CN105290393A - Hollow SiO2 wrapped hollow Au cage nanometer bell and preparing method and application thereof - Google Patents
Hollow SiO2 wrapped hollow Au cage nanometer bell and preparing method and application thereof Download PDFInfo
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- CN105290393A CN105290393A CN201410240022.5A CN201410240022A CN105290393A CN 105290393 A CN105290393 A CN 105290393A CN 201410240022 A CN201410240022 A CN 201410240022A CN 105290393 A CN105290393 A CN 105290393A
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Abstract
The invention discloses a hollow SiO2 wrapped hollow Au cage nanometer bell and a preparing method and application thereof. The nanometer bell comprises a hollow SiO2 micro ball and a hollow Au cage movably arranged in an inner cavity of the hollow SiO2 micro ball. The preparing method of the nanometer bell comprises the steps that an Ag cuboid and the like are utilized as a template, the hollow Au cage is manufactured, Raman signal molecule modification and SiO2 shell layer wrapping are carried out on the surface of the Au cage, and an SiO2 wrapped hollow Au cage core-shell structure nanometer particle is formed; and in addition, the selective surface etching is carried out on the core-shell structure nanometer particle, and the nanometer bell is prepared. The nanometer bell has high stability and biocompatibility and can serve as a good medicine carrier, the absorption in a near-infrared area can be adjusted, the light energy of near-infrared lasers is converted into heat energy, meanwhile, the Raman signal can be enhanced, and huge application prospects are achieved in the medical fields such as medicine carrying, photo-thermal treatment and Raman imaging.
Description
Technical field
The present invention relates to nano material of a kind of formula of ringing a bell and preparation method thereof, be specifically related to a kind of hollow SiO
2wrap the preparation method that hollow Au cage nanometer is rung a bell, belong to field of inorganic materials.
Technical background
Gold nano-material, due to chemistry and the physical property of its uniqueness, is with a wide range of applications in fields such as electronics, optics, catalysis and biomedicines.In recent years, the multiple gold nano structure comprising gold nanorods, gold nanoshell and gold nanometer cage causes at biomedical sector and pays close attention to widely (N.Li, P.X.Zhao, D.Astruc,
angew.Chem.Int.Ed. 2014, 53,1756).
These gold nano body structure surfaces have strong electromagnetic field, the effect that Raman can be had to strengthen to the Raman molecular being adsorbed in surface as surface enhanced Raman substrate, biological detection and imaging (M.Rycenga can be used for as Raman microprobe, Z.P.Wang, E.Gordon, C.M.Cobley, A.G.Schwartz, C.S.Lo, Y.N.Xia
angew.Chem.Int.Ed. 2009,
48, 9924).In addition, by chemical means, can by the absorption spectrum of these gold nano structures from visible accuracy controlling near infrared band, and under near infrared light, be effectively heat energy by light energy conversion, can be used as light thermotherapeutic agent and be applied to oncotherapy (S.Lal, S.E.Clare, N.J.Halas
acc.Chem.Res. 2008,
41, 1842).But, because most of Raman signal molecule solubility in water is very low, this must cause the gold nano grain modifying Raman signal molecule greatly to reduce at water stability, simultaneously, the drug carrying ability of gold nano structure is poor, hinders its application in medical consultations etc.
At present, the method overcoming stability reduction problem is at the gold nano structural outside layers coated Si O modifying Raman signal molecule
2layer.But solid SiO
2may Raman signal be shielded, the problem of low medicine carrying can not be solved simultaneously.Therefore, current active demand preparation can integrated Raman strengthen, the several functions such as photo-thermal and high medicine carrying, and on Raman image and oncotherapy, have the stable gold nano structure of potential application.
Summary of the invention
In view of deficiency of the prior art, an object of the present invention is to provide a kind of hollow SiO
2wrap hollow Au cage nanometer to ring a bell, it has good structural stability, biocompatibility, high medicine carrying and light thermal property etc.
Two of object of the present invention is to provide a kind of hollow SiO
2wrap the preparation method that hollow Au cage nanometer is rung a bell.
Another object of the present invention is to provide a kind of hollow SiO
2wrap the purposes that hollow Au cage nanometer is rung a bell as Raman spectrum enhancing matrix or pharmaceutical carrier.
For realizing aforementioned invention object, the technical solution used in the present invention comprises:
A kind of hollow SiO
2wrap hollow Au cage nanometer to ring a bell, comprising:
There is the hollow SiO of hollow cavity and porous ball wall
2microballoon;
And, be movably arranged at described hollow SiO
2hollow Au cage in microballoon inner chamber.
Further, described Au cage surface is also modified with Raman signal molecule.
Further, described hollow SiO
2microsphere surface is also modified with biocompatiblity molecules, such as biologically active peptide, but is not limited thereto.
A kind of hollow SiO
2wrap the preparation method that hollow Au cage nanometer is rung a bell, comprise the steps:
(1) hollow Au cage is provided,
(2) at described Au cage Surface coating SiO
2shell, forms SiO
2wrap hollow Au cage core-shell structure nanometer particle and (also can be described as " SiO
2wrap hollow Au cage nucleocapsid structure ");
(3) surperficial selective etch is carried out to described core-shell structure nanometer particle, obtained hollow SiO
2wrap hollow Au cage nanometer to ring a bell,
Described hollow SiO
2wrap hollow Au cage nanometer to ring a bell and comprise hollow SiO
2microballoon and be movably arranged at described hollow SiO
2au cage in microballoon inner chamber.
As one of comparatively preferred embodiment, step (1) can comprise: get Ag cube and react as sacrifice template and gold chloride, form described hollow Au cage.
Further, step (1) can comprise: the polyol process utilizing NaHS to mediate synthesizes described Ag cube.
Further, step (1) can comprise: be scattered in the aqueous solution containing stabilizing agent by Ag cube, be heated to 70-100 DEG C, and slowly add gold chloride, obtained described hollow Au cage.
Preferably, step (1) can comprise: the hollow Au cage finishing Raman signal molecule obtained.
Preferably, described hollow SiO
2wrap the preparation method that hollow Au cage nanometer rings a bell can also comprise: at obtained hollow SiO
2wrap the finishing biocompatiblity molecules that hollow Au cage nanometer is rung a bell, such as biologically active peptide etc.
Further, described Raman signal molecule at least can be selected from purinethol compounds, mercapto-thiophene compounds, 2-mercaptopyrimidine, 2-thyroidan, 2-mercapto benzyl alcohol, 2-mercaptobutyric acid, 2-sulfydryl pyrazine, mistabrom, 3-mercaptobenzoic acid, sulfydryl hexanol compounds, 2-sulfydryl-hypoxanthine, 2-mercaptobenzoate, 2-sulfydryl-3-aminopyridine, 4-amino-3-mercaptopyridine, 3-amino-4-mercaptopyridine, 4, 4-dimercapto diphenyl sulfide, dihydrolipoic acid, p-Mercaptoaniline, 4-amino-3-mercaptobenzoic acid and hydrochloride, 2 mercaptopropionic acid, 4, 5-diaminourea-6-mercaptopyrimidine, 2-mercaptobenzoic acid, sodium thioglycolate, 3-sulfydryl-2-butanols, 1, 3-dimercaptopropane, to mercaptobenzoic acid, Cys, TGA, D-Cys and hydrochloride, 2, 3-dimercaptosuccinic acid, 2 mercapto ethanol, 4-sulfydryl-2-methylphenol, dimercaprol dimercaptopropanol, Mercaptamine, two mercapto ethyl thioether and to any one in methylthio phenyl formaldehyde or two or more combinations, and be not limited thereto.
Further, described biologically active peptide comprises and is not limited to wear film peptide containing sulfydryl.
Compared with prior art, beneficial effect of the present invention comprises:
(1) a kind of hollow SiO is provided
2wrap hollow Au cage nanometer to ring a bell, wherein, hollow SiO
2shell both can guarantee fund's nanocages stability and improve the drug carrying ability of system, be also beneficial to Raman signal transmission and photothermal deformation simultaneously;
(2) further, by adopting hollow Au cage as moveable kernel, and Raman signal molecule is modified on hollow Au cage, make it can strengthen as Raman the Raman signal that substrate effectively strengthens signaling molecule, for highly accurate Raman image, and the hollow SiO by adopting finishing to have biocompatiblity molecules
2microballoon, as shell, can promote its biocompatibility further;
(3) this hollow SiO
2wrap that hollow Au cage nanometer is rung a bell at medicine carrying, photo-thermal treats and the medical domain such as Raman image has huge application prospect, such as, this hollow SiO
2wrap the SERS signal reproduction rate that hollow Au cage nanometer rings a bell and can reach more than 99.7%, and the hollow SiO contained by it
2microballoon can be used as the container of drug loading, thus makes this hollow SiO
2wrap hollow Au cage nanometer to ring a bell and can be used as good Raman and strengthen matrix, pharmaceutical carrier;
(4) this hollow SiO
2wrap hollow Au cage nanometer and ring a bell preparation technology simply, controllability is good, and be suitable for scale and implement, amplifying factors is produced.
Accompanying drawing explanation
Fig. 1 a-1d is obtained Ag cube, hollow Au cage, SiO in the embodiment of the present invention 1 respectively
2wrap hollow Au cage nucleocapsid structure and hollow SiO
2wrap the transmission electron microscope photo that hollow Au cage nanometer is rung a bell.
Fig. 2 a-2d is obtained Ag cube, hollow Au cage, SiO in the invention process 1 respectively
2wrap hollow Au cage nucleocapsid structure and hollow SiO
2wrap the grain size distribution that hollow Au cage nanometer is rung a bell.
Fig. 3 be obtained Ag cube in the embodiment of the present invention 1 (lines a), hollow Au cage (lines b), SiO
2wrap hollow Au cage nucleocapsid structure (lines c) and hollow SiO
2wrap hollow Au cage nanometer to ring a bell the UV-Vis curve map of (lines d);
Fig. 4 be obtained Ag cube in the embodiment of the present invention 1 (lines a), hollow Au cage (lines b), SiO
2wrap hollow Au cage nucleocapsid structure (lines c) and hollow SiO
2wrap hollow Au cage nanometer to ring a bell the SERS collection of illustrative plates of (lines d).
Fig. 5 a-5b is obtained hollow SiO in the embodiment of the present invention 1 respectively
2wrap hollow Au cage nanometer to ring a bell and modify the zeta current potential collection of illustrative plates worn before and after film peptide.
Fig. 6 a-6b is obtained hollow SiO in the embodiment of the present invention 1 respectively
2wrap hollow Au cage nanometer ring a bell modify wear the photograph via bright field entering cell before and after film peptide.
Fig. 7 be in the embodiment of the present invention 1 obtained concentration be respectively 0.12mg/mL(lines a), 0.24mg/mL(lines b), 0.60mg/mL(lines c) and 1.20mg/mL(lines d) hollow SiO
2wrap the SERS collection of illustrative plates that hollow Au cage nanometer is rung a bell.
Fig. 8 is the hollow SiO of obtained variable concentrations in the embodiment of the present invention 1
2wrapping hollow Au cage nanometer, to ring a bell in Raman shift be 1141cm
-1the linear fit of SERS intensity.
Fig. 9 is obtained hollow SiO in the embodiment of the present invention 1
2wrap hollow Au cage nanometer to ring a bell and enter the SERS imaging of cell situation at different time.
Figure 10 is obtained hollow SiO in the embodiment of the present invention 1
2wrap hollow Au cage nanometer and ring a bell that (lines a) and the photothermal conversion collection of illustrative plates of deionized water (lines b).
Figure 11 is obtained hollow SiO in the embodiment of the present invention 1
2wrap hollow Au cage nanometer to ring a bell after medicine carrying drug release patterns under neutral (pH=7.4) and acidity (pH=5.0) condition.
Figure 12 is hollow SiO obtained in the embodiment of the present invention 2
2wrap the transmission electron microscope photo that hollow Au cage nanometer is rung a bell.
Detailed description of the invention
One aspect of the present invention provides a kind of hollow SiO
2wrap hollow Au cage nanometer to ring a bell, it is moveable kernel with the hollow Au cage of hollow Au cage, particularly finishing Raman signal molecule, with hollow SiO
2microballoon, particularly the hollow SiO of modified biological biocompatiblity molecules
2microballoon is shell, thus there is higher stability and biocompatibility, can as good pharmaceutical carrier, and the light energy conversion of near-infrared laser is heat energy by the adjustable absorption near infrared region, to treat and the medical domain such as Raman image has huge application prospect at medicine carrying, photo-thermal.
Another aspect of the present invention provides one to prepare said hollow SiO
2wrap the method that hollow Au cage nanometer is rung a bell, it comprises:
Hollow Au cage is provided,
At described hollow Au cage Surface coating SiO
2shell, forms SiO
2wrap hollow Au cage nucleocapsid structure,
And, surperficial selective etch is carried out to described core-shell structure nanometer particle, obtained hollow SiO
2wrap hollow Au cage nanometer to ring a bell.
Further, described hollow SiO
2the internal diameter of microballoon is preferably 50-120nm, and external diameter is preferably 80-150nm.
Further, the particle diameter of described hollow Au cage is preferably 30-50nm, and wall thickness is preferably 3-5nm.
The method preparation that aforementioned hollow Au cage can adopt industry known, such as, can choose Ag cube and react as sacrifice template and gold chloride, form described hollow Au cage.
Aforesaid at hollow Au cage formation SiO
2the mode technique that the industries such as reverse microemulsion process also can be adopted known of layer.
Among one comparatively specific embodiment, this preparation method can comprise: first prepare Ag cube with the polyol process of NaHS mediation, then use HAuCl
4hollow Au cage is changed into by Ag cube in 100 DEG C of solution, preferably, also can at hollow Au cage finishing Raman signal molecule, and at the same time or afterwards coated Si O
2layer, then by selective etch by SiO
2layer change is hollow SiO
2, preferably, also can at SiO
2the biocompatiblity molecules such as finishing biologically active peptide.
Further, among one more specifically embodiment, a kind of in order to prepare described hollow SiO
2wrap the method that hollow Au cage nanometer rings a bell can comprise the following steps:
(1) the cubical preparation of Ag
With polyol process, by ethylene glycol (EG) at 100 ~ 200 DEG C of heating 1 ~ 60min, add NaHS (NaHS) successively, hydrochloric acid (HCl), polypyrrole alkane ketone (PVP) and trifluoroacetic acid silver (CF
3cOOAg), NaHS, HCl, PVP and CF in the mixed reactant of formation is made
3the EPC of COOAg is respectively 10 ~ 100 μMs, 10 ~ 100 μMs, 0.1 ~ 0.3mg/mL, 1 ~ 3mM, by mixed reactant at 100 ~ 200 DEG C of heating 30 ~ 120min, reaction system is cooled rapidly and stops reaction, centrifugal, washing, obtained Ag nanocube, and be scattered in deionized water.
(2) preparation of hollow Au cage
Electricity consumption replacement method, adds 50mL by the Ag cube dispersion liquid of preparation in 0.5 ~ 2.5mL step (1) and contains in the aqueous solution of 1 ~ 10mg/mLPVP, be heated to 70-100 DEG C, by 0.1 ~ 1mM gold chloride (HAuCl
4) solution drops in reactant liquor by 0.75mL/min speed, stops dripping, continues heating 10 ~ 30min, reaction flask is stopped reaction as in ice-water bath during 30 ~ 120min, centrifugal, washing, obtained hollow Au cage, and be scattered in deionized water.
(3) modification of hollow Au cage surface Raman signaling molecule and SiO
2wrap the preparation of hollow Au cage nucleocapsid structure
The Au cage dispersion liquid of preparation in 2 ~ 10mL step (2) is added in the mixed solution of 30 ~ 120mL isopropyl alcohol and 1 ~ 10mL water, ultrasonic 10 ~ 60min, add p-Mercaptoaniline that 100 μ L concentration are 1 ~ 10mM (
paTP) solution, stirs 10 ~ 60min, to modify Raman signal molecule.Then 10 ~ 1000 μ L ethyl orthosilicate (TEOS) and 0.2 ~ 2.4mL ammoniacal liquor are added, stirring at normal temperature 4 ~ 24h, centrifugal, washing, obtained SiO
2wrap hollow Au cage nucleocapsid structure, and be scattered in deionized water.
(4) hollow SiO
2wrap the preparation that hollow Au cage nanometer is rung a bell
By the SiO of preparation in 5 ~ 20mL step (3)
2wrap hollow Au cage nucleocapsid structure to add 10 ~ 100mL and contain in the aqueous solution of 1 ~ 5mg/mLPVP, be heated to 80 ~ 100 DEG C, reaction 1 ~ 4h, centrifugal washing, preparation hollow SiO
2wrap hollow Au cage nanometer to ring a bell, and be scattered in deionized water.
(5) hollow SiO
2film peptide is worn in finishing
By the hollow SiO of preparation in 1 ~ 10mL step (4)
2wrap hollow Au cage nanometer dispersion liquid of ringing a bell to add in 4 ~ 40mL ethanol and to mix.Add 3-aminopropyl triethoxysilane (APTES) solution that 100 ~ 1000 μ L concentration are 100mM wherein, reflux 4 ~ 12h at 25 ~ 50 DEG C.Centrifugal washing, is scattered in 1mLPBS buffer solution, adds the sulfo-SMCC solution that 100 ~ 1000 μ L concentration are 10mM wherein, and after 15 ~ 60min stirs, centrifugal washing, is scattered in 1mLPBS buffer solution again.Add 50 ~ 500 μ L more wherein, 20mg/mL wears film peptide, stirring at room temperature 12 ~ 48h, centrifugal washing, and is scattered in PBS buffer solution, thus at SiO
2film peptide is worn in finishing.
Preparation method of the present invention is simple, and controllability is good, and efficiency is higher, and reaction is mainly carried out in aqueous phase system, safety and environmental protection.
In order to understand essence of the present invention better, describe the technology contents of invention in detail below by embodiment, but content of the present invention is not limited thereto.
embodiment 1:
(1) the cubical preparation of Ag
With polyol process, by 25mL ethylene glycol (EG) at 150 DEG C of heating 30min, add the NaHS solution that 0.3mL concentration is 3mM successively, 2.5mL concentration is the hydrochloric acid of 3mM, and 6.25mL concentration is the PVP solution of 20mg/mL and 2.0mL concentration is the CF of 282mM
3the EG solution of COOAg, at 150 DEG C of heating 1h, stops reaction by reaction flask as in ice-water bath, centrifugal, washing, and is scattered in 10mL deionized water by obtained Ag cube.The cubical form of this Ag, domain size distribution, UV-Vis collection of illustrative plates and SERS collection of illustrative plates please consult Fig. 1 a, Fig. 2 a respectively, (lines a), (lines a) for Fig. 4 for Fig. 3.
(2) preparation of Au cage
Electricity consumption replacement method, the Ag cube dispersion liquid of preparation in 1mL step (1) is added 50mL and contains in the aqueous solution of 1mg/mLPVP, being heated to 100 DEG C, is the HAuCl of 0.2mM by concentration
4solution drops in reactant liquor by 0.75mL/min speed, stops dripping during 50min, continues heating 30min, reaction flask is stopped reaction as in ice-water bath, centrifugal, washing, and is scattered in 5mL deionized water by obtained Au cage.The form of this hollow Au cage, domain size distribution, UV-Vis collection of illustrative plates and SERS collection of illustrative plates please consult Fig. 1 b, Fig. 2 b, Fig. 3 (lines b), Fig. 4 (lines b) respectively.
(3) modification of hollow Au cage surface Raman signaling molecule and SiO
2wrap the preparation of hollow Au cage nucleocapsid structure
Add in the mixed solution of 59mL isopropyl alcohol and 2mL water by the Au cage dispersion liquid of preparation in 10mL step (2), ultrasonic 30min, adding 100 μ L concentration is 1mM's
paTP solution, stirs 10 ~ 60min, to modify Raman signal molecule.Then 100 μ LTEOS and 1.8mL ammoniacal liquor is added, stirring at normal temperature 10 hours, centrifugal, washing, obtained SiO
2wrap hollow Au cage nucleocapsid structure, and be scattered in 10mL deionized water.This SiO
2wrap the form of hollow Au cage nucleocapsid structure, domain size distribution, UV-Vis collection of illustrative plates and SERS collection of illustrative plates and please consult Fig. 1 c, Fig. 2 c, Fig. 3 (lines c), Fig. 4 (lines c) respectively.
(4) hollow SiO
2wrap the preparation that hollow Au cage nanometer is rung a bell
By the SiO of preparation in 10mL step (3)
2wrap hollow Au cage nucleocapsid structure dispersion liquid to add 40mL and contain in the aqueous solution of 1mg/mLPVP, be heated to 100 DEG C, react 2 hours, centrifugal washing, preparation hollow SiO
2wrap hollow Au cage nanometer to ring a bell, and be scattered in 10mL deionized water.This hollow SiO
2wrap form, domain size distribution, UV-Vis collection of illustrative plates and the SERS collection of illustrative plates that hollow Au nanocages rings a bell and please consult Fig. 1 d, Fig. 2 d, Fig. 3 (lines d), Fig. 4 (lines d) respectively.
(5) SiO
2film peptide is worn in finishing
By the hollow SiO of preparation in 1mL step (4)
2wrap hollow Au cage nanometer dispersion liquid of ringing a bell to add in 4mL ethanol and to mix.Add 100 μ L wherein, 100mMAPTES, reflux 4h at 35 DEG C, centrifugal washing, and be scattered in 1mLPBS buffer solution.Add the sulfo-SMCC solution that 100 μ L concentration are 10mM more wherein, after 15min stirs, centrifugal washing, is scattered in 1mLPBS buffer solution again.Add wherein again 50 μ L concentration be 20mg/mL wear film peptide solution, stirring at room temperature 24h.Centrifugal washing, and be scattered in 1mLPBS buffer solution, thus at SiO
2film peptide is worn in finishing, SiO
2finishing is worn the zeta Potential distribution before and after the modification of film peptide and is entered cell ability and please consults Fig. 5 a-Fig. 5 b, Fig. 6 a-Fig. 6 b respectively.Again, end product Raman-enhancing energy, by SERS signal detection hollow SiO
2wrap hollow Au cage nanometer to ring a bell into cell situation, photothermal conversion performance and medicament slow release ability and please consult Fig. 7 to Figure 11 respectively.
embodiment 2:
(1) the cubical preparation of Ag
With polyol process, by 25mL ethylene glycol (EG) at 160 DEG C of heating 30min, add the NaHS solution that 0.3mL concentration is 6mM successively, 2.5mL concentration is the hydrochloric acid of 6mM, and the EG solution of 6.25mL concentration to be the PVP solution of 20mg/mL and 2.0mL concentration the be CF3COOAg of 282mM, at 160 DEG C of heating 30min, reaction flask is stopped reaction as in ice-water bath, centrifugal, washing, and obtained Ag cube is scattered in 10mL deionized water.
(2) preparation of hollow Au cage
Electricity consumption replacement method, the Ag cube dispersion liquid of preparation in 1mL step (1) is added 50mL and contains in the aqueous solution of 2mg/mLPVP, being heated to 70 DEG C, is the HAuCl of 0.4mM by concentration
4solution drops in reactant liquor by 0.75mL/min speed, stops dripping during 30min, continues heating 30min, reaction flask is stopped reaction as in ice-water bath, centrifugal, washing, and obtained Au cage is scattered in 5mL deionized water.
(3) modification of hollow Au cage surface Raman signaling molecule and SiO
2wrap the preparation of hollow Au cage nucleocapsid structure
Add in the mixed solution of 53mL isopropyl alcohol and 8mL water by the hollow Au cage dispersion liquid of preparation in 10mL step (2), ultrasonic 30min, adding 200 μ L concentration is 1mM's
paTP solution, stirs 10 ~ 60min, to modify Raman signal molecule.Then 200 μ LTEOS and 2.2mL ammoniacal liquor is added, stirring at normal temperature 10 hours, centrifugal, washing, obtained SiO
2wrap hollow Au cage nucleocapsid structure, and be scattered in 10mL deionized water.
(4) hollow SiO
2wrap the preparation that hollow Au cage nanometer is rung a bell
By the SiO of preparation in 10mL step (3)
2wrap hollow Au cage nucleocapsid structure dispersion liquid to add 40mL and contain in the aqueous solution of 2mg/mLPVP, be heated to 100 DEG C, reaction 3h, centrifugal washing, preparation hollow SiO
2wrap hollow Au cage nanometer to ring a bell, and be scattered in 10mL deionized water.Ag nanocube, Au cage, SiO is obtained in the present embodiment
2wrap hollow Au cage nucleocapsid structure and hollow SiO
2wrapping the form, particle diameter etc. that hollow Au cage nanometer rings a bell all can adopt identical with embodiment 1 or close mode to characterize, and can obtain close test result.Such as, this hollow SiO
2wrap the form that hollow Au cage nanometer rings a bell to refer to shown in Figure 12.
(5) SiO
2film peptide is worn in finishing
By the hollow SiO of preparation in 1mL step (4)
2wrap hollow Au nanocages dispersion liquid of ringing a bell to add in 4mL ethanol and to mix.Add the APTES solution that 200 μ L concentration are 100mM wherein, reflux 4h at 35 DEG C.Centrifugal washing, is scattered in 1mLPBS buffer solution.Add the sulfo-SMCC solution that 200 μ L concentration are 10mM wherein, after 15min stirs, centrifugal washing, is scattered in 1mLPBS buffer solution again.Add wherein again 100 μ L concentration be 20mg/mL wear film peptide solution, stirring at room temperature 24h.Centrifugal washing, is scattered in 1mLPBS buffer solution, thus at SiO
2film peptide is worn in finishing.The mode addressed with reference to embodiment 1 is tested the performance that the final institute of the present embodiment obtains product, result display, the hollow SiO of the present embodiment
2wrap hollow Au cage nanometer to ring a bell also there is the performance close with embodiment 1.
Should be appreciated that above is only embodiment in the numerous embody rule example of the present invention, protection scope of the present invention is not constituted any limitation.The technical scheme that all employing equivalents or equivalence are replaced and formed, all drops within rights protection scope of the present invention.
Claims (12)
1. a hollow SiO
2wrap hollow Au cage nanometer to ring a bell, it is characterized in that comprising:
There is the hollow SiO of hollow cavity and porous ball wall
2microballoon;
And, be movably arranged at described hollow SiO
2hollow Au cage in microballoon inner chamber.
2. hollow SiO according to claim 1
2wrap hollow Au cage nanometer to ring a bell, it is characterized in that described Au cage surface is also modified with Raman signal molecule.
3. hollow SiO according to claim 2
2wrap hollow Au cage nanometer to ring a bell, it is characterized in that described Raman signal molecule at least selected from mercapto purine compound, mercapto-thiophene compounds, 2-mercaptopyrimidine, 2-thyroidan, 2-mercapto benzyl alcohol, 2-mercaptobutyric acid, 2-sulfydryl pyrazine, mistabrom, 3-mercaptobenzoic acid, sulfydryl hexanol compounds, 2-sulfydryl-hypoxanthine, 2-mercaptobenzoate, 2-sulfydryl-3-aminopyridine, 4-amino-3-mercaptopyridine, 3-amino-4-mercaptopyridine, 4, 4-dimercapto diphenyl sulfide, dihydrolipoic acid, p-Mercaptoaniline, 4-amino-3-mercaptobenzoic acid and hydrochloride, 2 mercaptopropionic acid, 4, 5-diaminourea-6-mercaptopyrimidine, 2-mercaptobenzoic acid, sodium thioglycolate, 3-sulfydryl-2-butanols, 1, 3-dimercaptopropane, to mercaptobenzoic acid, Cys, TGA, D-Cys and hydrochloride, 2, 3-dimercaptosuccinic acid, 2 mercapto ethanol, 4-sulfydryl-2-methylphenol, dimercaprol dimercaptopropanol, Mercaptamine, two mercapto ethyl thioether and to any one in methylthio phenyl formaldehyde or two or more combinations.
4. hollow SiO according to claim 1
2wrap hollow Au cage nanometer to ring a bell, it is characterized in that described hollow SiO
2microsphere surface is also modified with biocompatiblity molecules, and described biocompatiblity molecules comprises biologically active peptide.
5. hollow SiO according to claim 4
2wrap hollow Au cage nanometer to ring a bell, it is characterized in that described biologically active peptide comprises and wear film peptide containing sulfydryl.
6. a hollow SiO
2wrap the preparation method that hollow Au cage nanometer is rung a bell, it is characterized in that comprising the steps:
(1) hollow Au cage is provided,
(2) at described Au cage Surface coating SiO
2shell, forms SiO
2wrap hollow Au cage core-shell structure nanometer particle;
(3) surperficial selective etch is carried out to described core-shell structure nanometer particle, obtained hollow SiO
2wrap hollow Au cage nanometer to ring a bell,
Described hollow SiO
2wrap hollow Au cage nanometer to ring a bell the hollow SiO comprising and there is hollow cavity and porous ball wall
2microballoon and be movably arranged at described hollow SiO
2hollow Au cage in microballoon inner chamber.
7. hollow SiO according to claim 6
2wrap the preparation method that hollow Au cage nanometer is rung a bell, it is characterized in that step (1) comprising: get Ag cube and react as sacrifice template and gold chloride, form described hollow Au cage.
8. hollow SiO according to claim 7
2wrap the preparation method that hollow Au cage nanometer is rung a bell, it is characterized in that step (1) comprising: the polyol process utilizing NaHS to mediate synthesizes described Ag cube.
9. hollow SiO according to any one of claim 6-8
2wrap the preparation method that hollow Au cage nanometer is rung a bell, it is characterized in that step (1) comprising: be scattered in the aqueous solution containing stabilizing agent by Ag cube, be heated to 70-100 DEG C, and slowly add gold chloride, obtained described hollow Au cage.
10. hollow SiO according to any one of claim 6-8
2wrap the preparation method that hollow Au cage nanometer is rung a bell, it is characterized in that step (1) also comprises: at described hollow Au cage finishing Raman signal molecule.
11. according to any one of claim 6-8 hollow SiO
2wrap the preparation method that hollow Au cage nanometer is rung a bell, characterized by further comprising: at obtained hollow SiO
2wrap the finishing biocompatiblity molecules that hollow Au cage nanometer is rung a bell, described biocompatiblity molecules comprises biologically active peptide.
Hollow SiO according to any one of 12. claim 1-11
2wrap the purposes that hollow Au cage nanometer is rung a bell as Raman spectrum enhancing matrix or pharmaceutical carrier.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106947042A (en) * | 2017-03-10 | 2017-07-14 | 清华大学 | Photothermal deformation element, and aniline oligomer and its derivative application |
| CN107759941A (en) * | 2017-10-19 | 2018-03-06 | 宁波大学 | A kind of preparation method of quasi-waveguide structure dyestuff/thin polymer film doped with silver-colored cube silica core shell material |
| CN108672715A (en) * | 2018-04-25 | 2018-10-19 | 安徽师范大学 | Functional modification gold nanoparticle and preparation method thereof, the detection method of metal mercury ions and its application |
| CN111872377A (en) * | 2020-07-30 | 2020-11-03 | 复旦大学 | Hollow composite material and super-assembly method thereof |
| CN113720779A (en) * | 2021-08-24 | 2021-11-30 | 东莞理工学院 | Preparation method of SERS enhanced substrate based on electric displacement reaction |
| CN114034679A (en) * | 2021-10-15 | 2022-02-11 | 华东师范大学 | Construction and application of high-reproducibility surface-enhanced Raman spectrum platform |
| CN115365510A (en) * | 2022-08-26 | 2022-11-22 | 杭州师范大学 | Bi-metal multilayer porous hollow nano particle with Yolk-Shell structure and synthetic method thereof |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106947042A (en) * | 2017-03-10 | 2017-07-14 | 清华大学 | Photothermal deformation element, and aniline oligomer and its derivative application |
| CN107759941A (en) * | 2017-10-19 | 2018-03-06 | 宁波大学 | A kind of preparation method of quasi-waveguide structure dyestuff/thin polymer film doped with silver-colored cube silica core shell material |
| CN108672715A (en) * | 2018-04-25 | 2018-10-19 | 安徽师范大学 | Functional modification gold nanoparticle and preparation method thereof, the detection method of metal mercury ions and its application |
| CN111872377A (en) * | 2020-07-30 | 2020-11-03 | 复旦大学 | Hollow composite material and super-assembly method thereof |
| CN113720779A (en) * | 2021-08-24 | 2021-11-30 | 东莞理工学院 | Preparation method of SERS enhanced substrate based on electric displacement reaction |
| WO2023024312A1 (en) * | 2021-08-24 | 2023-03-02 | 东莞理工学院 | Galvanic replacement reaction-based sers enhanced substrate preparation method |
| CN114034679A (en) * | 2021-10-15 | 2022-02-11 | 华东师范大学 | Construction and application of high-reproducibility surface-enhanced Raman spectrum platform |
| CN114034679B (en) * | 2021-10-15 | 2023-11-10 | 华东师范大学 | Construction and application of high-reproducibility surface-enhanced Raman spectrum platform |
| CN115365510A (en) * | 2022-08-26 | 2022-11-22 | 杭州师范大学 | Bi-metal multilayer porous hollow nano particle with Yolk-Shell structure and synthetic method thereof |
| CN115365510B (en) * | 2022-08-26 | 2023-06-23 | 杭州师范大学 | Bimetal multilayer porous hollow nanoparticle with Yolk-Shell structure and synthesis method thereof |
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