CN105290393B - Hollow SiO2Wrap hollow Au cages nanometer ring a bell, its preparation method and application - Google Patents
Hollow SiO2Wrap hollow Au cages nanometer ring a bell, its preparation method and application Download PDFInfo
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- CN105290393B CN105290393B CN201410240022.5A CN201410240022A CN105290393B CN 105290393 B CN105290393 B CN 105290393B CN 201410240022 A CN201410240022 A CN 201410240022A CN 105290393 B CN105290393 B CN 105290393B
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Abstract
The invention discloses a kind of hollow SiO2Wrap hollow Au cages nanometer to ring a bell, its preparation method and application.The nanometer is rung a bell including hollow SiO2Microballoon and movably it is arranged at the hollow SiO2Hollow Au cages in microballoon inner chamber；Its preparation method includes：By the use of Ag cubes etc. as template, hollow Au cages are made, then in the Au cages surface modification Raman signal molecule and coated Si O2Shell, forms SiO2Hollow Au cages core-shell structure nanometer particle is wrapped, and, surface selective etch is carried out to the core-shell structure nanometer particle, the nanometer is made and rings a bell.The nanometer of the present invention is rung a bell with higher stability and biocompatibility, good pharmaceutical carrier can be used as, and the luminous energy of near-infrared laser is converted into heat energy by the absorption that can adjust near infrared region, it can also strengthen Raman signal simultaneously, there is huge application prospect carrying the medical domains such as medicine, photo-thermal treatment and Raman image.
Description
Technical field
The present invention relates to a kind of nano material for formula of ringing a bell and preparation method thereof, and in particular to a kind of hollow SiO2Bag is hollow
The preparation method that Au cages nanometer is rung a bell, belongs to field of inorganic materials.
Technical background
Gold nano-material, due to its unique chemical and physical features, in electronics, optics, catalysis and biomedicine etc.
Field is with a wide range of applications.In recent years, a variety of gold nanos including gold nanorods, gold nanoshell and gold nanometer cage
Structure causes extensive concern in biomedical sector（N. Li, P. X. Zhao, D. Astruc,Angew. Chem. Int. Ed.2014, 53, 1756）.
These gold nano body structure surfaces have strong electromagnetic field, can be as surface enhanced Raman substrate to being adsorbed in surface
Raman molecular have the enhanced effect of Raman, can as Raman microprobe be used for biological detection and imaging（M. Rycenga, 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 be by the absorption light of these gold nano structures
Spectrum under near infrared light, effectively converts light energy into heat energy from visible accuracy controlling near infrared band, can be used as light
Thermotherapeutic agent is applied to oncotherapy（S. Lal, S. E. Clare, N. J. Halas,Acc. Chem. Res. 2008,41, 1842）.But, due to most of Raman signal molecules, solubility is very low in water, and this necessarily causes to modify Raman signal
The gold nano grain of molecule is substantially reduced in water stability, meanwhile, the drug carrying ability of gold nano structure is poor, hinder its
Application in terms of medical consultations.
At present, the method that overcoming stability reduces problem is the gold nano structural outside layers cladding in modification Raman signal molecule
SiO2Layer.But solid SiO2Raman signal may be shielded, while the problem of low load medicine can not be solved.Therefore, current active demand
Prepare can the enhancing of integrated Raman, photo-thermal and it is high carry a variety of functions such as medicine, and have on Raman image and oncotherapy it is potential should
Stable gold nano structure.
The content of the invention
In view of deficiency of the prior art, an object of the present invention is to provide a kind of hollow SiO2Hollow Au cages are wrapped to receive
Rice is rung a bell, and it has good structural stability, biocompatibility, high load medicine and light thermal property etc..
The second object of the present invention is to provide a kind of hollow SiO2Wrap the preparation method that hollow Au cages nanometer is rung a bell.
A further object of the present invention is to provide a kind of hollow SiO2Wrap hollow Au cages nanometer and ring a bell and increase as Raman spectrum
The purposes of strong basis matter or pharmaceutical carrier.
To realize aforementioned invention purpose, the technical solution adopted by the present invention includes：
A kind of hollow SiO2Hollow Au cages nanometer is wrapped to ring a bell, including：
Hollow SiO with hollow cavity and porous ball wall2Microballoon；
And, movably it is arranged at the hollow SiO2Hollow Au cages in microballoon inner chamber.
Further, the Au cages surface is also modified with Raman signal molecule.
Further, the hollow SiO2Microsphere surface is also modified with biocompatiblity molecules, such as biologically active peptide, but
Not limited to this.
A kind of hollow SiO2The preparation method that hollow Au cages nanometer is rung a bell is wrapped, is comprised the following steps：
（1）Hollow Au cages are provided,
（2）In the Au cages Surface coating SiO2Shell, forms SiO2Wrap hollow Au cages core-shell structure nanometer particle（Also may be used
Referred to as " SiO2Wrap hollow Au cages core shell structure "）；
（3）Surface selective etch is carried out to the core-shell structure nanometer particle, hollow SiO is made2Hollow Au cages are wrapped to receive
Rice is rung a bell,
The hollow SiO2Hollow Au cages nanometer is wrapped to ring a bell including hollow SiO2Microballoon and be movably arranged at it is described in
Empty SiO2Au cages in microballoon inner chamber.
It is used as more one of preferred embodiment, step（1）It can include：Ag cubes are taken as sacrifice template and chlorine
Auric acid reacts, and forms the hollow Au cages.
Further, step（1）It can include：The polyol process mediated using NaHS synthesizes the Ag cubes.
Further, step（1）It can include：Ag cubes are scattered in the aqueous solution containing stabilizer, are heated to
70-100 DEG C, and gold chloride is slowly added to, the hollow Au cages are made.
It is preferred that, step（1）It can include：In the hollow Au cages surface modification Raman signal molecule of acquisition.
It is preferred that, the hollow SiO2Wrapping the preparation method that hollow Au cages nanometer rings a bell can also include：Obtained hollow
SiO2The surface modification biocompatiblity molecules that hollow Au cages nanometer is rung a bell are wrapped, such as biologically active peptide.
Further, the Raman signal molecule at least may be selected from purinethol class compound, mercapto-thiophene class compound,
2- mercaptopyrimidines, 2- thyroidans, 2- mercapto benzyl alcohols, 2- mercaptobutyric acids, 2- sulfydryl pyrazines, mistabrom, 3- sulfydryl benzene
Formic acid, the own alcohol compound of sulfydryl, 2- sulfydryls-hypoxanthine, 2- mercaptobenzoates, 2- sulfydryl -3- aminopyridines, 4-
Amino -3- mercaptopyridines, 3- amino -4- mercaptopyridines, 4,4- dimercapto diphenyl sulfides, dihydrolipoic acid, p-Mercaptoaniline, 4-
Amino -3- mercaptobenzoic acids and hydrochloride, 2 mercaptopropionic acid, 4,5- diaminourea -6- mercaptopyrimidines, 2- mercaptobenzoic acids, mercapto
Guanidine-acetic acid sodium, 3- sulfydryl -2- butanol, 1,3- dimercaptopropane, to mercaptobenzoic acid, Cys, TGA, the Guang ammonia of D- half
Acid and hydrochloride, DMSA, 2 mercapto ethanol, 4- sulfydryl -2- methylphenols, dimercaprol dimercaptopropanol, cysteamine salt
Hydrochlorate, double mercapto ethyl thioethers and to any one in methylthio phenyl formaldehyde or two or more combinations, and not limited to this.
Further, the biologically active peptide includes and is not limited to the cell-penetrating peptide containing sulfydryl.
Compared with prior art, beneficial effects of the present invention include：
（1）There is provided a kind of hollow SiO2Hollow Au cages nanometer is wrapped to ring a bell, wherein, hollow SiO2Shell both can be with guarantee fund
The stability of nanocages and the drug carrying ability for improving system, while being additionally favorable for Raman signal transmission and photothermal deformation；
（2）Further, by using hollow Au cages as moveable kernel, and the modification Raman letter on hollow Au cages
Number molecule, alloing it as Raman enhancing substrate effectively strengthens the Raman signal of signaling molecule, for the drawing of high precision
Graceful imaging, and have by using surface modification the hollow SiO of biocompatiblity molecules2Microballoon can be carried further as shell
Rise its biocompatibility；
（3）The hollow SiO2Wrapping hollow Au cages nanometer and ringing a bell in medical domains such as load medicine, photo-thermal treatment and Raman images has
Huge application prospect, for example, the hollow SiO2Wrap SERS signal fidelity factor that hollow Au cages nanometer rings a bell up to 99.7% with
On, and the hollow SiO contained by it2Microballoon can be as the container for loading medicine, so that the hollow SiO2Hollow Au cages nanometer is wrapped to shake
Bell can strengthen matrix, pharmaceutical carrier as good Raman；
（4）The hollow SiO2Wrap hollow Au cages nanometer and ring a bell preparation technology simply, controllability is good, implements suitable for scale,
Amplifying factors are produced.
Brief description of the drawings
Fig. 1 a-1d are obtained Ag cubes, hollow Au cages, SiO in the embodiment of the present invention 1 respectively2Wrap hollow Au cages core
Shell structure and hollow SiO2Wrap the transmission electron microscope photo that hollow Au cages nanometer is rung a bell.
Fig. 2 a-2d are obtained Ag cubes, hollow Au cages, SiO during the present invention implements 1 respectively2Wrap hollow Au cages nucleocapsid
Structure and hollow SiO2Wrap the grain size distribution that hollow Au cages nanometer is rung a bell.
Fig. 3 is obtained Ag cubes in the embodiment of the present invention 1（Lines a）, hollow Au cages（Lines b）、SiO2Bag is hollow
Au cage core shell structures（Lines c）With hollow SiO2Hollow Au cages nanometer is wrapped to ring a bell（Lines d）UV-Vis curve maps；
Fig. 4 is obtained Ag cubes in the embodiment of the present invention 1（Lines a）, hollow Au cages（Lines b）、SiO2Bag is hollow
Au cage core shell structures（Lines c）With hollow SiO2Hollow Au cages nanometer is wrapped to ring a bell（Lines d）SERS collection of illustrative plates.
Fig. 5 a-5b are obtained hollow SiO in the embodiment of the present invention 1 respectively2Wrap the modification of ringing a bell of hollow Au cages nanometer and wear film
Zeta current potential collection of illustrative plates before and after peptide.
Fig. 6 a-6b are obtained hollow SiO in the embodiment of the present invention 1 respectively2Wrap the modification of ringing a bell of hollow Au cages nanometer and wear film
Enter the photograph via bright field of cell before and after peptide.
Fig. 7 is that obtained concentration is respectively 0.12 mg/mL in the embodiment of the present invention 1（Lines a）、0.24 mg/mL（Lines
b）、0.60 mg/mL（Lines c）With 1.20 mg/mL（Lines d）Hollow SiO2Wrap the SERS figures that hollow Au cages nanometer is rung a bell
Spectrum.
Fig. 8 is the hollow SiO of obtained various concentrations in the embodiment of the present invention 12Hollow Au cages nanometer is wrapped to ring a bell in Raman
Displacement is 1141 cm-1The linear fit of SERS intensity.
Fig. 9 is obtained hollow SiO in the embodiment of the present invention 12Wrap hollow Au cages nanometer and ring a bell and enter thin in different time
The SERS imagings of born of the same parents' situation.
Figure 10 is obtained hollow SiO in the embodiment of the present invention 12Hollow Au cages nanometer is wrapped to ring a bell（Lines a）And deionization
Water（Lines b）Photothermal conversion collection of illustrative plates.
Figure 11 is obtained hollow SiO in the embodiment of the present invention 12Hollow Au cages nanometer is wrapped to ring a bell after load medicine in neutrality（pH=
7.4）And acidity（pH=5.0）Under the conditions of drug release patterns.
Figure 12 is obtained hollow SiO in the embodiment of the present invention 22Wrap the transmission electron microscopy that hollow Au cages nanometer is rung a bell
Mirror photo.
Embodiment
One aspect of the present invention provides a kind of hollow SiO2Wrap hollow Au cages nanometer to ring a bell, it is special with hollow Au cages
The hollow Au cages for not being surface modification Raman signal molecule are moveable kernel, with hollow SiO2Microballoon, particularly modification life
The hollow SiO of thing biocompatiblity molecules2Microballoon is shell, thus with higher stability and biocompatibility, can be as good
Pharmaceutical carrier, and the luminous energy of near-infrared laser is converted into heat energy by the absorption that can adjust near infrared region, is treated carrying medicine, photo-thermal
There is huge application prospect with the medical domain such as Raman image.
Another aspect of the present invention provides one kind and prepares said hollow SiO2The method that hollow Au cages nanometer is rung a bell is wrapped, its
Including：
Hollow Au cages are provided,
In the hollow Au cages Surface coating SiO2Shell, forms SiO2Hollow Au cages core shell structure is wrapped,
And, surface selective etch is carried out to the core-shell structure nanometer particle, hollow SiO is made2Wrap hollow Au cages
Nanometer is rung a bell.
Further, the hollow SiO2The internal diameter of microballoon is preferably 50-120 nm, and external diameter is preferably 80-150 nm.
Further, the particle diameter of the hollow Au cages is preferably 30-50 nm, and wall thickness is preferably 3-5 nm.
Aforementioned hollow Au cages can use method known to industry to prepare, for example, Ag cubes can be chosen as sacrificial mold
Plate reacts with gold chloride, forms the hollow Au cages.
Foregoing forms SiO in hollow Au cages2The mode of layer also can be using techniques known to industry such as reverse microemulsion process.
Among one more specific embodiment, the preparation method can include：What is first mediated with NaHS is polynary
Alcohol method prepares Ag cubes, then uses HAuCl4It is changed into hollow Au cages by Ag cubes in 100 DEG C of solution, it is preferred that may be used also
In hollow Au cages surface modification Raman signal molecule, and at the same time or afterwards coated Si O2Layer, then by selective etch by SiO2
Layer is changed into hollow SiO2, it is preferred that can also be in SiO2The biocompatiblity molecules such as surface modification biologically active peptide.
Further, among one more specifically embodiment, one kind is to prepare the hollow SiO2Wrap hollow Au
The method that cage nanometer is rung a bell may comprise steps of：
（1）Ag is cubical to be prepared
With polyol process, by ethylene glycol（EG）1 ~ 60 min is heated at 100 ~ 200 DEG C, NaHS is sequentially added
（NaHS）, hydrochloric acid（HCl）, polypyrrole alkanone（PVP）And silver trifluoroacetate（CF3COOAg）, make in the mixed reactant to be formed
NaHS, HCl, PVP and CF3COOAg equivalent concentration is respectively 10 ~ 100 μM, 10 ~ 100 μM, 0.1 ~ 0.3 mg/mL, 1 ~ 3
MM, 30 ~ 120 min are heated by mixed reactant at 100 ~ 200 DEG C, and reaction system is cooled down rapidly to stopping reaction, centrifugation, water
Wash, Ag nanocubes are made, and be scattered in deionized water.
（2）The preparation of hollow Au cages
Electricity consumption replacement method, by 0.5 ~ 2.5 mL steps（1）Ag cubes of dispersion liquid of middle preparation adds 50 mL and contained
In 1 ~ 10 mg/mL PVP aqueous solution, 70-100 DEG C is heated to, by 0.1 ~ 1 mM gold chlorides（HAuCl4）Solution presses 0.75
ML/min speed is added dropwise in reaction solution, stops being added dropwise during 30 ~ 120 min, continues to heat 10 ~ 30 min, by reaction flask extremely
Stop reaction in ice-water bath, centrifuge, hollow Au cages are made, and are scattered in deionized water in washing.
（3）The modification of hollow Au cages surface Raman signaling molecule and SiO2Wrap the preparation of hollow Au cages core shell structure
By 2 ~ 10 mL steps（2）Au cages dispersion liquid 30 ~ 120 mL isopropanols of addition of middle preparation and mixing for 1 ~ 10 mL water
Close in solution, 10 ~ 60 min of ultrasound, add the p-Mercaptoaniline that 100 μ L concentration are 1 ~ 10 mM（pATP）Solution, stirring 10 ~
60 min, to modify Raman signal molecule.Then 10 ~ 1000 μ L tetraethyl orthosilicates are added（TEOS）With 0.2 ~ 2.4 mL ammonia
Water, the h of stirring at normal temperature 4 ~ 24 is centrifuged, and SiO is made in washing2Hollow Au cages core shell structure is wrapped, and is scattered in deionized water.
（4）Hollow SiO2Wrap the preparation that hollow Au cages nanometer is rung a bell
By 5 ~ 20 mL steps（3）The SiO of middle preparation2Wrap 10 ~ 100 mL of hollow Au cages core shell structure addition and contain 1 ~ 5
In the mg/mL PVP aqueous solution, 80 ~ 100 DEG C are heated to, 1 ~ 4 h is reacted, centrifugation washing prepares hollow SiO2Wrap hollow Au cages
Nanometer is rung a bell, and is scattered in deionized water.
（5）Hollow SiO2Surface modification cell-penetrating peptide
By 1 ~ 10 mL steps（4）The hollow SiO of middle preparation2Wrap hollow Au cages nanometer dispersion liquid of ringing a bell and add 4 ~ 40 mL
In ethanol and it is well mixed.The 3- aminopropyl triethoxysilanes that 100 ~ 1000 μ L concentration are 100 mM are added thereto
（APTES）Solution, flow back 4 ~ 12 h at 25 ~ 50 DEG C.Centrifugation washing, is scattered in 1 mL PBSs, adds thereto
100 ~ 1000 μ L concentration are 10 mM sulfo-SMCC solution, after 15 ~ 60 min stirrings, and centrifugation washing is scattered in 1 again
In mL PBSs.Add 50 ~ 500 μ L thereto again, 12 ~ 48 h are stirred at room temperature in 20 mg/mL cell-penetrating peptides, and centrifugation is washed,
And be scattered in PBS, so that in SiO2Surface modification cell-penetrating peptide.
The 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.
Essence for a better understanding of the present invention, describes the technology contents of invention in detail below by embodiment, but
Present disclosure is not limited thereto.
Embodiment 1：
（1）Ag is cubical to be prepared
With polyol process, by 25 mL ethylene glycol（EG）30 min are heated at 150 DEG C, it is 3 to sequentially add 0.3 mL concentration
MM NaHS solution, 2.5 mL concentration are 3 mM hydrochloric acid, and 6.25 mL concentration are 20 mg/mL PVP solution and 2.0 mL
Concentration is 282 mM CF3COOAg EG solution, 1h is heated at 150 DEG C, and reaction flask is reacted as stopping in ice-water bath,
Centrifugation, washing, and obtained Ag cubes are scattered in 10 mL deionized waters.The cubical forms of the Ag, particle diameter distribution,
UV-Vis collection of illustrative plates and SERS collection of illustrative plates please refer to Fig. 1 a, Fig. 2 a, Fig. 3 respectively（Lines a）, Fig. 4（Lines a）.
（2）The preparation of Au cages
Electricity consumption replacement method, by 1 mL steps（1）Ag cubes of dispersion liquid of middle preparation adds 50 mL and contains 1 mg/
In the mL PVP aqueous solution, 100 DEG C are heated to, by the HAuCl that concentration is 0.2 mM4Solution is added dropwise by 0.75 mL/min speed
Stop being added dropwise into reaction solution, during 50 min, continue to heat 30 min, reaction flask is reacted as stopping in ice-water bath, from
The heart, washing, and obtained Au cages are scattered in 5 mL deionized waters.The form of the hollow Au cages, particle diameter distribution, UV-Vis figures
Spectrum and SERS collection of illustrative plates please refer to Fig. 1 b, Fig. 2 b, Fig. 3 respectively（Lines b）, Fig. 4（Lines b）.
（3）The modification of hollow Au cages surface Raman signaling molecule and SiO2Wrap the preparation of hollow Au cages core shell structure
By 10 mL steps（2）The Au cages dispersion liquid of middle preparation is added in the mixed solution of 59 mL isopropanols and 2 mL water,
30 min of ultrasound, it is 1 mM's to add 100 μ L concentrationpATP solution, stirs 10 ~ 60 min, to modify Raman signal molecule.
Then 100 μ L TEOS and 1.8 mL ammoniacal liquor are added, stirring at normal temperature 10 hours is centrifuged, and SiO is made in washing2Wrap hollow Au cages core
Shell structure, and be scattered in 10 mL deionized waters.The SiO2Wrap the form, particle diameter distribution, UV-Vis of hollow Au cages core shell structure
Collection of illustrative plates and SERS collection of illustrative plates please refer to Fig. 1 c, Fig. 2 c, Fig. 3 respectively（Lines c）, Fig. 4（Lines c）.
（4）Hollow SiO2Wrap the preparation that hollow Au cages nanometer is rung a bell
By 10 mL steps（3）The SiO of middle preparation2Wrap 40 mL of hollow Au cages core shell structure dispersion liquid addition and contain 1 mg/
In the mL PVP aqueous solution, 100 DEG C are heated to, is reacted 2 hours, centrifugation washing prepares hollow SiO2Hollow Au cages nanometer is wrapped to shake
Bell, and be scattered in 10 mL deionized waters.The hollow SiO2Wrap form, particle diameter distribution, UV-Vis that hollow Au nanocages ring a bell
Collection of illustrative plates and SERS collection of illustrative plates please refer to Fig. 1 d, Fig. 2 d, Fig. 3 respectively（Lines d）, Fig. 4（Lines d）.
（5）SiO2Surface modification cell-penetrating peptide
By 1 mL steps（4）The hollow SiO of middle preparation2Hollow Au cages nanometer dispersion liquid of ringing a bell is wrapped to add in 4 mL ethanol
And be well mixed.100 μ L, 100 mM APTES are added thereto, and flow back 4 h at 35 DEG C, centrifugation washing, and it is scattered in 1
In mL PBSs.Add the sulfo-SMCC solution that 100 μ L concentration are 10 mM thereto again, after 15 min stirrings,
Centrifugation washing, is scattered in 1 mL PBSs again.Add the cell-penetrating peptide that 50 μ L concentration are 20 mg/mL thereto again molten
Liquid, is stirred at room temperature 24 h.Centrifugation washing, and be scattered in 1 mL PBSs, so that in SiO2Surface modification cell-penetrating peptide,
SiO2Zeta Potential distributions before and after the modification of surface modification cell-penetrating peptide please refer to Fig. 5 a- Fig. 5 b, Fig. 6 a- respectively with cell ability is entered
Fig. 6 b.Also, the Raman-enhancing of final product, by SERS signal can detect hollow SiO2Hollow Au cages nanometer is wrapped to ring a bell into thin
Born of the same parents' situation, photothermal conversion performance and medicament slow release ability please refer to Fig. 7 to Figure 11 respectively.
Embodiment 2：
（1）Ag is cubical to be prepared
With polyol process, by 25 mL ethylene glycol（EG）30 min are heated at 160 DEG C, it is 6 to sequentially add 0.3 mL concentration
MM NaHS solution, 2.5 mL concentration are 6 mM hydrochloric acid, and 6.25 mL concentration are 20 mg/mL PVP solution and 2.0 mL
Concentration is 282 mM CF3COOAg EG solution, and 30 min are heated at 160 DEG C, and reaction flask is stopped as in ice-water bath
Reaction, is centrifuged, washing, and obtained Ag cubes are scattered in 10 mL deionized waters.
（2）The preparation of hollow Au cages
Electricity consumption replacement method, by 1 mL steps（1）Ag cubes of dispersion liquid of middle preparation adds 50 mL and contains 2 mg/
In the mL PVP aqueous solution, 70 DEG C are heated to, by the HAuCl that concentration is 0.4 mM4Solution is added dropwise by 0.75 mL/min speed
Stop being added dropwise into reaction solution, during 30 min, continue to heat 30 min, reaction flask is reacted as stopping in ice-water bath, from
The heart, washing is made Au cages and is scattered in 5 mL deionized waters.
（3）The modification of hollow Au cages surface Raman signaling molecule and SiO2Hollow Au cages core shell structure is wrapped to prepare
By 10 mL steps（2）The hollow Au cages dispersion liquid of middle preparation adds the mixed solution of 53 mL isopropanols and 8 mL water
In, ultrasonic 30 min, it is 1 mM's to add 200 μ L concentrationpATP solution, stirs 10 ~ 60 min, to modify Raman signal point
Son.Then 200 μ L TEOS and 2.2 mL ammoniacal liquor are added, stirring at normal temperature 10 hours is centrifuged, and SiO is made in washing2Wrap hollow Au
Cage core shell structure, and be scattered in 10 mL deionized waters.
（4）Hollow SiO2Wrap the preparation that hollow Au cages nanometer is rung a bell
By 10 mL steps（3）The SiO of middle preparation2Wrap 40 mL of hollow Au cages core shell structure dispersion liquid addition and contain 2 mg/
In the mL PVP aqueous solution, 100 DEG C are heated to, 3 h are reacted, centrifugation washing prepares hollow SiO2Hollow Au cages nanometer is wrapped to ring a bell,
And be scattered in 10 mL deionized waters.Ag nanocubes, Au cages, SiO are obtained in the present embodiment2Wrap hollow Au cages nucleocapsid knot
Structure and hollow SiO2Wrapping form, particle diameter that hollow Au cages nanometer is rung a bell etc. can be using same as Example 1 or close mode table
Levy, and close test result can be obtained.For example, the hollow SiO2Wrap the form that hollow Au cages nanometer rings a bell and refer to Figure 12 institutes
Show.
（5）SiO2Surface modification cell-penetrating peptide
By 1 mL steps（4）The hollow SiO of middle preparation2Wrap hollow Au nanocages ring a bell dispersion liquid add 4 mL ethanol in
And be well mixed.The APTES solution that 200 μ L concentration are 100 mM is added thereto, and flow back 4 h at 35 DEG C.Centrifugation washing,
It is scattered in 1 mL PBSs.The sulfo-SMCC solution that 200 μ L concentration are 10 mM is added thereto, and 15 min are stirred
After mixing, centrifugation washing is scattered in 1 mL PBSs again.Add 100 μ L concentration wearing for 20 mg/mL thereto again
Film peptide solution, is stirred at room temperature 24 h.Centrifugation washing, is scattered in 1 mL PBSs, so that in SiO2Surface modification wears film
Peptide.Test, as a result show, this reality with reference to the performance of the mode that embodiment 1 is addressed obtained product final to the present embodiment
Apply the hollow SiO of example2Wrapping hollow Au cages nanometer and ringing a bell also has the performance close with embodiment 1.
It should be appreciated that the above is only the embodiment in numerous concrete application examples of the invention, to protection scope of the present invention
It is not limited in any way.Technical scheme formed by all use equivalents or equivalence replacement, all falls within right of the present invention and protects
Within the scope of shield.
Claims (12)
1. a kind of hollow SiO2Hollow Au cages nanometer is wrapped to ring a bell, it is characterised in that including：
Hollow SiO with hollow cavity and porous ball wall2Microballoon, the hollow SiO2The internal diameter of microballoon is 50-120nm, external diameter
For 80-150nm；
And, movably it is arranged at the hollow SiO2Hollow Au cages in microballoon inner chamber, the particle diameter of the hollow Au cages is
30-50nm, wall thickness is 3-5nm.
2. hollow SiO according to claim 12Wrap hollow Au cages nanometer to ring a bell, it is characterised in that also repair on the Au cages surface
It is decorated with Raman signal molecule.
3. hollow SiO according to claim 22Wrap hollow Au cages nanometer to ring a bell, it is characterised in that the Raman signal molecule
Selected from purinethol class compound, mercapto-thiophene class compound, 2- mercaptopyrimidines, 2- thyroidans, 2- mercapto benzyl alcohols, 2- sulfydryls
Butyric acid, 2- sulfydryl pyrazines, mistabrom, 3- mercaptobenzoic acids, the own alcohol compound of sulfydryl, 2- sulfydryls-hypoxanthine,
2- mercaptobenzoates, 2- sulfydryl -3- aminopyridines, 4- amino -3- mercaptopyridines, 3- amino -4- mercaptopyridines, 4,4- bis-
Sulfydryl diphenyl sulfide, dihydrolipoic acid, p-Mercaptoaniline, 4- amino -3- mercaptobenzoic acids and hydrochloride, 2 mercaptopropionic acid,
4,5- diaminourea -6- mercaptopyrimidines, 2- mercaptobenzoic acids, sodium thioglycolate, 3- sulfydryl -2- butanol, 1,3- dimercaptopropane, to mercapto
Yl benzoic acid, Cys, TGA, D-Cys and hydrochloride, DMSA, 2 mercapto ethanol,
4- sulfydryl -2- methylphenols, dimercaprol dimercaptopropanol, Mercaptamine, double mercapto ethyl thioethers and in methylthio phenyl formaldehyde appoint
The combinations for one or more of anticipating.
4. hollow SiO according to claim 12Wrap hollow Au cages nanometer to ring a bell, it is characterised in that the hollow SiO2Microballoon
Surface is also modified with biocompatiblity molecules, and the biocompatiblity molecules include biologically active peptide.
5. hollow SiO according to claim 42Wrap hollow Au cages nanometer to ring a bell, it is characterised in that the biologically active peptide bag
Include the cell-penetrating peptide containing sulfydryl.
6. a kind of hollow SiO2Wrap the preparation method that hollow Au cages nanometer is rung a bell, it is characterised in that comprise the following steps：
(1) hollow Au cages are provided,
(2) in the Au cages Surface coating SiO2Shell, forms SiO2Wrap hollow Au cages core-shell structure nanometer particle；
(3) surface selective etch is carried out to the core-shell structure nanometer particle, hollow SiO is made2Hollow Au cages nanometer is wrapped to shake
Bell, the hollow SiO2Hollow Au cages nanometer is wrapped to ring a bell including the hollow SiO with hollow cavity and porous ball wall2Microballoon and
Movably it is arranged at the hollow SiO2Hollow Au cages in microballoon inner chamber, the hollow SiO2The internal diameter of microballoon is 50-
120nm, external diameter is 80-150nm, and the particle diameter of the hollow Au cages is 30-50nm, and wall thickness is 3-5nm.
7. hollow SiO according to claim 62Wrap the preparation method that hollow Au cages nanometer is rung a bell, it is characterised in that step (1)
Including：Ag cubes are taken as template is sacrificed to react with gold chloride, the hollow Au cages are formed.
8. hollow SiO according to claim 72Wrap the preparation method that hollow Au cages nanometer is rung a bell, it is characterised in that step (1)
Including：The polyol process mediated using NaHS synthesizes the Ag cubes.
9. the hollow SiO according to any one of claim 6-82The preparation method that hollow Au cages nanometer is rung a bell is wrapped, its feature exists
Include in step (1)：Ag cubes are scattered in the aqueous solution containing stabilizer, 70-100 DEG C are heated to, and be slowly added to
Gold chloride, is made the hollow Au cages.
10. the hollow SiO according to any one of claim 6-82Wrap the preparation method that hollow Au cages nanometer is rung a bell, its feature
It is that step (1) also includes：In the hollow Au cages surface modification Raman signal molecule.
11. the hollow SiO according to any one of claim 6-82Wrap the preparation method that hollow Au cages nanometer is rung a bell, its feature
It is also to include：In obtained hollow SiO2Wrap the surface modification biocompatiblity molecules that hollow Au cages nanometer is rung a bell, the biology
Biocompatiblity molecules include biologically active peptide.
12. hollow SiO any one of claim 1-52Wrap hollow Au cages nanometer ring a bell as Raman spectrum strengthen matrix or
The purposes of pharmaceutical carrier.
Priority Applications (1)
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