CN109893661A - Gold nanorods/zinc oxide/mesoporous silicon dioxide nano the composite material and preparation method and application of adriamycin insertion - Google Patents
Gold nanorods/zinc oxide/mesoporous silicon dioxide nano the composite material and preparation method and application of adriamycin insertion Download PDFInfo
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- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 title claims abstract description 119
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- 239000011787 zinc oxide Substances 0.000 title claims abstract description 60
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- AOJJSUZBOXZQNB-TZSSRYMLSA-N Doxorubicin Chemical compound O([C@H]1C[C@@](O)(CC=2C(O)=C3C(=O)C=4C=CC=C(C=4C(=O)C3=C(O)C=21)OC)C(=O)CO)[C@H]1C[C@H](N)[C@H](O)[C@H](C)O1 AOJJSUZBOXZQNB-TZSSRYMLSA-N 0.000 title claims abstract description 48
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- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 claims description 3
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 3
- 210000002969 egg yolk Anatomy 0.000 claims description 3
- FDWREHZXQUYJFJ-UHFFFAOYSA-M gold monochloride Chemical compound [Cl-].[Au+] FDWREHZXQUYJFJ-UHFFFAOYSA-M 0.000 claims description 3
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Abstract
The present invention discloses the gold nanorods/zinc oxide/mesoporous silicon dioxide nano composite material and preparation method and application of a kind of adriamycin insertion, the anti-tumor drug adriamycin (DOX) for including gold nanorods/zinc oxide/mesoporous silicon dioxide nano particle as carrier in the nanocomposite and being loaded in the nanoparticle duct, the partial size of the nano-complex particle are 130-150 nm.The nanocomposite partial size is small, specific surface is high, load capacity is big, good biocompatibility, one, which is successfully constructed, as a good carrier realizes that photo-thermal promotes the phototherapy of drug release and the treatment of cancer platform of amic therapy method one using gold nanorods as core, can be used as makes the active multifunctional treating system of each function with coordination mode, has preferable vivo biodistribution medical application prospect；And have that preparation process is simple, photothermal conversion efficiency is high and the technical advantages such as applied widely.
Description
Technical field
The invention belongs to nano material preparation technologies and special material technical field, and in particular to one kind is based on antineoplastic
Gold nanorods/zinc oxide/mesoporous silicon dioxide nano the composite material and preparation method and application of object adriamycin insertion.
Background technique
Currently, cancer has become one of the chief complaint for threatening human life.Classical oncotherapy approach usually has three
Kind: operation excision, radiotherapy and chemotherapy (Chemotherapy), but these methods are all swollen in the presence of that selectively targeted cannot treat
Tumor, normal tissue, cell have the shortcomings that biggish damage.In recent years, deepening continuously with nanosecond medical science research, about new
Concern of the research of the nano material applied to clinic diagnosis of type by more and more scholars.
Gold nanorods (AuNR) are because synthetic route is mature efficiently, be easy to surface modification, biocompatibility is good and SPR effect
, there is good development prospect in the advantages that adjustable in therapeutic field of tumor.Its effective spy for being not only used for imaging cancerous
Needle when being used as anti-cancer medicament carrier, can also be used in high temperature treatment of cancer by the heat that photo-thermal effect generates and trigger Chemo-Therapy
Treat the release of drug.Accordingly, there exist be applied to AuNR to realize imaging, chemotherapy and thermotherapy one in single treatment of cancer platform
A possibility that body, AuNR have the potentiality for establishing new treatment mode.Exploitation keeps each function active with coordination mode
Multifunctional treating system is vital for the therapeutic effect of optimizing therapeutic regimen and safety, not only can be on-demand
Treatment provides more chances, and can pave the way for personalized medicine.
ZnO is a kind of widely used semiconductor, and nano-ZnO can be with inducing cell DNA damage and inducing cell mitochondria
ROS is generated, can be applied to the elimination of cancer cell.But the water solubility of AuNR/ZnO nanoparticle is very poor, itself is difficult to directly molten
In biological friendly medium, and its there are stronger cytotoxicities, being directly entered cell can be while damaging cancer cell to just
Normal cell damages, and needs to carry out suitable chemical modification further to improve, these problems have become it in biomedicine
The major obstacle that field is further applied.
Mesoporous silicon oxide is widely distributed, has good biocompatibility, is a kind of with high-specific surface area, macropore appearance
The controllable novel inorganic biomaterial of amount, morphology and size.Simultaneously its with very high chemical stability, biocompatibility,
The features such as synthesis is convenient and low in cost, in addition to other than traditional mesoporous material application field, in other field such as biological medicine
Great application prospect is also shown with genetic engineering etc..It is modified in the surface ZnO, can both reduce nanoparticle
Cytotoxicity can improve the biocompatibility and stability of material again.Meanwhile mesoporous silicon oxide can be played as carrier it is negative
The effect for carrying chemicals, giving treatment of cancer platform realization chemotherapy that AuNR is core and thermotherapy integration, provide can
It can property.
Adriamycin (DOX) is a kind of antitumor antibiotics, can inhibit the synthesis of RNA and DNA, and antitumor spectra is wider, to a variety of
Tumour has certain effect.But it is individually not significant using adriamycin as the chemotherapy effect of therapeutic agent.
Summary of the invention
It is an object of the invention to solve deficiency in the prior art, building realizes that photo-thermal promotes drug using AuNR as core
The treatment of cancer platform of the phototherapy of release and amic therapy method one develops combination and cooperation treatment, realizes that multifunctional unit and collaboration increase
Benefit improves therapeutic effect, reduces toxic side effect, develops Ah mould that can be used for deep tumor treatment of efficient, less toxic side effect
Gold nanorods/zinc oxide/mesoporous silicon dioxide nano composite material of element insertion.
The specific technical solution of the present invention is as described below:
The present invention discloses a kind of gold nanorods/zinc oxide/mesoporous silicon dioxide nano composite material of adriamycin insertion, including makees
The nanoparticle sub-aperture is loaded into for gold nanorods/zinc oxide/mesoporous silicon dioxide nano particle of carrier and by Electrostatic Absorption
Drug DOX in road, the partial size of the nano-complex particle are 130-150 nm.
Gold nanorods/zinc oxide/mesoporous silicon dioxide nano composite material preparation method of adriamycin insertion, specifically
Preparation step are as follows:
1) preparation of crystal seed liquid: the CTAB aqueous solution of clear is prepared, after addition gold chloride forms orange-red clear solution
It instills the sodium borohydride ice water solution now prepared to be vigorously stirred ten minutes, seed solution is statically placed in stand-by after being protected from light place 2-3 h；
2) preparation of growth-promoting media: preparing the CTAB aqueous solution of clear, and concentrated hydrochloric acid is added thereto, adjusts pH to 1-2, then
Gold chloride, silver nitrate solution and the ascorbic acid solution now prepared are added in order and continues stirring to solution in colorless and transparent；
3) synthesis of gold nanorods: stand 12 h, gold nanorods after taking a certain amount of crystal seed liquid that acutely oscillation is added in growth-promoting media
It is spare after the completion of growth；
4) gold nanorods are dispersed in CTAB aqueous solution by gold nanorods/zinc oxide synthesis, sequentially add ascorbic acid, six
Nitric hydrate zinc, hexa, and reaction mixture is reacted 12 hours under the conditions of 90 DEG C, obtain gold nanorods/oxygen
Change zinc composite nanostructure；
5) gold nanorods/zinc oxide/mesoporous silicon oxide synthesis adds gold nanorods/burnett's solution prepared by step 4)
Enter into CTAB solution and stirs 10 min；The NaOH solution of existing configuration is slowly added dropwise in mixed solution, measures 300 μ L's
The methanol solution of TEOS 20%(v/v) is added in three times in above-mentioned solution, moderate-speed mixer one day under 26 DEG C of constant temperatures,
Obtain gold nanorods/zinc oxide/mesoporous silicon oxide yolk shell nano composite structure；
6) DOX solution is slowly stirred at a room temperature with gold nanorods/zinc oxide/mesoporous silicon oxide solution and reacts four days, i.e.,
Obtain target substance.
Further, ascorbic acid described in step 4), zinc nitrate hexahydrate, hexa molar ratio be 1:
1:4.
Further, DOX solution and gold nanorods/zinc oxide/mesoporous silicon oxide solution volume ratio are in step 6)
1:1.
Gold nanorods/zinc oxide/mesoporous silicon dioxide nano composite material based on adriamycin insertion is as optothermal material
Application in cancer cell and the photo-thermal therapy of tumour.
The invention has the following advantages:
1, the sub- nanocomposite partial size of gold nanorods/zinc oxide/mesoporous silicon dioxide nano particle of the present invention is small, compares table
Face is high, load capacity is big, good biocompatibility, successfully constructs one using gold nanorods as core reality as a good carrier
Existing photo-thermal promotes the phototherapy of drug release and the treatment of cancer platform of amic therapy method one, can be used as optothermal material applied to cancer cell
In the photo-thermal therapy of tumour, there is preferable vivo biodistribution medical application prospect；
2, the preparation method of the nanocomposite is simple, abundant raw material, it is applied widely, can be used for industrialized production.
Detailed description of the invention
Fig. 1 is the structure chart of the DOX-AuNR/ZnO/SiO2 material obtained in the embodiment of the present invention 1；
Fig. 2 is the scanning electron microscope diagram of the DOX-AuNR/ZnO/SiO2 material obtained in the embodiment of the present invention 2；
Fig. 3 is the transmission electron microscope figure of the DOX-AuNR/ZnO/SiO2 material obtained in the embodiment of the present invention 2；
Fig. 4 is the UV-visible absorption spectrum of the DOX-AuNR/ZnO/SiO2 material obtained in the embodiment of the present invention 2；
Fig. 5 is the various concentration for obtain after photo-thermal test to DOX-AuNR/ZnO/SiO2 material in the embodiment of the present invention 2
The material statistical chart that temperature changes over time upon laser irradiation；
Fig. 6 is the photostability for obtain after photo-thermal test to DOX-AuNR/ZnO/SiO2 material in the embodiment of the present invention 2
Figure.
Specific embodiment
Following embodiment further illustrates the contents of the present invention, but should not be construed as limiting the invention.Without departing substantially from
In the case where essence of the present invention, to modification made by the method for the present invention, step or condition and replaces, belong to model of the invention
It encloses.
Embodiment 1: gold nanorods/zinc oxide/mesoporous silicon dioxide nano based on the insertion of anti-tumor drug adriamycin is multiple
The preparation of condensation material
(1) it prepares crystal seed liquid: taking the CTAB of 0.4 g to be added in 100 mL round-bottomed flasks, the distilled water of 10 mL is added thereto,
Put it in constant temperature blender with magnetic force, 10-15 min stirred at 50 DEG C to whole dissolutions, after be transferred in 30 DEG C of water-baths,
It is constant to temperature, under conditions of being vigorously stirred, aqueous solution of chloraurate (0.01 mol/L) 250 μ L is added thereto；Now match
The sodium borohydride aqueous solution of 0.01 mol/L is prepared before then taking 600 μ L slowly to drop in -20 DEG C of refrigerator 6 min of storage
Solution in, acutely shake 10 min to solution be sepia, later constant temperature stand 2-3 h；
(2) it prepares growth-promoting media: taking the CTAB of 4 g to be added in beaker, the distilled water of 95 mL is added thereto, beaker is put into temperature
In 50 DEG C of oil bath pan, stirring 10-15 min is transferred to 30 DEG C of water to powder is visible by naked eyes after dissolution completely for degree control
In bath, to temperature stablize, 80 μ L concentrated hydrochloric acids are added dropwise thereto, after be slowly added dropwise 500 μ L, 0.1 mol/L gold chloride it is molten
Liquid may have insoluble matter, to shake to solution it is completely clear after can just add the AgNO of 100 μ L3Solution is eventually adding existing
The ascorbic acid solution of 0.1 mol/L of the 500 μ L matched；
(3) gold nanorods are synthesized: the crystal seed liquid of 240 μ L being added in the growth-promoting media prepared, 1 min are acutely vibrated, at 27 DEG C
Constant temperature under be protected from light stand 12 h, gold nanorods growth after the completion of it is spare；
(4) it synthesizes gold nanorods/zinc oxide: taking the gold nanorods of 0.015 mol to be distributed to 35 mL containing 0.3 g CTAB water-soluble
In liquid.0.02 g ascorbic acid, 0.04 g zinc nitrate hexahydrate and 0.08 g hexa are sequentially added, and reaction is mixed
Object is closed to react 12 hours under the conditions of 90 DEG C；
(5) it synthesizes gold nanorods/zinc oxide/mesoporous silicon oxide: taking 0.1 g CTAB to be dissolved into 15 mL pure water, by step
(4) gold nanorods/burnett's solution prepared, which is added in CTAB solution, stirs 10 min；By the NaOH solution (0.2 of existing configuration
Mol/L, 100 μ L) it is slowly added dropwise in mixed solution；Configure 20%(v/v) TEOS methanol solution, measure 300 μ L points three
Secondary to be added in above-mentioned solution, moderate-speed mixer one day under 26 DEG C of constant temperatures obtains gold nanorods/zinc oxide/mesoporous dioxy
SiClx yolk shell nanocomposite；
(6) by the DOX solution that concentration is 1 mg/mL and gold nanorods/zinc oxide/mesoporous silicon oxide that concentration is 1 mg/mL
Solution is slowly stirred at a room temperature reaction four days to get target substance.
Fig. 1 is gold nanorods/zinc oxide/mesoporous silicon dioxide nano composite material of adriamycin insertion obtained
Structural schematic diagram.
Embodiment 2: the performance for the target substance that the present embodiment 1 obtains in order to better understand is carried out by following test
Characterization:
1. gold nanorods/zinc oxide/mesoporous silicon oxide (i.e. DOX-AuNR/ZnO/SiO of adriamycin insertion2) nano combined
The pattern and particle diameter distribution of material are tested:
Fig. 2 is DOX-AuNR/ZnO/SiO provided by the invention2The scanning electron microscope diagram of nanocomposite.
Specific testing procedure is: taking the sample solution that 20 μ L concentration are 0.2 mg/mL to drip on silicon wafer, to sample drying
After carry out pattern test, DOX-AuNR/ZnO/SiO2The partial size of nanoparticle is 130-150 nm, aobvious from the scanning electron of Fig. 2
Micro mirror graphical results can be seen that the uniform particle diameter of nanoparticle provided by the invention, favorable dispersibility.
Fig. 3 is DOX-AuNR/ZnO/SiO provided by the invention2The transmission electron microscope figure of nanocomposite.
Specific testing procedure is: taking the sample solution that 20 μ L concentration are 0.2 mg/mL to drip on copper mesh, to sample drying
After carry out pattern test, DOX-AuNR/ZnO/SiO2The partial size of nanoparticle is 130-150 nm, from transmission electron microscope figure
Show that result can be seen that the uniform particle diameter of nanoparticle provided by the invention, shows that result is consistent with scanning electron microscope diagram.
2. absorption spectrum is tested
Fig. 4 is DOX-AuNR/ZnO/SiO provided by the invention2The ultraviolet-visible absorption spectroscopy figure of nanocomposite.It is specific to survey
Try is suddenly: taking 2 mL sample aqueous solutions, drug DOX solution and AuNR/ZnO/SiO respectively2Aqueous solution is surveyed in cuvette
Obtain the ultraviolet-visible absorption spectroscopy of three kinds of materials.As shown in Figure 4, DOX-AuNR/ZnO/SiO2Absorption peak and DOX absorption peak
Unanimously and red shift has occurred, while compared with AuNR/ZnO/SiO2Absorption peak blue shift has occurred, illustrate AuNR/ZnO/SiO2Nanoparticle
Son has successfully adsorbed DOX.
3. light thermal property is tested
By DOX-AuNR/ZnO/SiO obtained in embodiment 12Material be configured to various concentration solution (0,50,100,150,
200 and 250 μ g/L), with 1 W/cm under the laser of 808 nm29 min of power illumination, obtained various concentration
The temperature versus time curve of material is as shown in Figure 5.
As can be known from Fig. 5, DOX-AuNR/ZnO/SiO obtained2Material has the function of apparent photo-thermal, and with reaction
The increase of material concentration and the extension of light application time, the heating of material is further obvious, this kind of material will be expected to as optothermal material
For in cancer cell and the photo-thermal therapy of tumour.
4. dead cell fluorometric investigation living
With calcein (Calcein-AM) to DOX-AuNR/ZnO/SiO obtained in embodiment 12Controlling in HeLa cell
Therapeutic effect is investigated, and obtained dead cell fluorescence imaging living is as shown in Figure 6.
As can be known from Fig. 6, to incubation DOX-AuNR/ZnO/SiO2Hela cell carry out 808 nm NIR shine 10
Continue to find that strong green fluorescence disappears after cultivating 20 min after min, and is not incubated for DOX-AuNR/ZnO/SiO2Cell cultivating
30 min remain to observe green fluorescence, this illustrates material DOX-AuNR/ZnO/SiO2808 nm laser are obvious responsed to,
Realize the synergistic effect of light-triggered photo-thermal therapy-chemotherapy.Its principle is that Calcein-AM being capable of specificity and living cells
In Esterase reaction, AM group is sloughed, so that its strong green fluorescence shown can be observed in co-focusing imaging, thus available
Calcein-AM identifies living cells.
Basic principles and main features and advantage of the invention have been shown and described above.But the foregoing is merely this hairs
Bright specific embodiment, technical characteristic of the invention are not limited thereto, and any those skilled in the art is not departing from this hair
The other embodiments obtained under bright technical solution should all cover within the scope of the patent of the present invention.
Claims (5)
1. a kind of gold nanorods/zinc oxide/mesoporous silicon dioxide nano composite material of adriamycin insertion, which is characterized in that packet
It includes gold nanorods/zinc oxide as carrier/mesoporous silicon dioxide nano particle and the nanoparticle is loaded by Electrostatic Absorption
Drug DOX in sub-aperture road, the partial size of the nano-complex particle are 130-150 nm.
2. gold nanorods/zinc oxide/mesoporous silicon dioxide nano composite material of adriamycin insertion as described in claim 1
Preparation method, which is characterized in that specific preparation step are as follows:
1) preparation of crystal seed liquid: the CTAB aqueous solution of clear is prepared, after addition gold chloride forms orange-red clear solution
It instills the sodium borohydride ice water solution now prepared to be vigorously stirred ten minutes, seed solution is statically placed in stand-by after being protected from light place 2-3 h；
2) preparation of growth-promoting media: preparing the CTAB aqueous solution of clear, and concentrated hydrochloric acid is added thereto, adjusts pH to 1-2, then
Gold chloride, silver nitrate solution and the ascorbic acid solution now prepared are added in order and continues stirring to solution in colorless and transparent；
3) synthesis of gold nanorods: stand 12 h, gold nanorods after taking a certain amount of crystal seed liquid that acutely oscillation is added in growth-promoting media
It is spare after the completion of growth；
4) gold nanorods are dispersed in CTAB aqueous solution by gold nanorods/zinc oxide synthesis, sequentially add ascorbic acid, six
Nitric hydrate zinc, hexa, and reaction mixture is reacted 12 hours under the conditions of 90 DEG C, obtain gold nanorods/oxygen
Change zinc composite nanostructure；
5) gold nanorods/zinc oxide/mesoporous silicon oxide synthesis adds gold nanorods/burnett's solution prepared by step 4)
Enter into CTAB solution and stirs 10 min；The NaOH solution of existing configuration is slowly added dropwise in mixed solution, measures 300 μ L's
The methanol solution of TEOS 20%(v/v) is added in three times in above-mentioned solution, moderate-speed mixer one day under 26 DEG C of constant temperatures,
Obtain gold nanorods/zinc oxide/mesoporous silicon oxide yolk shell nano composite structure；
6) DOX solution is slowly stirred at a room temperature with gold nanorods/zinc oxide/mesoporous silicon oxide solution and reacts four days, i.e.,
Obtain target substance.
3. a kind of gold nanorods/zinc oxide/mesoporous silicon dioxide nano composite wood of adriamycin insertion as claimed in claim 2
The preparation method of material, which is characterized in that ascorbic acid described in step 4), zinc nitrate hexahydrate, hexa rub
You are than being 1:1:4.
4. a kind of gold nanorods/zinc oxide/mesoporous silicon dioxide nano composite wood of adriamycin insertion as claimed in claim 2
The preparation method of material, which is characterized in that DOX solution and gold nanorods/zinc oxide/mesoporous silicon oxide solution body in step 6)
Product is than being 1:1.
5. a kind of gold nanorods/zinc oxide/mesoporous silicon dioxide nano composite wood of adriamycin insertion as described in claim 1
Expect the application as optothermal material in cancer cell and the photo-thermal therapy of tumour.
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