CN105817617B - A kind of nano-hybrid material of gold nanorods/silicon/carbon dioxide point and its preparation method and application - Google Patents
A kind of nano-hybrid material of gold nanorods/silicon/carbon dioxide point and its preparation method and application Download PDFInfo
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Abstract
The invention discloses a kind of nano-hybrid material of gold nanorods/silicon/carbon dioxide point, the nano-hybrid material includes the gold nanorods as core, the silicon dioxide layer as shell and the carbon point for being distributed in silicon dioxide layer outer surface；The nano-hybrid material is as obtained from the silane-functionalized carbon point containing amino occurring coupled action for the silicon dioxide layer that gold nanorods outer surface coats；The invention also discloses a kind of preparation method of the nano-hybrid material of gold nanorods/silicon/carbon dioxide point.The preparation method of the nano-hybrid material of gold nanorods/silicon/carbon dioxide point of the present invention is simply controllable.The nano-hybrid material of gold nanorods/silicon/carbon dioxide point of the present invention realizes the application in diffusing reflection imaging by gold nanorods, application in fluorescence lifetime imaging is realized by carbon point, so as to realize non-intrusion type multi-modality imaging, there is good application prospect in cancer diagnosis.
Description
Technical field
The present invention relates to bio-imaging technical field.More particularly, to a kind of gold nanorods/silicon/carbon dioxide point
Nano-hybrid material and its preparation method and application.
Background technology
During non-intrusion type bio-imaging, the research to multi-modality imaging agent is a popular field.Gold nano
Particle has surface plasma bulk effect (SPR), has significant absorption and scattering property in visible ray and near infrared light region, because
This gold nano grain generally carries out high-resolution at tumour cell and atherosclerosis position, highly sensitive light scattering into
Picture.Because the unique size and dimension of gold nano grain relies on optical property, gold nano grain can be as good imaging system
Contrast agent in system.In lesions position, the optical property of gold nano grain can change so as to improve image contrast.It is unrestrained anti-
It is a kind of new optical diagnostic method to penetrate imaging (DR), its simple, safety, cheap, by lower emittance realize compared with
Big penetration depth, so as to show histiocytic pattern (Nano letters, 2014,14 (5):2681-2687.).In DR
In detection, the change of the distance between light source and detector, histiocytic intensity of reflected light on the detector is caused to change, from
And obtain histiocytic information.Gold nanorods are applied as " external absorbent " in tissue after being connected with fluorescent dye
In diffusing reflection and fluorescence lifetime imaging (FLIM), multi-modality imaging is realized, so as to judge the metabolic condition (ACS in tissue
photonics,2014,1(9):900-905).Traditional fluorescence imaging method is to be based on fluorescence intensity, and fluorescence lifetime imaging
(FLIM) fluorescence decay time is based on, based on the overall fluorescent intensity of the fluorescence of each pixel, rather than fluorescent material, so that
Form the imaging results of more high-contrast.Semiconductor-quantum-point and fluorescent dye can be applied because of its unique photoluminescent property
Optical imaging field, but scintillation fluor and toxicity greatly limit its application again, it is therefore desirable to find a kind of biocompatibility
Higher fluorescent material meets the needs of medical diagnosis on disease in organism.
The excellent photoluminescent property of carbon point, biocompatibility, environment-friend substitution, low cost and hypotoxicity and chemically stable
Property so that carbon point has wider array of application in biologic applications field.DR can provide organization internal according to the position of gold nanorods
Depth information and FLIM can provide the image information of tissue surface, therefore establish the multi-modality imaging that can combine FLIM and DR
Mechanism has very profound significance in non-intrusion type medical diagnosis on disease.
The content of the invention
First purpose of the present invention is the nano-hybrid material for providing a kind of gold nanorods/silicon/carbon dioxide point.
Second object of the present invention is the nano-hybrid material for providing a kind of gold nanorods/silicon/carbon dioxide point
Preparation method.
The nano-hybrid material that third object of the present invention is to provide a kind of gold nanorods/silicon/carbon dioxide point exists
Application in diffusing reflection imaging or fluorescence lifetime imaging.
To reach above-mentioned purpose, the present invention uses following technical proposals：
The present invention provides a kind of nano-hybrid material of gold nanorods/silicon/carbon dioxide point, the nano-hybrid material bag
Include the gold nanorods as core, the silicon dioxide layer as shell and the carbon point for being distributed in silicon dioxide layer outer surface；The nanometer
Hybrid material is that with the silane-functionalized carbon point containing amino coupling work occurs for the silicon dioxide layer coated by gold nanorods outer surface
Obtained from；
The gold nanorods length is 30-100nm, and the draw ratio of the gold nanorods is 2-6；
The thickness of the silicon dioxide layer is 10-40nm；
The particle diameter of the carbon point is 1-10nm.
The present invention provides a kind of preparation method of the nano-hybrid material of gold nanorods/silicon/carbon dioxide point, including as follows
Step：
1) preparation [reference literature ACS photonics, 2014,1 (9) of gold nanorods:900-905.]
By HAuCl4The aqueous solution, NaBH4The aqueous solution is added sequentially in the CTAB aqueous solution, and after constant temperature is stood, it is molten to obtain crystal seed
Liquid；
By HAuCl4The aqueous solution, AgNO3The aqueous solution, HCl/water solution, that aqueous ascorbic acid is added sequentially to CTAB is water-soluble
In liquid, the 4th mixture is obtained；When the 4th mixture is become colorless by orange-yellow, then it is molten to add the crystal seed into the 4th mixture
Liquid, then constant temperature standing, obtains the mixed liquor containing gold nanorods；Mixed liquor containing gold nanorods is subjected to centrifugal treating, obtains Jenner
Rice rod.
2) gold nanorods/silica composite
The gold nanorods prepared in step 1) are dispersed in water, obtain the dispersion liquid containing gold nanorods；Gold nanorods will be contained
Dispersion liquid, the methanol solution containing tetraethyl orthosilicate and aqueous slkali according to volume ratio be 1000-2000:8-16:1 ratio is mixed
Close, then stirring reaction 1-5h at normal temperatures, obtain the first mixture, first mixture is subjected to centrifugal treating, washed
Gold nanorods/silica composite；
3) the silane-functionalized carbon point containing amino
By citric acid, the silane containing amino and water according to mass ratio be 1:2-20:2-20 ratio mixing, then in 120-
4-10h is reacted in 200 DEG C of hydrothermal reaction kettle, obtains the second mixture, second mixture is extracted and rotated, must be flowed
The silane-functionalized carbon point containing amino of dynamic state；
4) nano-hybrid material of gold nanorods/silicon/carbon dioxide point
Gold nanorods/the silica composite is scattered in ethanol, obtain gold nanorods/silica composite
Dispersion liquid；The dispersion liquid of gold nanorods/silica composite, aqueous slkali and silane-functionalized carbon point containing amino are mixed,
Then the stirring reaction 3-10h at 20-30 DEG C, obtains the 3rd mixture；3rd mixture is subjected to centrifugal treating, washed
The nano-hybrid material of gold nanorods/silicon/carbon dioxide point.
The aqueous slkali is the aqueous solution of sodium hydroxide, potassium hydroxide or ammoniacal liquor；Preferably, the concentration of the aqueous slkali is
0.1-1mol/L。
In step 2), the volume ratio of tetraethyl orthosilicate and methanol is 1 in the methanol solution containing tetraethyl orthosilicate:3-
10。
The dispersion liquid concentration containing gold nanorods is 0.1-1g/L.
In step 3), the silane containing amino is N- (β-aminoethyl)-γ-aminopropyltriethoxy dimethoxysilane, N-
(β-aminopropyl)-γ-aminopropyltriethoxy trimethoxy silane or APTES.
In step 3), extractant is the mixed liquor of ethyl acetate and petroleum ether.
In step 4), the concentration of the dispersion liquid of the gold nanorods/silica composite is 3-10g/L.
In step 4), dispersion liquid, aqueous slkali and the silane functionality containing amino of the gold nanorods/silica composite
The volume ratio for changing carbon point is 50-500:1-20:1.
Further, the nano-hybrid material good dispersion of gold nanorods of the invention/silicon/carbon dioxide point, will not assemble,
With the silane-functionalized carbon point containing amino coupled action occurs for the silicon dioxide layer of the gold nanorods outer surface cladding, makes carbon point
It is evenly distributed in silicon dioxide layer.The nano-hybrid material of the gold nanorods/silicon/carbon dioxide point is based on Si-O-Si's
Covalent key connection, therefore the stability of the nano-hybrid material is higher.
Present invention also offers a kind of application of the nano-hybrid material of gold nanorods/silicon/carbon dioxide point, the Jenner
The nano-hybrid material application in diffusing reflection imaging and fluorescence imaging life-span respectively of rice rod/silicon/carbon dioxide point.
Beneficial effects of the present invention are as follows：
1st, the preparation method of the nano-hybrid material of gold nanorods/silicon/carbon dioxide point of the invention is simply controllable, not only
The aggregation of gold nanorods is inhibited, and remains the surface plasma resonance of gold nanorods.
2nd, the nano-hybrid material of gold nanorods/silicon/carbon dioxide point of the invention not only has the light of gold nano grain
Learn property, it may have the excellent photoluminescent property of carbon point.
3rd, the nano-hybrid material for gold nanorods/silicon/carbon dioxide point that the present invention passes through preparation, obtains ratio in body mould
The more preferable diffusing reflection imaging effect of gold nanorods, and obtained in fluorescence lifetime imaging than carbon point more preferably imaging effect.
4th, the nano-hybrid material of gold nanorods/silicon/carbon dioxide point of the invention is realized unrestrained anti-by gold nanorods
The application penetrated in imaging, the application in fluorescence lifetime imaging is realized by carbon point, so as to realize non-intrusion type multi-modality imaging.
5th, the nano-hybrid material of gold nanorods/silicon/carbon dioxide point of the invention has splendid biocompatibility and steady
It is qualitative, therefore there is good application prospect in cancer diagnosis.
Brief description of the drawings
The embodiment of the present invention is described in further detail below in conjunction with the accompanying drawings.
Fig. 1 shows the transmission electron microscope picture of gold nanorods/silicon/carbon dioxide point nano-hybrid material prepared by embodiment 1.
Fig. 2 shows gold nanorods (CNRs), gold nanorods/silica composite (CNRs/ prepared by embodiment 1
SiO2), the nano-hybrid material (CNRs/SiO of gold nanorods/silicon/carbon dioxide point2/ CDs) ultraviolet-visible absorption spectroscopy.
Fig. 3 shows the fluorescent emission of the nano-hybrid material of gold nanorods/silicon/carbon dioxide point prepared by embodiment 1
Spectrum.
Fig. 4 shows gold nanorods (CNRs), gold nanorods/silica composite (CNRs/ prepared by embodiment 1
SiO2), the nano-hybrid material (CNRs/SiO of gold nanorods/silicon/carbon dioxide point2/ CDs) diffusing reflection in simulated tissue
Imaging results.
Fig. 5 shows gold nanorods (CNRs), the nano hybridization of gold nanorods/silicon/carbon dioxide point prepared by embodiment 1
Material (CNRs/SiO2/ CDs) in simulated tissue diffusing reflection imaging G-bar.
Fig. 6 shows that dyestuff in comparative example 2, the nano-hybrid material of gold nanorods/dyestuff are unrestrained anti-in simulated tissue
Penetrate the G-bar of imaging.
Fig. 7 (a) and 7 (b) show the silicon of N- (β-aminoethyl)-γ-aminopropyltriethoxy dimethoxy prepared by embodiment 1
Alkoxyl functional carbon point and gold nanorods/fluorescence lifetime imaging figure of the silicon/carbon dioxide point nano-hybrid material in simulated tissue.
Embodiment
In order to illustrate more clearly of the present invention, the present invention is done further with reference to preferred embodiments and drawings
It is bright.It will be appreciated by those skilled in the art that specifically described content is illustrative and be not restrictive below, should not be with this
Limit the scope of the invention.
Embodiment 1
The preparation of the nano-hybrid material of gold nanorods/silicon/carbon dioxide point
1) preparation of gold nanorods
A. the HAuCl by 0.25ml concentration for 0.01mol/L4The concentration that the aqueous solution and 0.6ml ice baths are crossed is 0.01mol/L
NaBH4The aqueous solution is added sequentially in the CTAB aqueous solution that 7.5ml concentration is 0.01mol/L, after 30 DEG C of constant temperature stands 2h, is obtained
Seed-solution；
B. the HAuCl by 10ml concentration for 0.01mol/L4The aqueous solution, the AgNO that 1.5ml concentration is 0.01mol/L3It is water-soluble
The aqueous ascorbic acid that the HCl/water solution and 0.32ml concentration that liquid, 5ml concentration are 1mol/L are 0.1mol/L is added to
200ml concentration is in the 0.1mol/L CTAB aqueous solution, obtains the 4th mixture, when the 4th mixture is become colorless by orange-yellow,
Seed-solution described in 480 μ l is added into the 4th mixture, then 30 DEG C of standing 16h of constant temperature, obtain the mixed liquor containing gold nanorods；
Mixed liquor containing gold nanorods is subjected to centrifugal treating, obtains gold nanorods.
2) gold nanorods/silica composite
It is 0.1mol/L NaOH solutions and 1.6ml that 150 μ L concentration are sequentially added into 200ml gold nanorods dispersion liquids
(volume ratio of tetraethyl orthosilicate and methanol is methanol solution containing tetraethyl orthosilicate in the methanol solution containing tetraethyl orthosilicate
1:5) 1.5h, is stirred under normal temperature, obtains the first mixture, first mixture is subjected to centrifugal treating, washed 3 times with ethanol,
Obtain gold nanorods/silica composite.
3) the silane-functionalized carbon point of N- (β-aminoethyl)-γ-aminopropyltriethoxy dimethoxy
0.5g citric acids and 10g N- (β-aminoethyl)-γ-aminopropyltriethoxy dimethoxysilane and 10g water is abundant
After mixing, it is added in hydrothermal reaction kettle, reacts 8h in 150 DEG C, the second mixture is obtained, by the second mixture acetic acid second
The mixed liquor of ester and petroleum ether is extracted, and N- (β-aminoethyl)-γ-aminopropyltriethoxy diformazan of flow regime is obtained after revolving
The silane-functionalized carbon point of epoxide.
4) gold nanorods/silicon/carbon dioxide point nano-hybrid material
Gold nanorods/the silica composite is scattered in ethanol, and it is 3g/L gold nanorods/titanium dioxide to obtain concentration
The dispersion liquid of silicon compound；2ml concentration is added into gold nanorods described in 200ml/silica composite dispersion liquid is
0.1mol/L NaOH solution, is sufficiently stirred, and 800 μ l N- (β-aminoethyl)-γ-aminopropyl first is then added dropwise again
The silane-functionalized carbon point of base dimethoxy, reacts 4h under the conditions of 25 DEG C, obtains the 3rd mixture；3rd mixture is entered
Row centrifugal treating, washed 3 times with ethanol, obtain gold nanorods/silicon/carbon dioxide point nano-hybrid material (gold nanorods/dioxy
The transmission electron microscope picture of SiClx/carbon point nano-hybrid material is shown in Fig. 1).
The length 30-70nm of the gold nanorods, draw ratio 4, the nanometer of the gold nanorods/silicon/carbon dioxide point
A diameter of 2-3nm of carbon point in hybrid material, the thickness of silicon dioxide layer is 25nm.
With reference to Fig. 2, it is known that gold nanorods, gold nanorods/silica composite, gold nanorods/silicon/carbon dioxide point
The ultraviolet-visible absorption spectroscopy of nano-hybrid material.In ultraviolet-visible absorption spectroscopy, the gold nanorods respectively in 510nm and
There is absworption peak at 690nm；Gold nanorods/the silica composite has absworption peak at 510nm and 710nm respectively.It is described
The nano-hybrid material of gold nanorods/silicon/carbon dioxide point has absworption peak at 510nm and 760nm.
With reference to Fig. 3, it is known that the hair in the fluorescence emission spectrum of the nano-hybrid material of gold nanorods/silicon/carbon dioxide point
It is 400-500nm to penetrate peak.
Application of the nano-hybrid material of gold nanorods/silicon/carbon dioxide point in diffusing reflection imaging
Diffusing reflection is tested：Diffusing reflection is tested in the special equipment built based on lossless optical image technology
Carried out on (NEGOH-OP TECHNOLOGIES, Israel).According to document " Journal ofbiophotonics, 2012,
263-273. " and " International journal of nanomedicine, the method in 2012,7,449. ", by wavelength
Respectively 650nm and 780nm laser diode is used to radiate as light source, a diameter of 125 μm of optical fiber and photodiode
As detector, detection body mould surface diffusing reflection light intensity Γ (ρ) is with the change of light source and detector distance (ρ), its slope size
Show the imaging effect of the nano-hybrid material of gold nanorods/silicon/carbon dioxide point, slope is larger, and sensitivity is higher, more favourable
In imaging.During detection, light source is moved with 250 μm of step-lengths, and for initial distance close to 1mm, final distance is 5-6mm.Finally by body film
Surface diffusing reflection light intensity Γ (ρ) using digital instrument (Agilent Technologies, Mso7034a, Santa Clara, CA,
USA) test and be for data processing.The body mould refers to original mold or basement membrane.
Raw material：Intralipid is commercially available, and specifications and models are：Lipfundin MCT/LCT 20%, B.Braun
Melsungen AG,Germany；India ink is commercially available, mass concentration 0.1%；Agarose powder is commercially available, is purchased from
SeaKem LE Agarose,Lonza,USA。
The preparation of the body film includes the preparation of basic mode and the preparation of original mold.
The preparation of the basement membrane：By the intralipid of 10% volume, the india ink of 3% volume and 87% body
Product distilled water mixing, obtains the first mixed liquor；1.2g/100ml agarose powder, Ran Houjin are added into first mixed liquor
Row stirring, obtains the second mixed liquor；Second mixed liquor is poured into the container of certain volume, then put the container in vacuum
Put 5h, cooling and solidification；Obtain basement membrane.
The preparation of nano-hybrid material original mold containing gold nanorods/silicon/carbon dioxide point：By a small amount of gold nanorods/dioxy
The nano-hybrid material of SiClx/carbon point is dispersed in water, and obtains minute of the nano-hybrid material of gold nanorods/silicon/carbon dioxide point
Dispersion liquid.Except the distilled water of 87% volume in prepared by basement membrane changes the nanometer of gold nanorods/silicon/carbon dioxide point of 87% volume into
Outside the dispersion liquid of hybrid material, the same basement membrane of preparation method of the nano-hybrid material original mold containing gold nanorods/silicon/carbon dioxide point
Preparation method is the same.
Preparation containing gold nanorods/silica composite original mold：A small amount of gold nanorods/silica composite is disperseed
In water, the dispersion liquid of gold nanorods/silica composite is obtained.Except the distilled water of 87% volume in prepared by basement membrane changes into
Outside the dispersion liquid of gold nanorods/silica composite of 87% volume, the system containing gold nanorods/silica composite original mold
Preparation Method is the same with basement membrane preparation method.
Understood with reference to Fig. 4, the diffusing reflection of the nano-hybrid material of gold nanorods/silicon/carbon dioxide point prepared by the present invention
Image sensitivity is high, and imaging effect is more preferable.
Application of the nano-hybrid material of gold nanorods/silicon/carbon dioxide point in fluorescence lifetime imaging
Fluorescence lifetime imaging：Fluorescence signal is burnt micro- by the scanning copolymerization with time resolution single photon counting capability
The microscope (PQ MT200) of mirror PicoQuant Micro Time 200 are collected.Exciting light uses 473nm, 20MHz frequencies
Picosecond pulse laser.After exciting light is focused into body mould surface, it is imaged by receiving the fluorescent emission signals of collective modes.
Nano-hybrid material original mold containing gold nanorods/silicon/carbon dioxide point uses " gold nanorods/silicon/carbon dioxide point
Nano-hybrid material diffusing reflection imaging in application " in prepare the nano hybridization containing gold nanorods/silicon/carbon dioxide point
Material original mold.
N- (β-aminoethyl)-γ-aminopropyltriethoxy dimethoxy prepared with reference to Fig. 7 (a) and 7 (b), comparative example 1
Silane-functionalized carbon point and gold nanorods/silicon/carbon dioxide point nano-hybrid material original mold fluorescence lifetime imaging figure, can
Know the fluorescence lifetime imaging process of the nano-hybrid material of gold nanorods/silicon/carbon dioxide point compared with N- (β-aminoethyl)-γ-ammonia
Environment where the fluorescence lifetime imaging process of the silane-functionalized carbon point of hydroxypropyl methyl dimethoxy is changed.
Embodiment 2
Except by the silane-functionalized carbon of N- (β-aminoethyl)-γ-aminopropyltriethoxy dimethoxy of step 4) in embodiment 1
The volume of point is changed into outside 2ml, other gold nanorods/silicon/carbon dioxide points of preparing according to the same manner as in Example 1
Nano-hybrid material.
A diameter of 2-3nm of carbon point, silica in the nano-hybrid material of the gold nanorods/silicon/carbon dioxide point
The thickness of layer is 40nm；The nano-hybrid material of the gold nanorods/silicon/carbon dioxide point has in ultraviolet-visible absorption spectroscopy
Two absworption peaks of 510nm and 770nm, and the emission peak of its fluorescence emission spectrum is 400-500nm.
Application of the nano-hybrid material of gold nanorods/silicon/carbon dioxide point in diffusing reflection imaging
Method of testing with embodiment 1, the nano-hybrid material of the gold nanorods/silicon/carbon dioxide point unrestrained transmitting into
Performance as in is close with embodiment 1.
Application of the nano-hybrid material of gold nanorods/silicon/carbon dioxide point in fluorescence lifetime imaging
Imaging results of the nano-hybrid material of the gold nanorods/silicon/carbon dioxide point in fluorescence lifetime imaging with
Embodiment 1 is close.
Embodiment 3
In addition to the concentration of the NaOH solution of step 4) in embodiment 1 is changed into 0.5mol/L, it is other according to embodiment 1
Identical mode prepares the nano-hybrid material of gold nanorods/silicon/carbon dioxide point.
A diameter of 2-3nm of carbon point, silica in the nano-hybrid material of the gold nanorods/silicon/carbon dioxide point
Thickness degree is 15nm, and in ultraviolet-visible absorption spectroscopy, the nano-hybrid material of the gold nanorods/silicon/carbon dioxide point has
Two absworption peaks of 510nm and 710nm, and the emission peak of its fluorescence emission spectrum is 400-500nm.
Application of the nano-hybrid material of gold nanorods/silicon/carbon dioxide point in diffusing reflection imaging
Method of testing with embodiment 1, the nano-hybrid material of the gold nanorods/silicon/carbon dioxide point unrestrained transmitting into
Performance as in is close with embodiment 1.
Application of the nano-hybrid material of gold nanorods/silicon/carbon dioxide point in fluorescence lifetime imaging
Imaging results of the nano-hybrid material of the gold nanorods/silicon/carbon dioxide point in fluorescence lifetime imaging with
Embodiment 1 is close.
Embodiment 4
In addition to the reaction temperature of step 4) in embodiment 1 is changed into 20 DEG C, it is other according to the same manner as in Example 1
Prepare the nano-hybrid material of gold nanorods/silicon/carbon dioxide point.
A diameter of 2-3nm of carbon point, silica in the nano-hybrid material of the gold nanorods/silicon/carbon dioxide point
Thickness degree is 25nm, and in ultraviolet-visible absorption spectroscopy, the nano-hybrid material of the gold nanorods/silicon/carbon dioxide point has
Two absworption peaks of 510nm and 760nm, and the emission peak of its fluorescence emission spectrum is 400-500nm.
Application of the nano-hybrid material of gold nanorods/silicon/carbon dioxide point in diffusing reflection imaging
Method of testing with embodiment 1, the nano-hybrid material of the gold nanorods/silicon/carbon dioxide point unrestrained transmitting into
Performance as in is close with embodiment 1.
Application of the nano-hybrid material of gold nanorods/silicon/carbon dioxide point in fluorescence lifetime imaging
Imaging results of the nano-hybrid material of the gold nanorods/silicon/carbon dioxide point in fluorescence lifetime imaging with
Embodiment 1 is close.
Embodiment 5
It is other to make according to the same manner as in Example 1 in addition to the reaction time of step 4) in embodiment 1 is changed into 8h
The nano-hybrid material of standby gold nanorods/silicon/carbon dioxide point.
A diameter of 2-3nm of carbon point, silica in the nano-hybrid material of the gold nanorods/silicon/carbon dioxide point
Thickness degree is 20nm, and in ultraviolet-visible absorption spectroscopy, the nano-hybrid material of the gold nanorods/silicon/carbon dioxide point has
Two absworption peaks of 510nm and 750nm, and the emission peak of its fluorescence emission spectrum is 400-500nm.
Application of the nano-hybrid material of gold nanorods/silicon/carbon dioxide point in diffusing reflection imaging
Method of testing with embodiment 1, the nano-hybrid material of the gold nanorods/silicon/carbon dioxide point unrestrained transmitting into
Performance as in is close with embodiment 1.
Application of the nano-hybrid material of gold nanorods/silicon/carbon dioxide point in fluorescence lifetime imaging
Imaging results of the nano-hybrid material of the gold nanorods/silicon/carbon dioxide point in fluorescence lifetime imaging with
Embodiment 1 is close.
Embodiment 6
In addition to the reaction time of step 4) in embodiment 1 is changed into 10h, it is other according to the same manner as in Example 1
Prepare the nano-hybrid material of gold nanorods/silicon/carbon dioxide point.
A diameter of 2-3nm of carbon point, silica in the nano-hybrid material of the gold nanorods/silicon/carbon dioxide point
Thickness degree is 28nm, and in ultraviolet-visible absorption spectroscopy, the nano-hybrid material of the gold nanorods/silicon/carbon dioxide point has
Two absworption peaks of 510nm and 760nm, and the emission peak of its fluorescence emission spectrum is 400-500nm.
Application of the nano-hybrid material of gold nanorods/silicon/carbon dioxide point in diffusing reflection imaging
Method of testing with embodiment 1, the nano-hybrid material of the gold nanorods/silicon/carbon dioxide point unrestrained transmitting into
Performance as in is close with embodiment 1.
Application of the nano-hybrid material of gold nanorods/silicon/carbon dioxide point in fluorescence lifetime imaging
Imaging results of the nano-hybrid material of the gold nanorods/silicon/carbon dioxide point in fluorescence lifetime imaging with
Embodiment 1 is close.
Embodiment 7
Step 1) and step 2) are the same as embodiment 1.
3) preparation of APTES functionalized carbon point
After 0.5g citric acids, 1g APTESs and 10g water are sufficiently mixed, it is anti-to be added to hydro-thermal
Answer in kettle, react 8h in 150 DEG C, the second mixture is obtained, by the second mixture ethyl acetate and the mixed liquor of petroleum ether
Extracted, the silane-functionalized carbon point of 3- aminopropyl triethoxies is obtained after revolving.
4) gold nanorods/silicon/carbon dioxide point nano-hybrid material
Gold nanorods/the silica composite is scattered in ethanol, and it is 3g/L gold nanorods/titanium dioxide to obtain concentration
The dispersion liquid of silicon compound；It is 0.1mol/L's that 2ml concentration is added into gold nanorods/silica dispersions described in 200ml
NaOH solution, it is sufficiently stirred, the silane-functionalized carbon of 800 μ l 3- aminopropyl triethoxies is then added dropwise again
Point, 4h is reacted under the conditions of 25 DEG C, obtain the 3rd mixture；3rd mixture is subjected to centrifugal treating, 3 are washed with ethanol
It is secondary, obtain gold nanorods/silicon/carbon dioxide point nano-hybrid material.
Application of the nano-hybrid material of gold nanorods/silicon/carbon dioxide point in diffusing reflection imaging
Method of testing with embodiment 1, the nano-hybrid material of the gold nanorods/silicon/carbon dioxide point unrestrained transmitting into
Performance as in is close with embodiment 1.
Application of the nano-hybrid material of gold nanorods/silicon/carbon dioxide point in fluorescence lifetime imaging
Imaging results of the nano-hybrid material of the gold nanorods/silicon/carbon dioxide point in fluorescence lifetime imaging with
Embodiment 1 is close.
Comparative example 1
The preparation of gold nanorods
The preparation of gold nanorods is with embodiment 1, the length 30-70nm of the gold nanorods, draw ratio 4, it is ultraviolet can
See in absorption spectrum, the gold nanorods have absworption peak at 510nm and 690nm respectively.
Application of the gold nanorods in diffusing reflection imaging
Except changing the dispersion liquid of the nano-hybrid material of gold nanorods/silicon/carbon dioxide point into gold nanorods scattered
Outside liquid, it is other with embodiment 1 " nano-hybrid material of gold nanorods/silicon/carbon dioxide point diffusing reflection imaging in
Application " part is identical.
In diffusing reflection imaging, slope is bigger, and sensitivity is higher；Understood with reference to Fig. 5, gold nanorods prepared by comparative example 1
Diffusing reflection image sensitivity be less than the embodiment of the present invention 1 prepare gold nanorods/silicon/carbon dioxide point nano-hybrid material
Diffusing reflection image sensitivity, therefore the nano-hybrid material of gold nanorods/silicon/carbon dioxide point be particularly suited for diffusing reflection into
As in application.
Application of the gold nanorods in fluorescence lifetime imaging
Except changing the dispersion liquid of the nano-hybrid material of gold nanorods/silicon/carbon dioxide point into gold nanorods scattered
Outside liquid, it is other with embodiment 1 " nano-hybrid material of gold nanorods/silicon/carbon dioxide point is in fluorescence lifetime imaging
In application " part is identical.
As a result show, gold nanorods can not carry out the application of fluorescence lifetime imaging.
Comparative example 2
The preparation of gold nanorods is with embodiment 1, by the 5ml gold nanorods and 10ml methoxypolyethylene glycols-sulfydryl
(m-PEG-SH) (molecular weight of the m-PEG-SH is 5000) mixes, and is stirred 2h, then adding 12 μ L concentration is
100 μm of ol/L luciferin solution, stirring reaction 12h, is post-processed, and obtains the nano-hybrid material of gold nanorods/dyestuff.
Application of the nano-hybrid material of gold nanorods/dyestuff in diffusing reflection imaging
Except changing the dispersion liquid of the nano-hybrid material of gold nanorods/silicon/carbon dioxide point into gold nanorods/dyestuff
Outside the dispersion liquid of nano-hybrid material, it is other with the " nano hybridization of gold nanorods/silicon/carbon dioxide point in embodiment 1
Application of the material in diffusing reflection " part is identical.
In diffusing reflection imaging, slope is bigger, and sensitivity is higher；Understand that gold nanorods/dyestuff is received with reference to Fig. 5 and Fig. 6
The diffusing reflection image sensitivity of rice hybrid material is less than the diffusing reflection of the nano-hybrid material of gold nanorods/silicon/carbon dioxide point
Image sensitivity, therefore the nano-hybrid material of gold nanorods/silicon/carbon dioxide point is particularly suited for diffusing reflection imaging applications
In.
Application of the nano-hybrid material of gold nanorods/dyestuff in fluorescence lifetime imaging
Except changing the dispersion liquid of the nano-hybrid material of gold nanorods/silicon/carbon dioxide point into gold nanorods/dyestuff
Outside nano-hybrid material solution, it is other with the " nano-hybrid material of gold nanorods/silicon/carbon dioxide point in embodiment 1
Application in fluorescence lifetime imaging " part is identical.
As a result show, the imaging results and Jenner of the nano-hybrid material of gold nanorods/dyestuff in fluorescence lifetime imaging
Imaging results of the nano-hybrid material of rice rod/silicon/carbon dioxide point in fluorescence lifetime imaging are close.
Obviously, the above embodiment of the present invention is only intended to clearly illustrate example of the present invention, and is not pair
The restriction of embodiments of the present invention, for those of ordinary skill in the field, may be used also on the basis of the above description
To make other changes in different forms, all embodiments can not be exhaustive here, it is every to belong to this hair
Row of the obvious changes or variations that bright technical scheme is extended out still in protection scope of the present invention.
Claims (10)
- A kind of 1. nano-hybrid material of gold nanorods/silicon/carbon dioxide point, it is characterised in that the nano-hybrid material bag Include the gold nanorods as core, the silicon dioxide layer as shell and the carbon point for being distributed in silicon dioxide layer outer surface；The nanometer Hybrid material is that with the silane-functionalized carbon point containing amino coupling work occurs for the silicon dioxide layer coated by gold nanorods outer surface Obtained from；The gold nanorods length is 30-100 nm, and the draw ratio of the gold nanorods is 2-6；The thickness of the silicon dioxide layer is 10-40 nm；The particle diameter of the carbon point is 1-10nm.
- 2. a kind of preparation method of the nano-hybrid material of gold nanorods/silicon/carbon dioxide point as claimed in claim 1, its It is characterised by, comprises the following steps：1) preparation of gold nanorods2) gold nanorods/silica compositeBy step 1）The gold nanorods of middle preparation are dispersed in water, and obtain the dispersion liquid containing gold nanorods；By point containing gold nanorods Dispersion liquid, the methanol solution containing tetraethyl orthosilicate and aqueous slkali mixing, then stirring reaction 1-5h at normal temperatures, obtains the first mixing Thing, first mixture is subjected to centrifugal treating, washs to obtain gold nanorods/silica composite；3) the silane-functionalized carbon point containing aminoCitric acid, the silane containing amino and water are mixed, then 4-10h is reacted at 120-200 DEG C, the second mixture is obtained, by institute State the second mixture to be extracted and rotated, obtain the silane-functionalized carbon point containing amino；4) nano-hybrid material of gold nanorods/silicon/carbon dioxide pointBy step 2）Gold nanorods/silica composite of middle preparation is scattered in ethanol, and it is multiple to obtain gold nanorods/silica The dispersion liquid of compound；By the dispersion liquid of gold nanorods/silica composite, aqueous slkali and silane-functionalized carbon point containing amino Mixing, then the stirring reaction 3-10h at 20-30 DEG C, obtains the 3rd mixture；By the 3rd mixture carry out centrifugal treating, Wash gold nanorods/silicon/carbon dioxide point nano-hybrid material.
- 3. the preparation method of the nano-hybrid material of gold nanorods according to claim 2/silicon/carbon dioxide point, it is special Sign is, step 1）The preparation of middle gold nanorods is carried out as follows：1) by HAuCl4The aqueous solution, NaBH4The aqueous solution is added sequentially in the CTAB aqueous solution, after constant temperature is stood, obtains seed-solution；2）By HAuCl4The aqueous solution, AgNO3The aqueous solution, HCl/water solution, aqueous ascorbic acid are added sequentially to the CTAB aqueous solution In, obtain the 4th mixture；When the 4th mixture is become colorless by orange-yellow, then it is molten to add the crystal seed into the 4th mixture Liquid, then constant temperature standing, obtains the mixed liquor containing gold nanorods；Mixed liquor containing gold nanorods is subjected to centrifugal treating, obtains Jenner Rice rod.
- 4. the preparation method of the nano-hybrid material of gold nanorods according to claim 2/silicon/carbon dioxide point, it is special Sign is that the aqueous slkali is the aqueous solution of sodium hydroxide, potassium hydroxide or ammoniacal liquor；The concentration of the aqueous slkali is 0.1-1 mol/L。
- 5. the preparation method of the nano-hybrid material of gold nanorods according to claim 2/silicon/carbon dioxide point, it is special Sign is, step 2）In, the volume ratio of the dispersion liquid containing gold nanorods, the methanol solution containing tetraethyl orthosilicate and aqueous slkali For 1000-2000: 8-16:1；The volume ratio of tetraethyl orthosilicate and methanol is 1 in the methanol solution containing tetraethyl orthosilicate: 3-10。
- 6. the preparation method of the nano-hybrid material of gold nanorods according to claim 2/silicon/carbon dioxide point, its It is characterised by, the dispersion liquid concentration containing gold nanorods is 0.1-1g/L.
- 7. the preparation method of the nano-hybrid material of gold nanorods according to claim 2/silicon/carbon dioxide point, it is special Sign is, step 3）In, the silane containing amino is N-（β-aminoethyl）- γ-aminopropyltriethoxy dimethoxysilane, N- （β-aminopropyl）- γ-aminopropyltriethoxy trimethoxy silane or APTES.
- 8. the preparation method of the nano-hybrid material of gold nanorods according to claim 2/silicon/carbon dioxide point, it is special Sign is that the mass ratio of the citric acid, the silane containing amino and water is 1:2-20:2-20.
- 9. the preparation method of the nano-hybrid material of gold nanorods according to claim 2/silicon/carbon dioxide point, it is special Sign is, step 4）In, the concentration of the dispersion liquid of gold nanorods/silica composite is 3-10 g/L；The gold nanorods/ The volume ratio of the dispersion liquid of silica composite, aqueous slkali and the silane-functionalized carbon point containing amino is 50-500: 1-20: 1。
- 10. a kind of application of the nano-hybrid material of gold nanorods/silicon/carbon dioxide point as claimed in claim 1, its feature It is, the nano-hybrid material of the gold nanorods/silicon/carbon dioxide point is in diffusing reflection imaging or answering in the fluorescence imaging life-span With.
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| CN106983874B (en) * | 2017-04-11 | 2020-04-10 | 中国科学院理化技术研究所 | Gold nanorod/polyethylene glycol/carbon dot nano hybrid imaging contrast material and preparation method and application thereof |
| CN108949144A (en) * | 2018-08-27 | 2018-12-07 | 宝鸡文理学院 | A kind of Au@SiO2@CDs nanocomposite and preparation method thereof |
| CN109370574B (en) * | 2018-12-11 | 2021-07-16 | 山东理工大学 | Method for preparing methylene blue-containing silicon dioxide/carbon composite particles with high fluorescence intensity by hydrothermal method |
| CN109971460A (en) * | 2019-03-14 | 2019-07-05 | 天津大学 | A kind of preparation method of Ratiometric fluorescent probe and its application in detection water in terms of copper ion |
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