition - Google Patents

A kind of flexible Meta Materials and its preparation method and application of helical form gold nano grain composition Download PDF

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CN106692994B
CN106692994B CN201710045236.0A CN201710045236A CN106692994B CN 106692994 B CN106692994 B CN 106692994B CN 201710045236 A CN201710045236 A CN 201710045236A CN 106692994 B CN106692994 B CN 106692994B
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substrate
gold nano
nano grain
meta materials
helical form
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CN106692994A (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 kind of flexible Meta Materials and its preparation method and application of helical form gold nano grain composition, which is to have gold nano grain thereon using flexible screw shape Meta Materials as substrate.It is described flexibility Meta Materials be spirally Meta Materials ito film as substrate, and assembled by gold nano grain by LBL self-assembly method, it has the characteristic of resonance under microwave frequency band, an apparent formant can be detected in special frequency channel, this provides a feasible road to carry out vivo biodistribution detection using 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, in particular to a kind of helical form gold nano grain meta-material thin film and its Preparation method and application.
Background technique
Biomaterial has important role for tissue repair.For hard tissue repairing material, people have been at present Many bone renovating materials are developed, and are clinically widely used, good effect is produced to Bone Defect Repari.Nanometer Material has many unique and excellent property, discovered in recent years have important influence for organism activity, therefore increasingly Obtain the attention of biomaterial researcher.It is desirable that traditional biological material can be assigned in addition to promoting by the transformation of structure The outer function that can also perceive surrounding tissue growing state of cell growth.The Meta Materials of currently reported helical structure are in microwave Have the characteristic of resonance under frequency range, can detect an apparent formant in special frequency channel, this for we using electromagnetic field into The detection of row vivo biodistribution provides a feasible path, and it has been found that nanoparticle assemblies, which have, promotes marrow before us Cell differentiation is osteoblast, and promotes the property of Oesteoblast growth, therefore studies gold nano grain and assemble the spiral to be formed The microwave resonance property of shape superstructure has important research significance to exploitation multifunctional novel biological tissue repair materials.
Summary of the invention
To solve the above-mentioned problems of the prior art, the object of the present invention is to provide a kind of helical form gold nano grain groups At flexible Meta Materials and preparation method thereof.
To achieve the above object, the technical solution adopted by the present invention are as follows:
A kind of flexible Meta Materials of helical form gold nano grain composition, which is with flexible screw shape Meta Materials As substrate, there is gold nano grain thereon.
The substrate is ito film, and resistivity is 6 Ω/cm2。
The partial size of the gold nano grain is 18nm.
A kind of preparation method of the flexible Meta Materials of helical form gold nano grain composition, includes the following steps:
(1) substrate surface corona treatment 5 minutes；
(2) substrate is put into polyelectrolyte solution and is impregnated 10 minutes, guarantee that polyelectrolyte solution all submerges substrate；
(3) substrate is taken out from polyelectrolyte solution, is first rinsed 3 minutes with tap water, then divided with ultrapure water 3 Clock is dried up with liquid nitrogen later；
(4) substrate is put into gold nano-particle colloid solution and is impregnated 15 minutes, guarantee fund's nanoparticle colloid solution will Substrate all submerges；
(5) operation for repeating 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) step (2)-(5) are repeated, multi-layer spiral gold nano grain meta-material thin film is prepared.
In step (2), the polyelectrolyte is diallyl dimethyl ammoniumchloride (PDDA), 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), when flushing, it is rinsed along the same direction.
It is a further object to provide the flexible Meta Materials of above-mentioned helical form gold nano grain composition to examine in biology Application in survey, specifically comprises the following steps:
(1) it is repaired with the flexible Meta Materials that the helical form gold nano grain prepared forms 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 wave carries out external Non-invasive detection.
The utility model has the advantages that the flexible Meta Materials of helical form gold nano grain composition provided by the invention have altogether under microwave frequency band The characteristic of vibration can detect an apparent formant in special frequency channel, this is to carry out vivo biodistribution detection using electromagnetic field A feasible path is provided, 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.
Detailed description of the invention
Fig. 1 is the structural schematic diagram of the flexible Meta Materials film of helical form gold nano grain composition provided by the invention；
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, there is an apparent resonance peak at 1.6GHz.
Specific embodiment
The present invention will be further explained with reference to the accompanying drawing.
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 film is substrate, has helical form gold nano grain in substrate.With the method for LBL self-assembly, using polyelectrolyte as The superstructure film of helical form gold nano grain is formed on the substrate by electrostatic adsorption for adhesive.
Wherein, silicon materials substrate is High Resistivity Si, and resistivity is 6 Ω * cm2.The partial size of gold nano grain is 18nm.
The present invention will be further described combined with specific embodiments below:
Embodiment
As shown in Fig. 2, helical form gold nano grain meta-material thin film of the invention comprises the following steps:
(1) substrate surface corona treatment 5 minutes；
(2) it puts it into and impregnates 10 points in diallyl dimethyl ammoniumchloride (PDDA) solution that volume fraction is 2% Clock guarantees 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 tap water Clock, then with ultrapure water 3 minutes, pay attention to being rinsed along the same direction, be dried up later with liquid nitrogen；
(4) it puts it into the gold nano-particle colloid solution that concentration is 0.5mg/ml and impregnates 15 minutes, guarantee 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 gold nanoparticle film has just been prepared Finish；
(6) (2)-(5) step is repeated, 2,3,4 ... layers of helical form gold nano grain meta-material thin film are prepared.
Such as Fig. 3, according to 50 layers of helical form gold nano grain meta-material thin film made from aforesaid operations, in 1.6GHz frequency range There is an apparent resonance peak at place, 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 Expect response of the film to electromagnetic wave, the effect for carrying out internal Non-invasive detection is best.
The above is only a preferred embodiment of the present invention, it should be pointed out that: for the ordinary skill people of the art For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered It is considered as protection scope of the present invention.

Claims (7)

1. a kind of flexible Meta Materials of helical form gold nano grain composition, it is characterised in that: the flexibility Meta Materials are with flexible spiral shell Shape Meta Materials are revolved as substrate, there is gold nano grain thereon；The helical form is as shown in Figure 1；
The flexibility Meta Materials are prepared by the following steps to obtain:
(1) substrate surface corona treatment 5 minutes；
(2) substrate is put into polyelectrolyte solution and is impregnated 10 minutes, guarantee that polyelectrolyte solution all submerges substrate；
(3) substrate is taken out from polyelectrolyte solution, is first rinsed 3 minutes with tap water, then with ultrapure water 3 minutes, it It is dried up afterwards with liquid nitrogen；
(4) substrate is put into gold nano-particle colloid solution and is impregnated 15 minutes, guarantee fund's nanoparticle colloid solution is by substrate All submergences；
(5) operation for repeating 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) step (2)-(5) are repeated, multi-layer spiral gold nano grain meta-material thin film is prepared.
2. the flexible Meta Materials of helical form gold nano grain composition according to claim 1, it is characterised in that: the substrate For ito film, resistivity is 6 Ω/cm2。
3. the flexible Meta Materials of helical form gold nano grain composition according to claim 1, it is characterised in that: the Jenner The partial size of rice grain is 18nm.
4. a kind of preparation method of the flexible Meta Materials of helical form gold nano grain composition, characterized by the following steps:
(1) substrate surface corona treatment 5 minutes；
(2) substrate is put into polyelectrolyte solution and is impregnated 10 minutes, guarantee that polyelectrolyte solution all submerges substrate；
(3) substrate is taken out from polyelectrolyte solution, is first rinsed 3 minutes with tap water, then with ultrapure water 3 minutes, it It is dried up afterwards with liquid nitrogen；
(4) substrate is put into gold nano-particle colloid solution and is impregnated 15 minutes, guarantee fund's nanoparticle colloid solution is by substrate All submergences；
(5) operation for repeating 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) step (2)-(5) are repeated, multi-layer spiral gold nano grain meta-material thin film is prepared；
Wherein, the helical form is as shown in Figure 1.
5. the preparation method of the flexible Meta Materials of helical form gold nano grain composition according to claim 4, feature exist In: in step (2), the polyelectrolyte is diallyl dimethyl ammoniumchloride, the volume point in polyelectrolyte solution Number is 2%.
6. the preparation method of the flexible Meta Materials of helical form gold nano grain composition according to claim 4, feature exist 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 composition according to claim 4, feature exist In: in step (3) and (5), when flushing, it is rinsed along the same direction.
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CN107741278B (en) * 2017-09-30 2019-09-10 烟台睿创微纳技术股份有限公司 A kind of non refrigerating infrared imaging sensor and preparation method thereof based on super surface
CN110416740B (en) * 2019-08-09 2020-06-26 北京航空航天大学 Metamaterial based on micro-spiral structure and manufacturing method thereof

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