CN105817617A - Gold nanorod/silicon dioxide/carbon point nanometer hybrid material and preparation method and application thereof - Google Patents
Gold nanorod/silicon dioxide/carbon point nanometer hybrid material and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a gold nanorod/silicon dioxide/carbon point nanometer hybrid material. The nanometer hybrid material comprises a gold nanorod as a core, a silicon dioxide layer as a shell, and carbon points distributed on the outer surface of the silicon dioxide layer; and the nanometer hybrid material is obtained by a coupling effect between the silicon dioxide layer coating the outer surface of the gold nanorod and silane functional carbon points containing amido. The invention further discloses a preparation method of the gold nanorod/silicon dioxide/carbon point nanometer hybrid material. The preparation method of the gold nanorod/silicon dioxide/carbon point nanometer hybrid material is simple and controllable. The gold nanorod/silicon dioxide/carbon point nanometer hybrid material realizes application to diffuse reflection imaging through the gold nanorod, realizes application to fluorescent life imaging through the carbon points, realizes non-intrusive multi-mode imaging, and is excellent in application prospect in the cancer diagnosis.
Description
Technical field
The present invention relates to bio-imaging technical field.Nano-hybrid material more particularly, to a kind of gold nanorods/silicon/carbon dioxide point 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 grain has surface plasma bulk effect (SPR), have at visible ray and near infrared light region and significantly absorb and scattering property, therefore gold nano grain generally carries out high-resolution, highly sensitive light scattering imaging at tumor cell and atherosclerosis position.Because the size and dimension dependence optical property that gold nano grain is unique, gold nano grain can be as the contrast agent in good imaging system.At lesions position, the optical property of gold nano grain can change thus improve image contrast.Diffuse-reflectance imaging (DR) is a kind of novel optical diagnostic method, it simply, safely, inexpensively, realizes bigger length of penetration by lower emittance, thus shows histiocytic pattern (Nanoletters, 2014,14 (5): 2681-2687.).In DR detects, the distance change between light source and detector, cause histiocytic intensity of reflected light change on the detector, thus obtain histiocytic information.Gold nanorods is as " the external absorbent " in tissue, apply after being connected with fluorescent dye in diffuse-reflectance and fluorescence lifetime imaging (FLIM), achieve multi-modality imaging, thus judge in-house metabolic condition (ACSphotonics, 2014,1 (9): 900-905).Traditional fluorescence imaging method is based on fluorescence intensity, and fluorescence lifetime imaging (FLIM) is based on fluorescence decay time, fluorescence based on each pixel rather than the overall fluorescent intensity of fluorescent material, thus defines the imaging results of more high-contrast.Semiconductor-quantum-point and fluorescent dye can be applied in optical imaging field because of the photoluminescent property of its uniqueness, but scintillation fluor and toxicity greatly limit again its application, it is therefore desirable to find the higher fluorescent material of a kind of biocompatibility to meet the demand of medical diagnosis on disease in organism.
Photoluminescent property, biocompatibility, environment-friend substitution, low cost and the hypotoxicity of carbon point excellence and chemical stability so that carbon point has wider array of application in biologic applications field.DR can provide the image information of tissue surface by FLIM according to the depth information of the position offer organization internal of gold nanorods, hence sets up and can have very profound significance in non-intrusion type medical diagnosis on disease in conjunction with the multi-modality imaging mechanism of FLIM and DR.
Summary of the invention
First purpose of the present invention is to provide the nano-hybrid material of a kind of gold nanorods/silicon/carbon dioxide point.
Second object of the present invention is to provide the preparation method of the nano-hybrid material of a kind of gold nanorods/silicon/carbon dioxide point.
Third object of the present invention is the nano-hybrid material providing a kind of gold nanorods/silicon/carbon dioxide point application in diffuse-reflectance imaging or fluorescence lifetime imaging.
For reaching above-mentioned purpose, the present invention uses following technical proposals:
The present invention provides the nano-hybrid material of a kind of gold nanorods/silicon/carbon dioxide point, and described nano-hybrid material includes the gold nanorods as core, as the silicon dioxide layer of shell be distributed in the carbon point of silicon dioxide layer outer surface；Described nano-hybrid material be the silicon dioxide layer that is coated with by gold nanorods outer surface with the silane-functionalized carbon point generation coupled action containing amino and obtain；
The a length of 30-100nm of described gold nanorods, the draw ratio of described gold nanorods is 2-6；
The thickness of described silicon dioxide layer is 10-40nm；
The particle diameter of described carbon point is 1-10nm.
The present invention provides the preparation method of the nano-hybrid material of a kind of gold nanorods/silicon/carbon dioxide point, comprises the steps:
1) preparation [reference literature ACSphotonics, 2014,1 (9): 900-905.] of gold nanorods
By HAuCl4Aqueous solution, NaBH4Aqueous solution is added sequentially in CTAB aqueous solution, after constant temperature stands, obtains seed-solution；
By HAuCl4Aqueous solution, AgNO3Aqueous solution, HCl/water solution, aqueous ascorbic acid are added sequentially in CTAB aqueous solution, obtain the 4th mixture；When the 4th mixture is become colorless by orange-yellow, then adding described seed-solution in the 4th mixture, then constant temperature stands, and must contain the mixed liquor of gold nanorods；It is centrifuged the mixed liquor containing gold nanorods processing, obtains gold nanorods.
2) gold nanorods/silica composite
By step 1) in preparation gold nanorods be dispersed in water, the dispersion liquid of gold nanorods must be contained；By the dispersion liquid containing gold nanorods, methanol solution containing tetraethyl orthosilicate and aqueous slkali according to the ratio mixing that volume ratio is 1000-2000:8-16:1, the 1-5h of stirring reaction the most at normal temperatures, obtain the first mixture, be centrifuged described first mixture processing, washing to obtain gold nanorods/silica composite；
3) the silane-functionalized carbon point containing amino
By citric acid, silane containing amino and water according to the ratio mixing that mass ratio is 1:2-20:2-20, then in the hydrothermal reaction kettle of 120-200 DEG C, react 4-10h, obtain the second mixture, carry out extracting and revolving steaming by described second mixture, obtain the silane-functionalized carbon point containing amino of flow regime；
4) nano-hybrid material of gold nanorods/silicon/carbon dioxide point
Described gold nanorods/silica composite is disperseed in ethanol, obtains the dispersion liquid of gold nanorods/silica composite；By the dispersion liquid of gold nanorods/silica composite, aqueous slkali and the mixing of the silane-functionalized carbon point containing amino, then stirring reaction 3-10h at 20-30 DEG C, obtains the 3rd mixture；It is centrifuged described 3rd mixture processing, washing to obtain the nano-hybrid material of gold nanorods/silicon/carbon dioxide point.
Described aqueous slkali is the aqueous solution of sodium hydroxide, potassium hydroxide or ammonia；Preferably, the concentration of described aqueous slkali is 0.1-1mol/L.
Step 2) in, in the described methanol solution containing tetraethyl orthosilicate, the volume ratio of tetraethyl orthosilicate and methanol is 1:3-10.
The described dispersion liquid concentration containing gold nanorods is 0.1-1g/L.
Step 3) in, the described silane containing amino is N-(β-aminoethyl)-γ-aminopropyltriethoxy dimethoxysilane, N-(β-aminopropyl)-γ-aminopropyltriethoxy trimethoxy silane or APTES.
Step 3) in, extractant is the mixed liquor of ethyl acetate and petroleum ether.
Step 4) in, the concentration of the dispersion liquid of described gold nanorods/silica composite is 3-10g/L.
Step 4) in, the volume ratio of the dispersion liquid of described gold nanorods/silica composite, aqueous slkali and the silane-functionalized carbon point containing amino is 50-500:1-20:1.
Further, the nano-hybrid material good dispersion of the gold nanorods of the present invention/silicon/carbon dioxide point, will not assemble, the silicon dioxide layer of described gold nanorods outer surface cladding and the silane-functionalized carbon point generation coupled action containing amino, make carbon point be evenly distributed in silicon dioxide layer.The nano-hybrid material covalent bond based on Si-O-Si of described gold nanorods/silicon/carbon dioxide point connects, and the stability of the most described nano-hybrid material is higher.
Present invention also offers the application of the nano-hybrid material of a kind of gold nanorods/silicon/carbon dioxide point, the nano-hybrid material of described gold nanorods/silicon/carbon dioxide point is respectively in diffuse-reflectance imaging and the application in the fluorescence imaging life-span.
Beneficial effects of the present invention is as follows:
1, the preparation method of the nano-hybrid material of the gold nanorods of the present invention/silicon/carbon dioxide point is the most controlled, not only inhibits the gathering of gold nanorods, and remains the surface plasma resonance of gold nanorods.
2, the nano-hybrid material of the gold nanorods of the present invention/silicon/carbon dioxide point not only has the optical property of gold nano grain, it may have the photoluminescent property that carbon point is excellent.
3, the present invention is by the nano-hybrid material of the gold nanorods/silicon/carbon dioxide point of preparation, obtains diffuse-reflectance imaging effect more more preferable than gold nanorods, and obtain than carbon point more preferably imaging effect in fluorescence lifetime imaging in body mould.
4, the application that the nano-hybrid material of the gold nanorods of the present invention/silicon/carbon dioxide point is realized in diffuse-reflectance imaging by gold nanorods, the application realized in fluorescence lifetime imaging by carbon point, thus realize non-intrusion type multi-modality imaging.
5, the nano-hybrid material of the gold nanorods of the present invention/silicon/carbon dioxide point has splendid biocompatibility and stability, therefore has good application prospect in cancer diagnosis.
Accompanying drawing explanation
Below in conjunction with the accompanying drawings the detailed description of the invention of the present invention is described in further detail.
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/SiO prepared by embodiment 12), the nano-hybrid material (CNRs/SiO of gold nanorods/silicon/carbon dioxide point2/ CDs) ultraviolet-visible absorption spectroscopy.
Fig. 3 shows the fluorescence emission spectrum of the nano-hybrid material of gold nanorods/silicon/carbon dioxide point prepared by embodiment 1.
Fig. 4 shows gold nanorods (CNRs), gold nanorods/silica composite (CNRs/SiO prepared by embodiment 12), the nano-hybrid material (CNRs/SiO of gold nanorods/silicon/carbon dioxide point2/ CDs) diffuse-reflectance imaging results in simulated tissue.
Fig. 5 shows gold nanorods (CNRs), the nano-hybrid material (CNRs/SiO of gold nanorods/silicon/carbon dioxide point prepared by embodiment 12/ CDs) G-bar of diffuse-reflectance imaging in simulated tissue.
Fig. 6 shows the G-bar of the nano-hybrid material diffuse-reflectance imaging in simulated tissue of dyestuff in comparative example 2, gold nanorods/dyestuff.
Fig. 7 (a) and 7 (b) show silane-functionalized carbon point and the gold nanorods/silicon/carbon dioxide point nano-hybrid material fluorescence lifetime imaging figure in simulated tissue of N-(β-aminoethyl)-γ-aminopropyltriethoxy dimethoxy prepared by embodiment 1.
Detailed description of the invention
In order to be illustrated more clearly that the present invention, below in conjunction with preferred embodiments and drawings, the present invention is described further.It will be appreciated by those skilled in the art that following specifically described content is illustrative and be not restrictive, should not limit the scope of the invention with this.
Embodiment 1
The preparation of the nano-hybrid material of gold nanorods/silicon/carbon dioxide point
1) preparation of gold nanorods
A. it is the HAuCl of 0.01mol/L by 0.25ml concentration4The NaBH that concentration is 0.01mol/L that aqueous solution and 0.6ml ice bath are crossed4Aqueous solution is added sequentially in the CTAB aqueous solution that 7.5ml concentration is 0.01mol/L, after constant temperature 30 DEG C stands 2h, obtains seed-solution；
B. it is the HAuCl of 0.01mol/L by 10ml concentration4Aqueous solution, 1.5ml concentration are the AgNO of 0.01mol/L3Aqueous solution, 5ml concentration are the HCl/water solution of 1mol/L and the aqueous ascorbic acid that 0.32ml concentration is 0.1mol/L joins in the CTAB aqueous solution that 200ml concentration is 0.1mol/L, obtain the 4th mixture, when the 4th mixture is become colorless by orange-yellow, seed-solution described in 480 μ l is added in the 4th mixture, then constant temperature 30 DEG C stands 16h, must contain the mixed liquor of gold nanorods；It is centrifuged the mixed liquor containing gold nanorods processing, obtains gold nanorods.
2) gold nanorods/silica composite
The methanol solution (in the described methanol solution containing tetraethyl orthosilicate, the volume ratio of tetraethyl orthosilicate and methanol is 1:5) containing tetraethyl orthosilicate that 150 μ L concentration are 0.1mol/LNaOH solution and 1.6ml it is sequentially added in 200ml gold nanorods dispersion liquid, 1.5h is stirred under room temperature, obtain the first mixture, it is centrifuged described first mixture processing, by washing with alcohol 3 times, obtain gold nanorods/silica composite.
3) the silane-functionalized carbon point of N-(β-aminoethyl)-γ-aminopropyltriethoxy dimethoxy
After the water of 0.5g citric acid and 10gN-(β-aminoethyl)-γ-aminopropyltriethoxy dimethoxysilane and 10g is sufficiently mixed, join in hydrothermal reaction kettle, 8h is reacted in 150 DEG C, obtain the second mixture, being extracted by the mixed liquor of described second mixture ethyl acetate and petroleum ether, rotation obtains the silane-functionalized carbon point of N-(β-aminoethyl)-γ-aminopropyltriethoxy dimethoxy of flow regime after steaming.
4) gold nanorods/silicon/carbon dioxide point nano-hybrid material
Described gold nanorods/silica composite is disperseed in ethanol, obtains the dispersion liquid that concentration is 3g/L gold nanorods/silica composite；Adding 2ml concentration in gold nanorods described in 200ml/silica composite dispersion liquid is the NaOH solution of 0.1mol/L, it is sufficiently stirred for, it is added dropwise over the silane-functionalized carbon point of N-(β-aminoethyl)-γ-aminopropyltriethoxy dimethoxy of 800 μ l the most again, under the conditions of 25 DEG C, react 4h, obtain the 3rd mixture；It is centrifuged described 3rd mixture processing, by washing with alcohol 3 times, obtains gold nanorods/silicon/carbon dioxide point nano-hybrid material (transmission electron microscope picture of gold nanorods/silicon/carbon dioxide point nano-hybrid material is shown in Fig. 1).
Length 30-70nm of described gold nanorods, draw ratio is 4, and a diameter of 2-3nm of carbon point in the nano-hybrid material of described gold nanorods/silicon/carbon dioxide point, the thickness of silicon dioxide layer is 25nm.
In conjunction with Fig. 2, it is known that the ultraviolet-visible absorption spectroscopy of the nano-hybrid material of gold nanorods, gold nanorods/silica composite, gold nanorods/silicon/carbon dioxide point.In ultraviolet-visible absorption spectroscopy, described gold nanorods has absworption peak respectively at 510nm and 690nm；Described gold nanorods/silica composite has absworption peak respectively at 510nm and 710nm.The nano-hybrid material of described gold nanorods/silicon/carbon dioxide point has absworption peak at 510nm and 760nm.
In conjunction with Fig. 3, it is known that the emission peak in the fluorescence emission spectrum of the nano-hybrid material of gold nanorods/silicon/carbon dioxide point is 400-500nm.
The application in diffuse-reflectance imaging of the nano-hybrid material of gold nanorods/silicon/carbon dioxide point
Diffuse-reflectance is tested: diffuse-reflectance test is carried out on the special equipment (NEGOH-OPTECHNOLOGIES, Israel) built based on lossless optical image technology.According to document " Journalofbiophotonics, 2012, 263-273. " and " Internationaljournalofnanomedicine, 2012, 7, 449. the method in ", wavelength is respectively the laser diode of 650nm and 780nm as light source, the optical fiber of a diameter of 125 μm is for radiating with photodiode as detector, detection bodies mould surface diffuse reflectance light intensity Γ (ρ) is with the change of light source Yu detector distance (ρ), its slope size shows the imaging effect of the nano-hybrid material of gold nanorods/silicon/carbon dioxide point, slope is bigger, sensitivity is the highest, more be conducive to imaging.During detection, light source moves with 250 μm step-lengths, and initial distance is close to 1mm, and final distance is 5-6mm.Finally body film surface diffuse reflectance light intensity Γ (ρ) Applied Digital instrument (AgilentTechnologies, Mso7034a, SantaClara, CA, USA) is tested and is for data processing.Described body mould refers to original mold or basement membrane.
Raw material: intralipid is commercially available, specifications and models are: LipfundinMCT/LCT20%, B.BraunMelsungenAG, Germany；India ink is commercially available, and mass concentration is 0.1%；Agarose powder is commercially available, purchased from SeaKemLEAgarose, Lonza, USA.
The preparation of described body film includes the preparation of basic mode and the preparation of original mold.
The preparation of described basement membrane: by the intralipid of 10% volume, the india ink of 3% volume and the mixing of 87% volume distilled water, obtain the first mixed liquor；In described first mixed liquor, add the agarose powder of 1.2g/100ml, be then stirred, obtain the second mixed liquor；Second mixed liquor is poured in the container of certain volume, then described container is placed in vacuum 5h, cools down and solidify；Obtain basement membrane.
Preparation containing the nano-hybrid material original mold of gold nanorods/silicon/carbon dioxide point: be dispersed in water by the nano-hybrid material of a small amount of gold nanorods/silicon/carbon dioxide point, obtains the dispersion liquid of the nano-hybrid material of gold nanorods/silicon/carbon dioxide point.In being prepared by basement membrane in addition to the dispersion liquid of the nano-hybrid material that the distilled water of 87% volume changes the gold nanorods/silicon/carbon dioxide point of 87% volume into, the preparation method containing the nano-hybrid material original mold of gold nanorods/silicon/carbon dioxide point is the same with basement membrane preparation method.
Preparation containing gold nanorods/silica composite original mold: a small amount of gold nanorods/silica composite is dispersed in water, obtains the dispersion liquid of gold nanorods/silica composite.In being prepared by basement membrane, the distilled water of 87% volume changes in addition to the dispersion liquid of gold nanorods/silica composite of 87% volume, and the preparation method containing gold nanorods/silica composite original mold is the same with basement membrane preparation method.
Understanding in conjunction with Fig. 4, the diffuse-reflectance image sensitivity of the nano-hybrid material of gold nanorods prepared by the present invention/silicon/carbon dioxide point is high, and imaging effect is more preferable.
The application in fluorescence lifetime imaging of the nano-hybrid material of gold nanorods/silicon/carbon dioxide point
Fluorescence lifetime imaging: fluorescence signal is to be collected by the scanning confocal microscope PicoQuantMicroTime200microscope (PQMT200) with time resolution single photon counting capability.Exciting light uses the picosecond pulse laser of 473nm, 20MHz frequency.After exciting light is focused to body mould surface, carry out imaging by the fluorescent emission signals receiving collective modes.
Nano-hybrid material original mold containing gold nanorods/silicon/carbon dioxide point uses the nano-hybrid material original mold containing gold nanorods/silicon/carbon dioxide point of preparation in " application in diffuse-reflectance imaging of the nano-hybrid material of gold nanorods/silicon/carbon dioxide point ".
In conjunction with Fig. 7 (a) and 7 (b), the silane-functionalized carbon point of N-(β-aminoethyl)-γ-aminopropyltriethoxy dimethoxy of comparative example 1 preparation and the fluorescence lifetime imaging figure of the nano-hybrid material original mold of gold nanorods/silicon/carbon dioxide point, it is known that the environment at the fluorescence lifetime imaging process place of the silane-functionalized carbon point of fluorescence lifetime imaging process relatively N-(β-aminoethyl)-γ-aminopropyltriethoxy dimethoxy of the nano-hybrid material of gold nanorods/silicon/carbon dioxide point there occurs change.
Embodiment 2
Except by step 4 in embodiment 1) the volume of silane-functionalized carbon point of N-(β-aminoethyl)-γ-aminopropyltriethoxy dimethoxy become 2ml in addition to, other prepares the nano-hybrid material of gold nanorods/silicon/carbon dioxide point the most according to the same manner as in Example 1.
A diameter of 2-3nm of carbon point in the nano-hybrid material of described gold nanorods/silicon/carbon dioxide point, the thickness of silicon dioxide layer is 40nm；The nano-hybrid material of described gold nanorods/silicon/carbon dioxide point has two absworption peaks of 510nm and 770nm in ultraviolet-visible absorption spectroscopy, and the emission peak of its fluorescence emission spectrum is 400-500nm.
The application in diffuse-reflectance imaging of the nano-hybrid material of gold nanorods/silicon/carbon dioxide point
Method of testing is with embodiment 1, and the nano-hybrid material of described gold nanorods/silicon/carbon dioxide point performance in unrestrained transmitting imaging is close with embodiment 1.
The application in fluorescence lifetime imaging of the nano-hybrid material of gold nanorods/silicon/carbon dioxide point
The nano-hybrid material of described gold nanorods/silicon/carbon dioxide point imaging results in fluorescence lifetime imaging is close with embodiment 1.
Embodiment 3
Except by step 4 in embodiment 1) the concentration of NaOH solution become 0.5mol/L in addition to, other prepares the nano-hybrid material of gold nanorods/silicon/carbon dioxide point the most according to the same manner as in Example 1.
A diameter of 2-3nm of carbon point in the nano-hybrid material of described gold nanorods/silicon/carbon dioxide point, silicon dioxide layer thickness is 15nm, in ultraviolet-visible absorption spectroscopy, the nano-hybrid material of described 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.
The application in diffuse-reflectance imaging of the nano-hybrid material of gold nanorods/silicon/carbon dioxide point
Method of testing is with embodiment 1, and the nano-hybrid material of described gold nanorods/silicon/carbon dioxide point performance in unrestrained transmitting imaging is close with embodiment 1.
The application in fluorescence lifetime imaging of the nano-hybrid material of gold nanorods/silicon/carbon dioxide point
The nano-hybrid material of described gold nanorods/silicon/carbon dioxide point imaging results in fluorescence lifetime imaging is close with embodiment 1.
Embodiment 4
Except by step 4 in embodiment 1) reaction temperature become 20 DEG C in addition to, other prepares the nano-hybrid material of gold nanorods/silicon/carbon dioxide point the most according to the same manner as in Example 1.
A diameter of 2-3nm of carbon point in the nano-hybrid material of described gold nanorods/silicon/carbon dioxide point, silicon dioxide layer thickness is 25nm, in ultraviolet-visible absorption spectroscopy, the nano-hybrid material of described 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.
The application in diffuse-reflectance imaging of the nano-hybrid material of gold nanorods/silicon/carbon dioxide point
Method of testing is with embodiment 1, and the nano-hybrid material of described gold nanorods/silicon/carbon dioxide point performance in unrestrained transmitting imaging is close with embodiment 1.
The application in fluorescence lifetime imaging of the nano-hybrid material of gold nanorods/silicon/carbon dioxide point
The nano-hybrid material of described gold nanorods/silicon/carbon dioxide point imaging results in fluorescence lifetime imaging is close with embodiment 1.
Embodiment 5
Except by step 4 in embodiment 1) response time become 8h in addition to, other prepares the nano-hybrid material of gold nanorods/silicon/carbon dioxide point the most according to the same manner as in Example 1.
A diameter of 2-3nm of carbon point in the nano-hybrid material of described gold nanorods/silicon/carbon dioxide point, silicon dioxide layer thickness is 20nm, in ultraviolet-visible absorption spectroscopy, the nano-hybrid material of described 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.
The application in diffuse-reflectance imaging of the nano-hybrid material of gold nanorods/silicon/carbon dioxide point
Method of testing is with embodiment 1, and the nano-hybrid material of described gold nanorods/silicon/carbon dioxide point performance in unrestrained transmitting imaging is close with embodiment 1.
The application in fluorescence lifetime imaging of the nano-hybrid material of gold nanorods/silicon/carbon dioxide point
The nano-hybrid material of described gold nanorods/silicon/carbon dioxide point imaging results in fluorescence lifetime imaging is close with embodiment 1.
Embodiment 6
Except by step 4 in embodiment 1) response time become 10h in addition to, other prepares the nano-hybrid material of gold nanorods/silicon/carbon dioxide point the most according to the same manner as in Example 1.
A diameter of 2-3nm of carbon point in the nano-hybrid material of described gold nanorods/silicon/carbon dioxide point, silicon dioxide layer thickness is 28nm, in ultraviolet-visible absorption spectroscopy, the nano-hybrid material of described 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.
The application in diffuse-reflectance imaging of the nano-hybrid material of gold nanorods/silicon/carbon dioxide point
Method of testing is with embodiment 1, and the nano-hybrid material of described gold nanorods/silicon/carbon dioxide point performance in unrestrained transmitting imaging is close with embodiment 1.
The application in fluorescence lifetime imaging of the nano-hybrid material of gold nanorods/silicon/carbon dioxide point
The nano-hybrid material of described gold nanorods/silicon/carbon dioxide point imaging results in fluorescence lifetime imaging is close with embodiment 1.
Embodiment 7
Step 1) and step 2) with embodiment 1.
3) preparation of APTES functionalized carbon point
After 0.5g citric acid, 1g3-aminopropyltriethoxywerene werene and 10g water are sufficiently mixed, join in hydrothermal reaction kettle, 8h is reacted in 150 DEG C, obtain the second mixture, being extracted by the mixed liquor of described second mixture ethyl acetate and petroleum ether, rotation obtains the silane-functionalized carbon point of 3-aminopropyl triethoxy after steaming.
4) gold nanorods/silicon/carbon dioxide point nano-hybrid material
Described gold nanorods/silica composite is disperseed in ethanol, obtains the dispersion liquid that concentration is 3g/L gold nanorods/silica composite；Adding 2ml concentration in gold nanorods/silica dispersions described in 200ml is the NaOH solution of 0.1mol/L, it is sufficiently stirred for, it is added dropwise over the silane-functionalized carbon point of the 3-aminopropyl triethoxy of 800 μ l the most again, under the conditions of 25 DEG C, reacts 4h, obtain the 3rd mixture；It is centrifuged described 3rd mixture processing, by washing with alcohol 3 times, obtains gold nanorods/silicon/carbon dioxide point nano-hybrid material.
The application in diffuse-reflectance imaging of the nano-hybrid material of gold nanorods/silicon/carbon dioxide point
Method of testing is with embodiment 1, and the nano-hybrid material of described gold nanorods/silicon/carbon dioxide point performance in unrestrained transmitting imaging is close with embodiment 1.
The application in fluorescence lifetime imaging of the nano-hybrid material of gold nanorods/silicon/carbon dioxide point
The nano-hybrid material of described gold nanorods/silicon/carbon dioxide point imaging results in fluorescence lifetime imaging is close with embodiment 1.
Comparative example 1
The preparation of gold nanorods
The preparation of gold nanorods is with embodiment 1, length 30-70nm of described gold nanorods, and draw ratio is 4, and in ultraviolet-visible absorption spectroscopy, described gold nanorods has absworption peak respectively at 510nm and 690nm.
Gold nanorods application in diffuse-reflectance imaging
In addition to the dispersion liquid of the nano-hybrid material of gold nanorods/silicon/carbon dioxide point changes into the dispersion liquid of gold nanorods, other is all identical with " application in diffuse-reflectance imaging of the nano-hybrid material of the gold nanorods/silicon/carbon dioxide point " part in embodiment 1.
In diffuse-reflectance imaging, slope is the biggest, and sensitivity is the highest；Understand in conjunction with Fig. 5, the diffuse-reflectance image sensitivity of the gold nanorods of comparative example 1 preparation is less than the diffuse-reflectance image sensitivity of the nano-hybrid material of the gold nanorods/silicon/carbon dioxide point of the embodiment of the present invention 1 preparation, and therefore the nano-hybrid material of gold nanorods/silicon/carbon dioxide point is particularly suited in diffuse-reflectance imaging applications.
Gold nanorods application in fluorescence lifetime imaging
In addition to the dispersion liquid of the nano-hybrid material of gold nanorods/silicon/carbon dioxide point changes into the dispersion liquid of gold nanorods, other is all identical with " application in fluorescence lifetime imaging of the nano-hybrid material of the gold nanorods/silicon/carbon dioxide point " part in embodiment 1.
Result shows, gold nanorods cannot be carried out the application of fluorescence lifetime imaging.
Comparative example 2
The preparation of gold nanorods is with embodiment 1, described 5ml gold nanorods is mixed mutually with 10ml methoxypolyethylene glycol-sulfydryl (m-PEG-SH) (molecular weight of described m-PEG-SH is 5000), it is stirred 2h, then the luciferin solution that 12 μ L concentration are 100 μm ol/L is added, stirring reaction 12h, carry out post processing, obtain the nano-hybrid material of gold nanorods/dyestuff.
The application in diffuse-reflectance imaging of the nano-hybrid material of gold nanorods/dyestuff
In addition to the dispersion liquid of the nano-hybrid material changing the dispersion liquid of the nano-hybrid material of gold nanorods/silicon/carbon dioxide point into gold nanorods/dyestuff, other is all identical with " application in diffuse-reflectance of the nano-hybrid material of the gold nanorods/silicon/carbon dioxide point " part in embodiment 1.
In diffuse-reflectance imaging, slope is the biggest, and sensitivity is the highest；Understand in conjunction with Fig. 5 and Fig. 6, the diffuse-reflectance image sensitivity of the nano-hybrid material of gold nanorods/dyestuff is less than the diffuse-reflectance image sensitivity of the nano-hybrid material of gold nanorods/silicon/carbon dioxide point, and therefore the nano-hybrid material of gold nanorods/silicon/carbon dioxide point is particularly suited in diffuse-reflectance imaging applications.
The application in fluorescence lifetime imaging of the nano-hybrid material of gold nanorods/dyestuff
In addition to the dispersion liquid of the nano-hybrid material of gold nanorods/silicon/carbon dioxide point changes into the nano-hybrid material solution of gold nanorods/dyestuff, other is all identical with " application in fluorescence lifetime imaging of the nano-hybrid material of the gold nanorods/silicon/carbon dioxide point " part in embodiment 1.
Result shows, the nano-hybrid material of the nano-hybrid material of gold nanorods/dyestuff imaging results in fluorescence lifetime imaging and gold nanorods/silicon/carbon dioxide point imaging results in fluorescence lifetime imaging is close.
Obviously; the above embodiment of the present invention is only for clearly demonstrating example of the present invention; and it is not the restriction to embodiments of the present invention; for those of ordinary skill in the field; can also make other changes in different forms on the basis of the above description; here cannot all of embodiment be given exhaustive, every belong to obvious change that technical scheme extended out or the variation row still in protection scope of the present invention.
Claims (10)
1. the nano-hybrid material of gold nanorods/silicon/carbon dioxide point, it is characterised in that described nano-hybrid material includes the gold nanorods as core, as the silicon dioxide layer of shell be distributed in the carbon point of silicon dioxide layer outer surface；Described nano-hybrid material be the silicon dioxide layer that is coated with by gold nanorods outer surface with the silane-functionalized carbon point generation coupled action containing amino and obtain；
The a length of 30-100nm of described gold nanorods, the draw ratio of described gold nanorods is 2-6；
The thickness of described silicon dioxide layer is 10-40nm；
The particle diameter of described carbon point is 1-10nm.
2. the preparation method of the nano-hybrid material of gold nanorods as claimed in claim 1/silicon/carbon dioxide point, it is characterised in that comprise the steps:
1) preparation of gold nanorods
2) gold nanorods/silica composite
By step 1) in preparation gold nanorods be dispersed in water, the dispersion liquid of gold nanorods must be contained；By the dispersion liquid containing gold nanorods, methanol solution containing tetraethyl orthosilicate and aqueous slkali mixing, the 1-5h of stirring reaction the most at normal temperatures, obtain the first mixture, be centrifuged described first mixture processing, washing to obtain gold nanorods/silica composite；
3) the silane-functionalized carbon point containing amino
By citric acid, silane containing amino and water mixing, then react 4-10h at 120-200 DEG C, obtain the second mixture, carry out extracting and revolving steaming by described second mixture, the silane-functionalized carbon point of amino must be contained；
4) nano-hybrid material of gold nanorods/silicon/carbon dioxide point
By step 2) in the gold nanorods/silica composite of preparation disperse in ethanol, obtain the dispersion liquid of gold nanorods/silica composite；By the dispersion liquid of gold nanorods/silica composite, aqueous slkali and the mixing of the silane-functionalized carbon point containing amino, then stirring reaction 3-10h at 20-30 DEG C, obtains the 3rd mixture；It is centrifuged described 3rd mixture processing, washing to obtain the nano-hybrid material of gold nanorods/silicon/carbon dioxide point.
The preparation method of the nano-hybrid material of gold nanorods the most according to claim 2/silicon/carbon dioxide point, it is characterised in that step 1) in the preparation of gold nanorods carry out as follows:
1) by HAuCl4Aqueous solution, NaBH4Aqueous solution is added sequentially in CTAB aqueous solution, after constant temperature stands, obtains seed-solution；
2) by HAuCl4Aqueous solution, AgNO3Aqueous solution, HCl/water solution, aqueous ascorbic acid are added sequentially in CTAB aqueous solution, obtain the 4th mixture；When the 4th mixture is become colorless by orange-yellow, then adding described seed-solution in the 4th mixture, then constant temperature stands, and must contain the mixed liquor of gold nanorods；It is centrifuged the mixed liquor containing gold nanorods processing, obtains gold nanorods.
The preparation method of the nano-hybrid material of gold nanorods the most according to claim 2/silicon/carbon dioxide point, it is characterised in that described aqueous slkali is the aqueous solution of sodium hydroxide, potassium hydroxide or ammonia；Preferably, the concentration of described aqueous slkali is 0.1-1mol/L.
The preparation method of the nano-hybrid material of gold nanorods the most according to claim 2/silicon/carbon dioxide point, it is characterized in that, step 2) in, the volume ratio of the described dispersion liquid containing gold nanorods, the methanol solution containing tetraethyl orthosilicate and aqueous slkali is 1000-2000:8-16:1；In the described methanol solution containing tetraethyl orthosilicate, the volume ratio of tetraethyl orthosilicate and methanol is 1:3-10.
The preparation method of the nano-hybrid material of gold nanorods the most according to claim 2/silicon/carbon dioxide point, it is characterised in that the described dispersion liquid concentration containing gold nanorods is 0.1-1g/L.
The preparation method of the nano-hybrid material of gold nanorods the most according to claim 2/silicon/carbon dioxide point, it is characterized in that, step 3) in, the described silane containing amino is N-(β-aminoethyl)-γ-aminopropyltriethoxy dimethoxysilane, N-(β-aminopropyl)-γ-aminopropyltriethoxy trimethoxy silane or APTES.
The preparation method of the nano-hybrid material of gold nanorods the most according to claim 2/silicon/carbon dioxide point, it is characterised in that the mass ratio of described citric acid, silane containing amino and water is 1:2-20:2-20.
The preparation method of the nano-hybrid material of gold nanorods the most according to claim 2/silicon/carbon dioxide point, it is characterised in that step 4) in, the concentration of the dispersion liquid of gold nanorods/silica composite is 3-10g/L；Preferably, the volume ratio of the dispersion liquid of described gold nanorods/silica composite, aqueous slkali and the silane-functionalized carbon point containing amino is 50-500:1-20:1.
10. the application of the nano-hybrid material of gold nanorods as claimed in claim 1/silicon/carbon dioxide point, it is characterised in that the nano-hybrid material of described gold nanorods/silicon/carbon dioxide point is in diffuse-reflectance imaging or the application in the fluorescence imaging life-span.
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