CN106620729B - A kind of inorganic-inorganic nano-hybrid material and the preparation method and application thereof of double mesoporous core-shell structures - Google Patents
A kind of inorganic-inorganic nano-hybrid material and the preparation method and application thereof of double mesoporous core-shell structures Download PDFInfo
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Abstract
The invention discloses a kind of inorganic-inorganic nano-hybrid materials and the preparation method and application thereof of double mesoporous core-shell structures.Firstly, in the presence of surfactants, being restored using ascorbic acid to metal salt, obtaining mesoporous inorganic nanoparticle；Then cetyl trimethylammonium bromide wraps up one layer of mesoporous silicon oxide on its surface as surfactant；Mesoporous silicon oxide shell covalently grafts diethyl pentetic acid after amido modified；Finally, being coordinated it with metal ion to get the double mesoporous inorganic-inorganic nano hybrid materials of core-shell structure are arrived.Resulting material has core-shell structure, and core is mesoporous inorganic nanoparticle, and shell is mesoporous silicon oxide shell, and the mesoporous silicon oxide shell layer surface is modified by inorganic metal hybrid.It has many advantages, such as size uniformity, good biocompatibility, and photostability is high, photothermal conversion rate is high, magnetic resonance imaging high resolution is, it can be achieved that magnetic resonance radiography is integrated with photo-thermal therapy.
Description
Technical field
The present invention relates to a kind of nano-hybrid material and the preparation method and application thereof, and in particular to a kind of core-shell structure is double mesoporous
Inorganic-inorganic nano-hybrid material and the preparation method and application thereof.
Background technique
In recent years, cancer is to lead to the one of the major reasons of human death, the detection and treatment of tumour are all the time all
It is a great problem for perplexing people.Current main treatment method has chemotherapy and radiation, but its serious side effect is also not
Hold ignorance.It is even more extremely urgent for the detection and its immunotherapy targeted autoantibody of tumour.Photo-thermal therapy is excited using near infrared light, tool
There is biggish penetration depth, be effective therapeutic modality emerging in recent years, but that there are light is steady for reported some photothermal reagents
Qualitative disadvantage poor, photothermal conversion rate is low.Therefore, the photo-thermal therapy reagent that preparation photostability is high, photothermal conversion rate is high has weight
Want meaning.
Currently, imaging means mainly have CT scan (CT), single-photon emission tomography (SPECT),
Magnetic resonance imaging (MRI).In contrast to first two imaging technique, magnetic resonance imaging is minimum to biological bulk damage, therefore becomes recent
One of hot spot of research.But magnetic resonance contrast agent commercial at present haves the shortcomings that the relaxation time is long, cycle period is short, group
Part stability, consistency Shortcomings, and preparation method is relatively complicated, industrialization difficulty is big.Therefore a kind of cycle period is synthesized
Long, high resolution magnetic resonance contrast agent is particularly important.
Summary of the invention
The present invention be directed to deficiencies in the prior art, and provide a kind of inorganic-inorganic nanometer of double mesoporous core-shell structures
Hybrid material and the preparation method and application thereof overcomes the shortcomings of its component stability, consistency, simplifies preparation method, makes it easily
In industrialization；It enables the material to meet magnetic resonance radiography demand integrated with photo-thermal therapy, and significantly improves photostability, light
Heat conversion, magnetic resonance imaging resolution ratio.
To achieve the above object, the technical solution adopted by the present invention is that:
A kind of preparation method of the inorganic-inorganic nano-hybrid material of double mesoporous core-shell structures, comprising the following steps:
(1) with N, N- dimethyl hexadecyl base ammonium bromide sodium acetate (OTAB-Na) is surfactant, ascorbic acid, gold
Category salt is raw material, is restored using ascorbic acid to metal salt, synthesising mesoporous inorganic nano-particle；
(2) with cetyl trimethylammonium bromide (CATB) for surfactant, sodium hydroxide, dehydrated alcohol, positive silicic acid
Ethyl ester (TEOS) and the mesoporous inorganic nanoparticle of step (1) synthesis are raw material, wrap up and being situated between in mesoporous inorganic nanoparticle surface
Hole silica shell reuses ammonium nitrate ethanol solution and removes CTAB, obtains double mesoporous inorganic-silica of core-shell structure
Nanoparticle；
(3) with double mesoporous inorganic-Nano particles of silicon dioxide, three ethoxy of aminopropyl of the core-shell structure of step (2) synthesis
Base silane, diethyl pentetic acid, 1- (3- dimethylamino-propyl) -3- ethyl-carbodiimide hydrochloride and N- hydroxysuccinimidyl
Acid imide is raw material, aminopropyl triethoxysilane is first used, by silicone hydroxyl hydrolytie polycondensation to double mesoporous inorganics-of core-shell structure
The mesoporous silicon oxide shell layer surface progress of Nano particles of silicon dioxide is amido modified, passes through 1- (3- dimethylamino third again thereafter
Base) -3- ethyl-carbodiimide hydrochloride and n-hydroxysuccinimide amido bond in modified mesoporous silicon oxide shell
Diethyl pentetic acid is covalently grafted on surface, obtains double mesoporous inorganic-silica dioxide nano particles of modified core-shell structure
Son；
(4) using double mesoporous inorganic-Nano particles of silicon dioxide of modified core-shell structure and metal chlorination salt as raw material,
Double mesoporous inorganic-Nano particles of silicon dioxide of metal ion and modified core-shell structure in metal chlorination salt are matched
Position obtains the inorganic-inorganic nano-hybrid material of double mesoporous core-shell structures.
As a further improvement of the present invention, the step (1) specifically: by N, N- dimethyl hexadecyl base ammonium bromide second
Sour sodium (OTAB-Na) aqueous solution is warming up to 50-100 DEG C, adds aqueous metal salt and fresh aqueous ascorbic acid, stirs
1~3h is mixed, is centrifuged, after washing, obtains product i.e. mesoporous inorganic nanoparticle.
As a further improvement of the present invention, the step (2) specifically: first by mesoporous inorganic nanoparticle be dissolved in from
In sub- water, mesoporous inorganic nanoparticle dispersion liquid is obtained, it is mixed with CTAB, the first mixed liquor is formed, is stirred at 50-80 DEG C
Sodium hydroxide and dehydrated alcohol are added thereafter in the first mixed liquor, TEOS is added after being warming up to 50-80 DEG C by 0.5-1h, flow back
2-4h is reacted under state, centrifuge washing in ethanol by product dispersion obtains the second mixed liquor, then adds into the second mixed liquor
Enter ammonium nitrate ethanol solution, back flow reaction 2-4h removes CTAB at 50-80 DEG C, and centrifuge washing obtains double mesoporous inorganic-dioxies
SiClx nanoparticle.
As a further improvement of the present invention, the step (3) specifically: by double mesoporous inorganic-silica dioxide nano particles
Son is dissolved in ethyl alcohol or toluene, obtains the first dispersion liquid, aminopropyl triethoxysilane is added in the first dispersion liquid, in 80-
For 24 hours, product is dissolved in dimethylformamide by centrifuge washing, obtains the second dispersion liquid for 120 DEG C of reflux；Thereafter by diethyl three
Triamine pentaacetic acid is dissolved in dimethylformamide, and 1- (3- dimethylamino-propyl) -3- ethyl-carbodiimide hydrochloride and N- is added
HOSu NHS, room temperature are added in the second dispersion liquid after activating 1h, and centrifuge washing after stirring at room temperature for 24 hours is obtained through repairing
Double mesoporous inorganic-Nano particles of silicon dioxide of the core-shell structure of decorations.
As a further improvement of the present invention, the step (4) specifically: by double mesoporous nothings of modified core-shell structure
Machine-Nano particles of silicon dioxide dispersion in deionized water, obtains third dispersion liquid, chlorination metal is added into third dispersion liquid
Salting liquid, after 100-120 DEG C of back flow reaction 3-6h, centrifuge washing obtains inorganic-nothing that product is double mesoporous core-shell structures
Machine nano-hybrid material.
Wherein, the metal salt in the step (1) is one of chloroplatinic acid, palladium chloride, gold chloride, the step (4)
In metal chlorination salt be one of gadolinium chloride, iron chloride, manganese chloride.
A kind of inorganic-inorganic nano-hybrid material of double mesoporous core-shell structures, is core-shell structure, kernel is mesoporous inorganic
Nanoparticle, shell is mesoporous silicon oxide shell, and the mesoporous silicon oxide shell layer surface is modified by inorganic metal hybrid.
Wherein, the mesoporous inorganic nanoparticle is mesoporous nano platinum particle, mesoporous Pd nano particle and mesoporous gold nano
One of particle, the mesoporous silicon oxide shell layer surface is by hydridization modification a kind of in gadolinium, iron and manganese.
A kind of application of the inorganic-inorganic nano-hybrid material of double mesoporous core-shell structures, is used as near infrared light photo-thermal
The photothermal reagent for the treatment of.
A kind of application of the inorganic-inorganic nano-hybrid material of double mesoporous core-shell structures, is used as magnetic resonance imaging
Contrast agent.
The present invention has the advantages that
(1) preparation method of the inorganic-inorganic nano-hybrid material of double mesoporous core-shell structures provided by the invention, overcomes
The deficiency of existing preparation process, processing step is few, easy to operate, process is easily-controllable, and repeatability with higher is easy to industry
Change.
(2) the inorganic-inorganic nano-hybrid material of double mesoporous core-shell structures provided by the invention, has nanosizing uniqueness group
The advantages that part and structure, overcome the limitation of current material, and of uniform size, good biocompatibility, stability are good.
(3) the inorganic-inorganic nano-hybrid material of double mesoporous core-shell structures provided by the invention, breaches current material
The deficiency of performance and structure, performance characteristics meet clinical diagnosis demand integrated with treatment, are suitable for magnetic resonance radiography and light
Heat cure integration, and it is remarkably improved photostability, photothermal conversion rate, magnetic resonance imaging resolution ratio, biomedical applications
Prospect is boundless.
With reference to the accompanying drawing with specific embodiment, the present invention is described in more detail.
Detailed description of the invention
Fig. 1 is the mesoporous nano platinum particle and the double mesoporous platinum-gadolinium nano-hybrid materials of core-shell structure of the embodiment of the present invention 1
TEM photo；
Fig. 2 is the photo-thermal effect figure of the double mesoporous platinum-gadolinium nano-hybrid materials of core-shell structure of the embodiment of the present invention 6；
Fig. 3 is that the double mesoporous platinum-gadolinium nano-hybrid materials of core-shell structure magnetic resonance in Mice Body of the embodiment of the present invention 7 is imitated
Fruit figure；
Fig. 4 is the double mesoporous platinum-gadolinium nano-hybrid materials of core-shell structure of the embodiment of the present invention 8 at mouse subcutaneous tumor position
The thermograph of photo-thermal effect.
Specific embodiment
Embodiment 1
Platinum-gadolinium nano-hybrid material and preparation method thereof of double mesoporous core-shell structures provided in this embodiment, including it is following
Step:
(1) with N, N- dimethyl hexadecyl base ammonium bromide sodium acetate (OTAB-Na) is surfactant, utilizes ascorbic acid
Chloroplatinic acid is restored, synthesising mesoporous inorganic nano platinum particle: by 80mg surfactant N, N- dimethyl hexadecyl bromide
Change ammonium sodium acetate (OTAB-Na) to be added in 10mL deionized water, is warming up to 70 DEG C of dissolutions, is subsequently added into 2mL0.01mol/L chlorine
Platinic acid aqueous solution and the fresh aqueous ascorbic acid of 2mL0.2mol/L, stir 3h, are centrifuged, and washing, product is dissolved in deionized water
In, form mesoporous nano platinum particle dispersion liquid.
(2) with cetyl trimethylammonium bromide (CATB) for surfactant, in mesoporous inorganic nanoparticle surface packet
Mesoporous silicon oxide shell is wrapped up in, then removes CTAB, obtains double mesoporous platinum-Nano particles of silicon dioxide of core-shell structure: by 0.1g
Cetyl trimethylammonium bromide (CTAB) is dispersed in 30mL water, the mesoporous nano platinum particle dispersion liquid obtained with step (1)
Mixing, forms the first mixed liquor, stirs 0.5h at 70 DEG C, be added in the first mixed liquor thereafter 100 μ L, 30% sodium hydroxide with
100 μ L ethyl orthosilicates (TEOS) are added in 1mL dehydrated alcohol after being warming up to 70 DEG C, react 2h under reflux state, centrifuge washing,
Product is dispersed in 10mL dehydrated alcohol, the second mixed liquor is obtained, then the ammonium nitrate containing 0.6g is added into the second mixed liquor
Ammonium nitrate ethanol solution removes CTAB, 60 DEG C of back flow reaction 2h, and centrifuge washing obtains double mesoporous platinum-Nano particles of silicon dioxide,
It is dissolved in ethyl alcohol, obtains the first dispersion liquid.
(3) aminopropyl triethoxysilane is used, by silicone hydroxyl hydrolytie polycondensation to double mesoporous platinum-titanium dioxides of core-shell structure
The mesoporous silicon oxide shell layer surface progress of silicon nano is amido modified, passes through 1- (3- dimethylamino-propyl) -3- again thereafter
The amido bond of ethyl-carbodiimide hydrochloride and n-hydroxysuccinimide is total in modified mesoporous silicon oxide shell layer surface
Valence grafts diethyl pentetic acid, obtains double mesoporous platinum-Nano particles of silicon dioxide of modified core-shell structure: toward step
(2) 200 μ L aminopropyl triethoxysilanes are added in the first dispersion liquid made from, flow back at 100 DEG C for 24 hours, centrifuge washing will
Product is dissolved in 10mL dimethylformamide (DMF), obtains the second dispersion liquid；Thereafter 50mg diethyl pentetic acid is dissolved in
In dimethylformamide (DMF), and 30mg 1- (3- dimethylamino-propyl) -3- ethyl-carbodiimide hydrochloride and 30mg is added
N-hydroxysuccinimide is added in the second dispersion liquid after activating 1h at room temperature, centrifuge washing after being sufficiently stirred at room temperature for 24 hours,
Double mesoporous platinum-Nano particles of silicon dioxide of modified core-shell structure are obtained, is dispersed in 10mL deionized water, obtains
Third dispersion liquid.
(4)GdCl3In Gd3+It is coordinated with double mesoporous platinum-Nano particles of silicon dioxide of modified core-shell structure,
It obtains the double mesoporous platinum-gadolinium nano-hybrid materials of core-shell structure: 2mol/L is added in the third dispersion liquid made from step (3)
20mL GdCl3Solution, at 100 DEG C after back flow reaction 3h, centrifuge washing obtains the platinum-that product is double mesoporous core-shell structures
Gadolinium nano-hybrid material.
It is core-shell structure using the inorganic-inorganic nano-hybrid material of double mesoporous core-shell structures of above method preparation,
Kernel is mesoporous inorganic nanoparticle, and shell is mesoporous silicon oxide shell, and the mesoporous silicon oxide shell layer surface passes through nothing
The modification of machine metal hybrid；Wherein, the mesoporous inorganic nanoparticle is mesoporous nano platinum particle, mesoporous Pd nano particle and is situated between
One of hole gold nanoparticle, the mesoporous silicon oxide shell layer surface is by hydridization modification a kind of in gadolinium, iron and manganese.
The application of the inorganic-inorganic nano-hybrid material of above-mentioned double mesoporous core-shell structures, is used as near infrared light photo-thermal
The photothermal reagent for the treatment of.
The application of the inorganic-inorganic nano-hybrid material of above-mentioned double mesoporous core-shell structures, is used as magnetic resonance imaging
Contrast agent.
As shown in FIG. 1, FIG. 1 is the platinum-gadolinium nano hybridization materials of (a) mesoporous nano platinum particle and (b) double mesoporous core-shell structures
The TEM photo of material, as can be seen from the figure mesoporous nano platinum particle particle diameter distribution is uniform, and has apparent pore structure.This hair
Platinum-gadolinium nano-hybrid material of double mesoporous core-shell structures of bright offer, the mesoporous layer energy hole path visible in detail in outside,
Illustrating this method can obtain that pattern is good, dispersion performance is good, double hybrid mesoporous nano materials；And the nanometer material after the functionalization
Material, average grain diameter is about 100~150nm, because nano spherical particle is easier by cell endocytic, this is used as biology for it and visits
Needle recycles be of great significance in vivo.
Embodiment 2
It palladium-gadolinium nano-hybrid material of double mesoporous core-shell structure provided in this embodiment and preparation method thereof, material and answers
With, it is substantially the same manner as Example 1, the difference is that comprising following steps:
(1) with N, N- dimethyl hexadecyl base ammonium bromide sodium acetate (OTAB-Na) is surfactant, utilizes ascorbic acid
Palladium chloride is restored, synthesising mesoporous inorganic palladium particle: by 100mg surfactant (OTAB-Na) be added to 10mL go from
In sub- water, 50 DEG C of dissolutions are warming up to, are subsequently added into 1mL 0.01mol/L palladium chloride aqueous solution and fresh anti-of 1mL0.2mol/L
Bad hematic acid aqueous solution stirs 1h, is centrifuged, and washing, product is dissolved in deionized water, forms mesoporous Pd nano particle dispersion liquid.
(2) with cetyl trimethylammonium bromide (CATB) for surfactant, in mesoporous inorganic nanoparticle surface packet
Mesoporous silicon oxide shell is wrapped up in, then removes CTAB, obtains double mesoporous palladium-Nano particles of silicon dioxide of core-shell structure: by 0.2g
Cetyl trimethylammonium bromide (CTAB) is dispersed in 30mL water, the mesoporous Pd nano particle dispersion liquid obtained with step (1)
Mixing, forms the first mixed liquor, stirs 1h at 50 DEG C, be added in the first mixed liquor thereafter 300 μ L, 30% sodium hydroxide with
300 μ L ethyl orthosilicates (TEOS) are added in 3mL dehydrated alcohol after being warming up to 80 DEG C, react 4h under reflux state, centrifuge washing,
Product is dispersed in 10mL dehydrated alcohol, the second mixed liquor is obtained, then the ammonium nitrate containing 0.3g is added into the second mixed liquor
Ammonium nitrate ethanol solution removes CTAB, and 4h is reacted under 70 DEG C of reflux states, and centrifuge washing obtains double mesoporous palladium-silica and receives
Rice corpuscles is dissolved in toluene, obtains the first dispersion liquid.
(3) aminopropyl triethoxysilane is used, by silicone hydroxyl hydrolytie polycondensation to double mesoporous palladium-titanium dioxides of core-shell structure
The mesoporous silicon oxide shell layer surface progress of silicon nano is amido modified, passes through 1- (3- dimethylamino-propyl) -3- again thereafter
The amido bond of ethyl-carbodiimide hydrochloride and n-hydroxysuccinimide is total in modified mesoporous silicon oxide shell layer surface
Valence grafts diethyl pentetic acid, obtains double mesoporous palladium-Nano particles of silicon dioxide of modified core-shell structure: toward step
(2) 100 μ L aminopropyl triethoxysilanes are added in the first dispersion liquid made from, flow back at 80 DEG C for 24 hours, after fully reacting,
Product is dissolved in 10mL dimethylformamide (DMF), obtains the second dispersion liquid by centrifuge washing；Thereafter by 30mg diethyl three
Triamine pentaacetic acid is dissolved in dimethylformamide (DMF), and 20mg 1- (3- dimethylamino-propyl) -3- ethyl carbodiimide is added
Hydrochloride and 20mg n-hydroxysuccinimide, room temperature are added in the second dispersion liquid after activating 1h, are sufficiently stirred at room temperature
Centrifuge washing after for 24 hours obtains double mesoporous palladium-Nano particles of silicon dioxide of modified core-shell structure, is dispersed in 10mL
In deionized water, third dispersion liquid is obtained.
(4)GdCl3In Gd3+It is coordinated with palladium-Nano particles of silicon dioxide of modified double mesoporous core-shell structures,
It obtains the double mesoporous platinum-gadolinium nano-hybrid materials of core-shell structure: 2mol/L20mL is added in the third dispersion liquid made from step (3)
GdCl3Solution, after reacting 6h under 110 DEG C of reflux states, centrifuge washing obtains the palladium-that product is double mesoporous core-shell structures
Gadolinium nano-hybrid material.
Embodiment 3
It gold-gadolinium nano-hybrid material of double mesoporous core-shell structure provided in this embodiment and preparation method thereof, material and answers
With, it is essentially identical with embodiment 1 or 2, the difference is that comprising following steps:
(1) with N, N- dimethyl hexadecyl base ammonium bromide sodium acetate (OTAB-Na) is surfactant, utilizes ascorbic acid
Gold chloride is restored, synthesising mesoporous inorganic gold particle: 90mg surfactant (OTAB-Na) is added to 10mL deionization
In water, 100 DEG C of dissolutions are warming up to, 1.5mL 0.01mol/L aqueous solution of chloraurate is subsequently added into and 1.5mL 0.2mol/L is fresh
Aqueous ascorbic acid, stir 2h, be centrifuged, washing, product is dissolved in deionized water, forms mesoporous gold nanoparticle dispersion
Liquid.
(2) with cetyl trimethylammonium bromide (CATB) for surfactant, in mesoporous inorganic nanoparticle surface packet
Mesoporous silicon oxide shell is wrapped up in, then removes CTAB, obtains double mesoporous gold-Nano particles of silicon dioxide of core-shell structure: by 0.15g
Cetyl trimethylammonium bromide (CTAB) is dispersed in 30mL water, the mesoporous golden nanometer particle dispersion liquid obtained with step (1)
Mixing, forms the first mixed liquor, stirs 1h at 80 DEG C, be added in the first mixed liquor thereafter 150 μ L, 30% sodium hydroxide with
200 μ L ethyl orthosilicates (TEOS) are added in 5mL dehydrated alcohol after being warming up to 50 DEG C, react 3h under reflux state, centrifuge washing,
Product is dispersed in 10mL dehydrated alcohol, the second mixed liquor is obtained, then the ammonium nitrate containing 0.4g is added into the second mixed liquor
Ammonium nitrate ethanol solution removes CTAB, and 3h is reacted under 50 DEG C of reflux states, and centrifuge washing obtains double mesoporous gold-silica and receives
Rice corpuscles is dissolved in ethyl alcohol, obtains the first dispersion liquid.
(3) aminopropyl triethoxysilane is used, by silicone hydroxyl hydrolytie polycondensation to double mesoporous gold-titanium dioxides of core-shell structure
The mesoporous silicon oxide shell layer surface progress of silicon nano is amido modified, passes through 1- (3- dimethylamino-propyl) -3- again thereafter
The amido bond of ethyl-carbodiimide hydrochloride and n-hydroxysuccinimide is total in modified mesoporous silicon oxide shell layer surface
Valence grafts diethyl pentetic acid, obtains double mesoporous gold-Nano particles of silicon dioxide of modified core-shell structure: toward step
(2) 150 μ L aminopropyl triethoxysilanes are added in the first dispersion liquid made from, flow back at 120 DEG C for 24 hours, centrifuge washing will
Product is dissolved in 10mL dimethylformamide (DMF), obtains the second dispersion liquid；Thereafter 40mg diethyl pentetic acid is dissolved in
In dimethylformamide (DMF), and 25mg 1- (3- dimethylamino-propyl) -3- ethyl-carbodiimide hydrochloride and 25mg is added
N-hydroxysuccinimide is added in the second dispersion liquid after activating 1h under room temperature, is sufficiently stirred to be centrifuged afterwards for 24 hours at room temperature and wash
It washs, obtains gold-Nano particles of silicon dioxide of modified double mesoporous core-shell structures, be dispersed in 10mL deionized water,
Obtain third dispersion liquid.
(4)GdCl3In Gd3+It is coordinated with double mesoporous gold-Nano particles of silicon dioxide of modified core-shell structure,
It obtains the double mesoporous gold-gadolinium nano-hybrid materials of core-shell structure: 2mol/L20mL is added in the third dispersion liquid made from step (3)
GdCl3Solution, after reacting 5h under 120 DEG C of reflux states, centrifuge washing obtains the gold-that product is double mesoporous core-shell structures
Gadolinium nano-hybrid material.
Embodiment 4
It platinum-iron nano-hybrid material of double mesoporous core-shell structure provided in this embodiment and preparation method thereof, material and answers
With, it is essentially identical with embodiment 1-3, the difference is that comprising following steps:
(1) with N, N- dimethyl hexadecyl base ammonium bromide sodium acetate (OTAB-Na) is surfactant, utilizes ascorbic acid
Chloroplatinic acid is restored, synthesising mesoporous inorganic nano platinum particle: 85mg surfactant (OTAB-Na) is added to 10mL
In ionized water, 60 DEG C of dissolutions are warming up to, 2mL0.01mol/L aqueous solution of chloraurate is subsequently added into and 2mL 0.2mol/L is fresh
Aqueous ascorbic acid stirs 2.5h, is centrifuged, and washing, product is dissolved in deionized water, forms mesoporous nano platinum particle dispersion
Liquid.
(2) with cetyl trimethylammonium bromide (CATB) for surfactant, in mesoporous inorganic nanoparticle surface packet
Mesoporous silicon oxide shell is wrapped up in, then removes CTAB, obtains double mesoporous platinum-Nano particles of silicon dioxide of core-shell structure: by 0.2g
Cetyl trimethylammonium bromide (CTAB) is dispersed in 30mL water, the mesoporous nano platinum particle dispersion liquid obtained with step (1)
Mixing, forms the first mixed liquor, stirs 0.5h at 60 DEG C, be added in the first mixed liquor thereafter 200 μ L, 30% sodium hydroxide with
2mL dehydrated alcohol is added 200 μ L ethyl orthosilicates (TEOS), reacts 2.5h under reflux state, centrifugation is washed after being warming up to 60 DEG C
It washs, product is dispersed in 10mL dehydrated alcohol, obtain the second mixed liquor, then ammonium nitrate containing 0.5g is added into the second mixed liquor
Ammonium nitrate ethanol solution remove CTAB, 3h is reacted under 80 DEG C of reflux states, centrifuge washing obtains double mesoporous platinum-silica
Nanoparticle is dissolved in toluene, obtains the first dispersion liquid.
(3) aminopropyl triethoxysilane is used, by silicone hydroxyl hydrolytie polycondensation to double mesoporous platinum-titanium dioxides of core-shell structure
The mesoporous silicon oxide shell layer surface progress of silicon nano is amido modified, passes through 1- (3- dimethylamino-propyl) -3- again thereafter
The amido bond of ethyl-carbodiimide hydrochloride and n-hydroxysuccinimide is total in modified mesoporous silicon oxide shell layer surface
Valence grafts diethyl pentetic acid, obtains double mesoporous platinum-Nano particles of silicon dioxide of modified core-shell structure: toward step
(2) 200 μ L aminopropyl triethoxysilanes are added in the first dispersion liquid made from, under 100 DEG C of reflux states after fully reacting,
Product is dissolved in 10mL dimethylformamide (DMF), obtains the second dispersion liquid by centrifuge washing；Thereafter by 35mg diethyl three
Triamine pentaacetic acid is dissolved in dimethylformamide (DMF), and 20mg 1- (3- dimethylamino-propyl) -3- ethyl carbodiimide is added
Hydrochloride and 20mg n-hydroxysuccinimide are added in the second dispersion liquid after activating 1h at room temperature, are sufficiently stirred at room temperature
Centrifuge washing after for 24 hours obtains platinum-Nano particles of silicon dioxide of modified double mesoporous core-shell structures, is dispersed in 10mL
In deionized water, third dispersion liquid is obtained.
(4)FeCl3In Fe3+It is coordinated with double mesoporous platinum-Nano particles of silicon dioxide of modified core-shell structure,
It obtains the double mesoporous platinum-iron nano-hybrid materials of core-shell structure: 2mol/L is added in the third dispersion liquid made from step (3)
20mLFeCl3Solution, after reacting 4h under 100 DEG C of reflux states, centrifuge washing, obtaining product is double mesoporous core-shell structures
Platinum-iron nano-hybrid material.
Embodiment 5
It platinum-manganese nano-hybrid material of double mesoporous core-shell structure provided in this embodiment and preparation method thereof, material and answers
With, it is essentially identical with embodiment 1-4, the difference is that comprising following steps:
(1) with N, N- dimethyl hexadecyl base ammonium bromide sodium acetate (OTAB-Na) is surfactant, utilizes ascorbic acid
Chloroplatinic acid is restored, synthesising mesoporous inorganic platinum particles: 95mg surfactant (OTAB-Na) is added to 10mL deionization
In water, 80 DEG C of dissolutions are warming up to, are subsequently added into 2mL0.01mol/L aqueous solution of chloraurate and the fresh Vitamin C of 2mL0.2mol/L
Aqueous acid stirs 3h, is centrifuged, and washing, product is dissolved in deionized water, forms mesoporous nano platinum particle dispersion liquid.
(2) with cetyl trimethylammonium bromide (CATB) for surfactant, in mesoporous inorganic nanoparticle surface packet
Mesoporous silicon oxide shell is wrapped up in, then removes CTAB, obtains double mesoporous platinum-Nano particles of silicon dioxide of core-shell structure: by 0.2g
Cetyl trimethylammonium bromide (CTAB) is dispersed in 30mL water, the mesoporous nano platinum particle dispersion liquid obtained with step (1)
Mixing, forms the first mixed liquor, stirs 1h at 70 DEG C, be added in the first mixed liquor thereafter 200 μ L, 30% sodium hydroxide with
200 μ L ethyl orthosilicates (TEOS) are added in 4mL dehydrated alcohol after being warming up to 70 DEG C, react 2h under reflux state, centrifuge washing,
Product is dispersed in 10mL dehydrated alcohol, the second mixed liquor is obtained, then the ammonium nitrate containing 0.5g is added into the second mixed liquor
Ammonium nitrate ethanol solution removes CTAB, and 3h is reacted under 70 DEG C of reflux states, and centrifuge washing obtains double mesoporous platinum-silica and receives
Rice corpuscles is dissolved in toluene, obtains the first dispersion liquid.
(3) aminopropyl triethoxysilane is used, by silicone hydroxyl hydrolytie polycondensation to double mesoporous platinum-titanium dioxides of core-shell structure
The mesoporous silicon oxide shell layer surface progress of silicon nano is amido modified, passes through 1- (3- dimethylamino-propyl) -3- again thereafter
The amido bond of ethyl-carbodiimide hydrochloride and n-hydroxysuccinimide is total in modified mesoporous silicon oxide shell layer surface
Valence grafts diethyl pentetic acid, obtains double mesoporous platinum-Nano particles of silicon dioxide of modified core-shell structure: toward step
(2) 200 μ L aminopropyl triethoxysilanes are added in the first dispersion liquid made from, flow back at 100 DEG C for 24 hours, centrifuge washing will
Product is dissolved in 10mL dimethylformamide (DMF), obtains the second dispersion liquid；Thereafter 40mg diethyl pentetic acid is dissolved in
In dimethylformamide (DMF), and 1- (3- the dimethylamino-propyl) -3- ethyl-carbodiimide hydrochloride and 30mg of 30mg is added
N-hydroxysuccinimide is added in the second dispersion liquid after activating 1h at room temperature, centrifuge washing after being sufficiently stirred at room temperature for 24 hours,
Double mesoporous platinum-Nano particles of silicon dioxide of modified core-shell structure are obtained, is dispersed in 10mL deionized water, obtains
Third dispersion liquid.
(4)MnCl2In Mn2+It is coordinated with double mesoporous platinum-Nano particles of silicon dioxide of modified core-shell structure,
It obtains the double mesoporous platinum-manganese nano-hybrid materials of core-shell structure: 2mol/ is added in the third dispersion liquid made from step (3)
L20mLMnCl2Solution, after reacting 6h under 100 DEG C of reflux states, centrifuge washing, obtaining product is double mesoporous core-shell structures
Platinum-manganese nano-hybrid material.
Embodiment 6
The present embodiment provides a kind of platinum-gadolinium nano-hybrid material applications by double mesoporous core-shell structures made from embodiment 1
In the method for photo-thermal test, comprising the following steps:
(1) the double mesoporous platinum-gadolinium nano-hybrid materials of the core-shell with deionized water with 0~400 μ g/mL；
It (2) is 1.5w/cm with power density25~15min of 808nm laser illumination；
(3) temperature change of different time points sample is recorded.
As shown in Fig. 2, as sample concentration increases, the temperature of sample gradually rises, most full-page proof after 808nm laser irradiation
Temperature is increased under product concentration conditions can reach 30 DEG C or so, and platinum-gadolinium nano-hybrid material of double mesoporous core-shell structures has good
Photo-thermal effect, photothermal conversion efficiency is high, and photostability is high.
Embodiment 7
The present embodiment provides a kind of platinum-gadolinium nano-hybrid material applications by double mesoporous core-shell structures made from embodiment 1
In the method for living body magnetic resonance imaging, comprising the following steps:
(1) platinum-gadolinium nano-hybrid material of double mesoporous core-shell structures of preparation is configured to phosphate buffer (PBS)
The dispersion liquid of 1~2mg/mL；
(2) by tail vein injection into Kunming mouse body, the Magnetic Resonance Imaging after different time sections respectively.
As shown in figure 3, (a) is the magnetic resonance imaging of mouse after injecting the double mesoporous platinum-gadolinium nano-hybrid materials of core-shell structure
Anterior view, (b) be the magnetic resonance figure in mouse liver section after injecting the double mesoporous platinum-gadolinium nano-hybrid materials of core-shell structure,.It can be with
Find out there is the signal of apparent magnetic resonance after the double mesoporous platinum-gadolinium nano-hybrid materials of injection core-shell structure in mouse liver, and
At 2 hours, signal reached maximum, and signal weakens after injection 24 hours, illustrated that the double mesoporous platinum-gadolinium nanometers of core-shell structure are miscellaneous
Changing material, the nano-hybrid material has relatively long cycle period relative to other materials, and there is no long-term stagnant in vivo
The problem of staying.
Embodiment 8
The present embodiment provides a kind of platinum-gadolinium nano-hybrid material applications by double mesoporous core-shell structures made from embodiment 1
In the method for living body subcutaneous tumor thermal imaging experiment, comprising the following steps:
(1) platinum-gadolinium nano-hybrid material of double mesoporous core-shell structures of preparation is configured to point of 1~2mg/mL with PBS
Dispersion liquid；
(2) by intratumor injection into being used as experimental group, the conduct control of injection PBS buffer solution in nude mice by subcutaneous tumour
Group observes the temperature change of tumor locus by thermal imaging system with 808nm laser irradiation 5min.
As shown in figure 4, nano-hybrid material is significantly improved in tumor locus temperature after 808nm laser irradiation,
Temperature needed for can achieve tumor thermal therapy.
Of the invention focuses on, can the double mesoporous cores of mass preparation by unique component and the preparation process simplified
The inorganic-inorganic nano-hybrid material of shell structure, and it is easy to operate, process is easily-controllable, stable structure, repeatability is high, is easy to produce
Industry；Its nano-hybrid material size uniformity synthesized significantly improves its photostability, photothermal conversion rate, magnetic resonance imaging
Resolution ratio, while the material meets the needs of clinical diagnosis and treatment, and it is raw to can be widely applied to diagnosing and treating of tumour etc.
Object medical domain.
As described in the above embodiment the present invention, obtained other for synthesizing double Jie using same or similar method
The method of the nano-hybrid material of hole core-shell, such as by change reactant prepare different mesoporous inorganic nanoparticles or
Regulate and control mesoporous silicon oxide shell thickness by changing the amount of reactant, pass through silicone hydroxyl hydrolytie polycondensation in mesoporous silicon oxide
Shell layer surface modification different functional groups all fall in the scope of protection of the present invention to connect different metal complex.
Claims (7)
1. a kind of preparation method of the inorganic-inorganic nano-hybrid material of double mesoporous core-shell structures, which is characterized in that including following
Step:
It (1) is surfactant with N, N- dimethyl hexadecyl base ammonium bromide sodium acetate OTAB-Na, ascorbic acid, metal salt are
Raw material restores metal salt using ascorbic acid, synthesising mesoporous inorganic nano-particle；The metal salt is chloroplatinic acid, chlorine
Change one of palladium, gold chloride；
(2) using cetyl trimethylammonium bromide CTAB as surfactant, sodium hydroxide, dehydrated alcohol, ethyl orthosilicate
TEOS and the mesoporous inorganic nanoparticle of step (1) synthesis are raw material, wrap up mesoporous dioxy in mesoporous inorganic nanoparticle surface
SiClx shell reuses ammonium nitrate ethanol solution and removes CTAB, obtains double mesoporous inorganic-silica dioxide nano particles of core-shell structure
Son；
(3) with double mesoporous inorganic-Nano particles of silicon dioxide, the aminopropyl-triethoxy silicon of the core-shell structure of step (2) synthesis
Alkane, diethyl pentetic acid, 1- (3- dimethylamino-propyl) -3- ethyl-carbodiimide hydrochloride and N- hydroxysuccinimidyl acyl are sub-
Amine is raw material, aminopropyl triethoxysilane is first used, by silicone hydroxyl hydrolytie polycondensation to double mesoporous inorganic-dioxies of core-shell structure
The mesoporous silicon oxide shell layer surface progress of SiClx nanoparticle is amido modified, passes through-(3- dimethylamino-propyl) -3- again thereafter
The amido bond of ethyl-carbodiimide hydrochloride and n-hydroxysuccinimide is total in modified mesoporous silicon oxide shell layer surface
Valence grafts diethyl pentetic acid, obtains double mesoporous inorganic-Nano particles of silicon dioxide of modified core-shell structure；
(4) using double mesoporous inorganic-Nano particles of silicon dioxide of modified core-shell structure and metal chlorination salt as raw material, metal
Double mesoporous inorganic-Nano particles of silicon dioxide of metal ion and modified core-shell structure in chlorate are coordinated, and are obtained
To the inorganic-inorganic nano-hybrid material of double mesoporous core-shell structures；The metal chlorination salt is gadolinium chloride, iron chloride, manganese chloride
One of.
2. the preparation method of the inorganic-inorganic nano-hybrid material of double mesoporous core-shell structures as described in claim 1, feature
It is, the step (1) specifically: by N, N- dimethyl hexadecyl base ammonium bromide sodium acetate OTAB-Na aqueous solution is warming up to 50-
100 DEG C, aqueous metal salt and fresh aqueous ascorbic acid are added, stirs 1~3h, centrifugation after washing, is produced
Object, that is, mesoporous inorganic nanoparticle.
3. the preparation method of the inorganic-inorganic nano-hybrid material of double mesoporous core-shell structures as described in claim 1, feature
It is, the step (2) specifically: first mesoporous inorganic nanoparticle is dissolved in deionized water, obtains mesoporous inorganic nanoparticle
Sub- dispersion liquid mixes it with CTAB, forms the first mixed liquor, stirs 0.5-1h under the conditions of 50-80 DEG C, thereafter in the first mixing
Sodium hydroxide and dehydrated alcohol are added in liquid, TEOS is added after being warming up to 50-80 DEG C, 2-4h is reacted under reflux state, centrifugation is washed
It washs, in ethanol by product dispersion, the second mixed liquor is obtained, then ammonium nitrate ethanol solution is added into the second mixed liquor, in 50-
Back flow reaction 2-4h at 80 DEG C, removes CTAB, and centrifuge washing obtains double mesoporous inorganic-Nano particles of silicon dioxide.
4. the preparation method of the inorganic-inorganic nano-hybrid material of double mesoporous core-shell structures as described in claim 1, feature
It is, the step (3) specifically: double mesoporous inorganic-Nano particles of silicon dioxide are dissolved in ethyl alcohol or toluene, obtain first
Aminopropyl triethoxysilane is added in the first dispersion liquid in dispersion liquid, flows back under the conditions of 80-120 DEG C for 24 hours, centrifuge washing,
Product is dissolved in dimethylformamide, the second dispersion liquid is obtained；Thereafter diethyl pentetic acid is dissolved in dimethyl formyl
In amine, and 1- (3- dimethylamino-propyl) -3- ethyl-carbodiimide hydrochloride and n-hydroxysuccinimide is added, lives at room temperature
It is added in the second dispersion liquid after changing 1h, centrifuge washing after stirring at room temperature for 24 hours, obtains double mesoporous nothings of modified core-shell structure
Machine-Nano particles of silicon dioxide.
5. the preparation method of the inorganic-inorganic nano-hybrid material of double mesoporous core-shell structures as described in claim 1, feature
It is, the step (4) specifically: be dispersed in double mesoporous inorganic-Nano particles of silicon dioxide of modified core-shell structure
In deionized water, third dispersion liquid is obtained, chlorination metal salt solution is added into third dispersion liquid, flows back at 100-120 DEG C
After reacting 3-6h, centrifuge washing obtains the inorganic-inorganic nano-hybrid material that product is double mesoporous core-shell structures.
6. a kind of inorganic-inorganic of mesoporous core-shell structures double as made from the described in any item preparation methods of Claims 1 to 5 is received
Rice hybrid material, which is characterized in that it is core-shell structure, and kernel is mesoporous inorganic nanoparticle, and shell is mesoporous silicon oxide
Shell, and the mesoporous silicon oxide shell layer surface is modified by inorganic metal hybrid.
7. the inorganic-inorganic nano-hybrid material of double mesoporous core-shell structures as claimed in claim 6, which is characterized in that described
Mesoporous inorganic nanoparticle is one of mesoporous nano platinum particle, mesoporous Pd nano particle and mesoporous gold nanoparticle, described
Mesoporous silicon oxide shell layer surface is by hydridization modification a kind of in gadolinium, iron and manganese.
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