CN106620729A - Inorganic-inorganic nano hybrid material of bimodal mesoporous core-shell structure as well as preparation method and application of inorganic-inorganic nano hybrid material - Google Patents
Inorganic-inorganic nano hybrid material of bimodal mesoporous core-shell structure as well as preparation method and application of inorganic-inorganic nano hybrid material Download PDFInfo
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Abstract
The invention discloses an inorganic-inorganic nano hybrid material of a bimodal mesoporous core-shell structure as well as a preparation method and an application of the inorganic-inorganic nano hybrid material. The bimodal mesoporous inorganic-inorganic nano hybrid material of the core-shell structure is prepared by the following steps: firstly, with the presence of a surfactant, reducing metal salt by virtue of ascorbic acid, so that mesoporous inorganic nanoparticles are obtained; then, covering the surface of hexadecyl trimethyl ammonium bromide, which serves as a surfactant, with a layer of mesoporous silicon dioxide; covalently grafting diethyltriamine pentaacetic acid after modifying a mesoporous silicon dioxide shell layer by virtue of amino; and finally, coordinating with metal ions, so that the bimodal mesoporous inorganic-inorganic nano hybrid material of the core-shell structure is obtained. The prepared material has the core-shell material, wherein a core is constituted by the mesoporous inorganic nanoparticles and a shell is formed by the mesoporous silicon dioxide shell layer, and the surface of the mesoporous silicon dioxide shell layer is hybridized and modified by virtue of inorganic metals. The inorganic-inorganic nano hybrid material has the advantages of being uniform in dimension, good in biocompatibility and the like, and the inorganic-inorganic nano hybrid material is high in optical stability, high in photo-thermal conversion rate and high in magnetic resonance imaging resolution ratio; and integration of magnetic resonance imaging and photo-thermal therapy can be achieved.
Description
Technical field
The present invention relates to a kind of nano-hybrid material and preparation method and application, and in particular to a kind of core shell structure is double mesoporous
Inorganic-inorganic nano-hybrid material and preparation method and application.
Background technology
In the last few years, cancer was one of the major reason for causing human death, and the detection and treatment of tumour all the time
It is a great problem for perplexing people.Treatment method main at present has chemotherapy and radiation, but its serious side effect is also not
Hold what is ignored.For tumour detection and its immunotherapy targeted autoantibody it is even more extremely urgent.Photo-thermal therapy is excited using near infrared light, tool
There is larger penetration depth, be effectively treatment mode emerging in recent years, but to there is light steady for some photothermal reagents reported
The low shortcoming of qualitative difference, photothermal conversion rate.Therefore, preparing the high photo-thermal therapy reagent of photostability height, photothermal conversion rate has weight
Want meaning.
At present, 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 damages minimum to organism, therefore becomes recent
One of focus of research.But at present commercial magnetic resonance contrast agent haves the shortcomings that relaxation time length, cycle period are short, its group
Part stability, uniformity Shortcomings, and preparation method is relatively complicated, industrialization difficulty is big.Therefore a kind of cycle period is synthesized
The long, magnetic resonance contrast agent of high resolution is particularly important.
The content of the invention
The present invention be directed to deficiency of the prior art, and a kind of inorganic-inorganic nanometer of double mesoporous core shell structures is provided
Hybrid material and preparation method and application, overcomes its component stability, conforming deficiency, simplifies preparation method so as to easily
In industrialization；Enable the material to meet magnetic resonance radiography demand integrated with photo-thermal therapy, and significantly improve photostability, light
Heat conversion, magnetic resonance imaging resolution ratio.
For achieving the above object, the technical solution used in the present invention is：
A kind of preparation method of the inorganic-inorganic nano-hybrid material of double mesoporous core shell structures, comprises the following steps：
(1) with N, N- dimethyl hexadecyls base ammonium bromide sodium acetate (OTAB-Na) be surfactant, ascorbic acid, gold
Category salt is raw material, slaine is reduced using ascorbic acid, synthesising mesoporous inorganic nano-particle；
(2) with cetyl trimethylammonium bromide (CATB) as surfactant, NaOH, absolute ethyl alcohol, positive silicic acid
Ethyl ester (TEOS) and the mesoporous inorganic nano-particle of step (1) synthesis are raw material, are situated between in mesoporous inorganic nanoparticle surface parcel
Hole silica shell, reuses ammonium nitrate ethanol solution and removes CTAB, obtains double mesoporous inorganic-silica of core shell structure
Nano-particle；
(3) double mesoporous inorganic-Nano particles of silicon dioxide, the ethoxy of aminopropyl three of the core shell structure synthesized with step (2)
Base silane, diethyl pentetic acid, 1- (3- dimethylamino-propyls) -3- ethyl-carbodiimide hydrochlorides and N- hydroxysuccinimidyls
Acid imide is raw material, first with aminopropyl triethoxysilane, by silicone hydroxyl hydrolytie polycondensation to double mesoporous inorganics of core shell structure-
The mesoporous silicon oxide shell layer surface of Nano particles of silicon dioxide carry out it is amido modified, thereafter again pass through 1- (3- dimethylaminos third
Base) -3- ethyl-carbodiimide hydrochlorides and N-hydroxy-succinamide amido link in modified mesoporous silicon oxide shell
The covalent grafting diethyl pentetic acid in surface, obtains double mesoporous inorganic-silica dioxide nano particles of modified core shell structure
Son；
(4) with double mesoporous inorganic-Nano particles of silicon dioxide of modified core shell structure and metal chlorination salt as raw material,
Metal ion in metal chlorination salt is matched somebody with somebody with double mesoporous inorganic-Nano particles of silicon dioxide of modified core shell structure
Position, obtains the inorganic-inorganic nano-hybrid material of double mesoporous core shell structures.
As a further improvement on the present invention, the step (1) is specially：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, obtain product i.e. mesoporous inorganic nano-particle.
As a further improvement on the present invention, the step (2) is specially：First by mesoporous inorganic nano-particle be dissolved in from
In sub- water, mesoporous inorganic nanoparticle dispersion liquid is obtained, it is mixed with CTAB, form the first mixed liquor, stirred at 50-80 DEG C
0.5-1h, adds thereafter NaOH and absolute ethyl alcohol in the first mixed liquor, and TEOS is added after being warming up to 50-80 DEG C, flows back
2-4h is reacted under state, centrifuge washing disperses product in ethanol, to obtain the second mixed liquor, then adds in the second mixed liquor
Enter ammonium nitrate ethanol solution, back flow reaction 2-4h removes CTAB at 50-80 DEG C, centrifuge washing obtains double mesoporous inorganic-dioxies
SiClx nano-particle.
As a further improvement on the present invention, the step (3) is specially：By double mesoporous inorganic-silica dioxide nano particles
Son is dissolved in ethanol or toluene, obtains the first dispersion liquid, aminopropyl triethoxysilane is added in the first dispersion liquid, in 80-
120 DEG C of backflow 24h, centrifuge washing is dissolved in product in dimethylformamide, obtains the second dispersion liquid；Thereafter by diethyl three
Triamine pentaacetic acid is dissolved in dimethylformamide, and adds 1- (3- dimethylamino-propyls) -3- ethyl-carbodiimide hydrochlorides and N-
HOSu NHS, adds in the second dispersion liquid after room temperature activation 1h, and centrifuge washing after 24h is stirred under room temperature, obtains Jing and repaiies
Double mesoporous inorganic-Nano particles of silicon dioxide of the core shell structure of decorations.
As a further improvement on the present invention, the step (4) is specially：By the double mesoporous nothing of modified core shell structure
Machine-Nano particles of silicon dioxide disperses in deionized water, obtains the 3rd dispersion liquid, and chlorination metal is added toward the 3rd 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 slaine in the step (1) is the one kind in chloroplatinic acid, palladium bichloride, gold chloride, the step (4)
In metal chlorination salt be gadolinium chloride, iron chloride, manganese chloride in one kind.
A kind of inorganic-inorganic nano-hybrid material of double mesoporous core shell structures, it is core shell structure, and kernel is mesoporous inorganic
Nano-particle, shell is mesoporous silicon oxide shell, and the mesoporous silicon oxide shell layer surface is through inorganic metal hybrid modification.
Wherein, the mesoporous inorganic nano-particle is mesoporous nano platinum particle, mesoporous Pd nano particle and mesoporous gold nano
One kind in particle, a kind of mesoporous silicon oxide shell layer surface hydridization modification 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 preparation.
It is an advantage of the current invention that：
(1) preparation method of the inorganic-inorganic nano-hybrid material of the double mesoporous core shell structure that the present invention is provided, overcomes
The deficiency of existing preparation technology, processing step is few, easy to operate, process is easily-controllable, with higher repeatability, it is easy to industry
Change.
(2) the inorganic-inorganic nano-hybrid material of the double mesoporous core shell structure that the present invention is provided, with nanosizing uniqueness group
Part and structure, the advantages of overcome the limitation of current material, size uniform, good biocompatibility, good stability.
(3) the inorganic-inorganic nano-hybrid material of the double mesoporous core shell structure that the present invention is provided, breaches current material
The deficiency of performance and structure, its performance characteristics meet clinical diagnosis with the integrated demand for the treatment of, it is adaptable to magnetic resonance radiography and light
Heat cure integration, and it is remarkably improved photostability, photothermal conversion rate, magnetic resonance imaging resolution ratio, its biomedical applications
Prospect is boundless.
Below in conjunction with the accompanying drawings with specific embodiment, the present invention is described in more detail.
Description of the drawings
Fig. 1 is the double mesoporous platinum-gadolinium nano-hybrid materials of mesoporous nano platinum particle and core shell structure of the embodiment of the present invention 1
TEM photos；
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 imitated for core shell structure double mesoporous platinum-gadolinium nano-hybrid materials magnetic resonance in mouse body of the embodiment of the present invention 7
Fruit is schemed；
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 hypodermic tumour position
The thermograph of photo-thermal effect.
Specific embodiment
Embodiment 1
Platinum-gadolinium nano-hybrid material of double mesoporous core shell structure that the present embodiment is provided and preparation method thereof, including it is following
Step：
(1) with N, N- dimethyl hexadecyls base ammonium bromide sodium acetate (OTAB-Na) is surfactant, using ascorbic acid
Chloroplatinic acid is reduced, synthesising mesoporous inorganic nano platinum particle：By 80mg surfactant N, N- dimethyl hexadecyl bromides
Change ammonium sodium acetate (OTAB-Na) to be added in 10mL deionized waters, be warmed up to 70 DEG C of dissolvings, be subsequently added into 2mL0.01mol/L chlorine
The platinic acid aqueous solution and 2mL0.2mol/L fresh aqueous ascorbic acid, stirs 3h, and centrifugation, washing, product is dissolved in deionized water
In, form mesoporous nano platinum particle dispersion liquid.
(2) with cetyl trimethylammonium bromide (CATB) as surfactant, in mesoporous inorganic nanoparticle surface bag
Mesoporous silicon oxide shell is wrapped up in, then removes CTAB, obtain the 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, formed the first mixed liquor, 0.5h is stirred at 70 DEG C, add in the first mixed liquor thereafter the NaOH of 100 μ L 30% with
1mL absolute ethyl alcohols, add 100 μ L tetraethyl orthosilicates (TEOS) after being warming up to 70 DEG C, react 2h under reflux state, centrifuge washing,
Product is dispersed in 10mL absolute ethyl alcohols, the second mixed liquor is obtained, then is added containing 0.6g ammonium nitrate in the second mixed liquor
Ammonium nitrate ethanol solution removes CTAB, and 60 DEG C of back flow reactions 2h, centrifuge washing obtains double mesoporous platinum-Nano particles of silicon dioxide,
In being dissolved in ethanol, the first dispersion liquid is obtained.
(3) aminopropyl triethoxysilane is used, by double mesoporous platinum-titanium dioxide of the silicone hydroxyl hydrolytie polycondensation to core shell structure
The mesoporous silicon oxide shell layer surface of silicon nano carry out it is amido modified, thereafter again pass through 1- (3- dimethylamino-propyls) -3-
The amido link of ethyl-carbodiimide hydrochloride and N-hydroxy-succinamide is common in modified mesoporous silicon oxide shell layer surface
Valency grafting diethyl pentetic acid, obtains the 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 obtained in, flow back 24h at 100 DEG C, centrifuge washing, will
Product is dissolved in 10mL dimethylformamides (DMF), obtains the second dispersion liquid；Thereafter 50mg diethyl pentetic acids are dissolved in
In dimethylformamide (DMF), and add 30mg 1- (3- dimethylamino-propyls) -3- ethyl-carbodiimide hydrochlorides and 30mg
N-hydroxy-succinamide, activates under room temperature and is added in the second dispersion liquid after 1h, and centrifuge washing after 24h is sufficiently stirred under room temperature,
The double mesoporous platinum-Nano particles of silicon dioxide of modified core shell structure is obtained, in being dispersed in 10mL deionized waters, is obtained
3rd dispersion liquid.
(4)GdCl3In Gd3+It is coordinated with the double mesoporous platinum-Nano particles of silicon dioxide of modified core shell structure,
Obtain the double mesoporous platinum-gadolinium nano-hybrid materials of core shell structure：2mol/L is added toward the 3rd dispersion liquid obtained in step (3)
20mL GdCl3Solution, after back flow reaction 3h at 100 DEG C, centrifuge washing, obtain product be the platinum of double mesoporous core shell structures-
Gadolinium nano-hybrid material.
The inorganic-inorganic nano-hybrid material of the double mesoporous core shell structure prepared using said method, it is core shell structure,
Kernel is mesoporous inorganic nano-particle, and shell is mesoporous silicon oxide shell, and the mesoporous silicon oxide shell layer surface is through nothing
Machine metal hybrid is modified；Wherein, the mesoporous inorganic nano-particle is mesoporous nano platinum particle, mesoporous Pd nano particle and is situated between
One kind in the golden nanometer particle of hole, a kind of mesoporous silicon oxide shell layer surface hydridization modification 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 preparation.
As shown in figure 1, Fig. 1 is the platinum-gadolinium nano hybridization material of (a) mesoporous nano platinum particle and (b) double mesoporous core shell structures
The TEM photos of material, as can be seen from the figure mesoporous nano platinum particle even particle size distribution, and have obvious pore structure.This
The platinum of the double mesoporous core shell structure of bright offer-gadolinium nano-hybrid material, in outside mesoporous layer energy hole path visible in detail,
Illustrate that the method can obtain that pattern is good, dispersive property 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 biological spy for it
Pin circulates in vivo significant.
Embodiment 2
Palladium-gadolinium nano-hybrid material of double mesoporous core shell structure and preparation method thereof that the present embodiment is provided, material and answer
With substantially the same manner as Example 1, its difference is that it is comprised the following steps：
(1) with N, N- dimethyl hexadecyls base ammonium bromide sodium acetate (OTAB-Na) is surfactant, using ascorbic acid
Palladium bichloride is reduced, synthesising mesoporous inorganic palladium particle：By 100mg surfactants (OTAB-Na) be added to 10mL go from
In sub- water, 50 DEG C of dissolvings are warmed up to, are subsequently added into 1mL 0.01mol/L palladium chloride aqueous solutions and fresh anti-of 1mL0.2mol/L
The bad hematic acid aqueous solution, stirs 1h, and centrifugation, washing, product is dissolved in deionized water, forms mesoporous Pd nano particle dispersion liquid.
(2) with cetyl trimethylammonium bromide (CATB) as surfactant, in mesoporous inorganic nanoparticle surface bag
Mesoporous silicon oxide shell is wrapped up in, then removes CTAB, obtain the 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, formed the first mixed liquor, 1h is stirred at 50 DEG C, add in the first mixed liquor thereafter the NaOH of 300 μ L 30% with
3mL absolute ethyl alcohols, add 300 μ L tetraethyl orthosilicates (TEOS) after being warming up to 80 DEG C, react 4h under reflux state, centrifuge washing,
Product is dispersed in 10mL absolute ethyl alcohols, the second mixed liquor is obtained, then is added containing 0.3g ammonium nitrate in 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, in being dissolved in toluene, obtains the first dispersion liquid.
(3) aminopropyl triethoxysilane is used, by double mesoporous palladium-titanium dioxide of the silicone hydroxyl hydrolytie polycondensation to core shell structure
The mesoporous silicon oxide shell layer surface of silicon nano carry out it is amido modified, thereafter again pass through 1- (3- dimethylamino-propyls) -3-
The amido link of ethyl-carbodiimide hydrochloride and N-hydroxy-succinamide is common in modified mesoporous silicon oxide shell layer surface
Valency grafting diethyl pentetic acid, obtains the 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 obtained in, flow back 24h at 80 DEG C, after reaction completely,
Centrifuge washing, product is dissolved in 10mL dimethylformamides (DMF), obtains the second dispersion liquid；Thereafter by 30mg diethyl three
Triamine pentaacetic acid is dissolved in dimethylformamide (DMF), and adds 20mg 1- (3- dimethylamino-propyls) -3- ethyl carbodiimides
Hydrochloride and 20mg N-hydroxy-succinamides, are added in the second dispersion liquid after room temperature activation 1h, are sufficiently stirred under room temperature
Centrifuge washing after 24h, obtains the double mesoporous palladium-Nano particles of silicon dioxide of modified core shell structure, is dispersed in 10mL
In deionized water, the 3rd dispersion liquid is obtained.
(4)GdCl3In Gd3+It is coordinated with the palladium-Nano particles of silicon dioxide of modified double mesoporous core shell structure,
Obtain the double mesoporous platinum-gadolinium nano-hybrid materials of core shell structure：2mol/L20mL is added toward the 3rd dispersion liquid obtained in step (3)
GdCl3Solution, reacts after 6h, centrifuge washing under 110 DEG C of reflux states, obtain product be the palladium of double mesoporous core shell structures-
Gadolinium nano-hybrid material.
Embodiment 3
Gold-gadolinium nano-hybrid material of double mesoporous core shell structure and preparation method thereof that the present embodiment is provided, material and answer
With essentially identical with embodiment 1 or 2, its difference is that it is comprised the following steps：
(1) with N, N- dimethyl hexadecyls base ammonium bromide sodium acetate (OTAB-Na) is surfactant, using ascorbic acid
Gold chloride is reduced, synthesising mesoporous inorganic gold particle：90mg surfactants (OTAB-Na) are added into 10mL deionizations
In water, 100 DEG C of dissolvings are warmed up to, are subsequently added into 1.5mL 0.01mol/L aqueous solution of chloraurate and 1.5mL 0.2mol/L are fresh
Aqueous ascorbic acid, stir 2h, centrifugation, washing, product is dissolved in deionized water, forms mesoporous golden nanometer particle dispersion
Liquid.
(2) with cetyl trimethylammonium bromide (CATB) as surfactant, in mesoporous inorganic nanoparticle surface bag
Mesoporous silicon oxide shell is wrapped up in, then removes CTAB, obtain the 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, formed the first mixed liquor, 1h is stirred at 80 DEG C, add in the first mixed liquor thereafter the NaOH of 150 μ L 30% with
5mL absolute ethyl alcohols, add 200 μ L tetraethyl orthosilicates (TEOS) after being warming up to 50 DEG C, react 3h under reflux state, centrifuge washing,
Product is dispersed in 10mL absolute ethyl alcohols, the second mixed liquor is obtained, then is added containing 0.4g ammonium nitrate in 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, in being dissolved in ethanol, obtains the first dispersion liquid.
(3) aminopropyl triethoxysilane is used, by double mesoporous gold-titanium dioxide of the silicone hydroxyl hydrolytie polycondensation to core shell structure
The mesoporous silicon oxide shell layer surface of silicon nano carry out it is amido modified, thereafter again pass through 1- (3- dimethylamino-propyls) -3-
The amido link of ethyl-carbodiimide hydrochloride and N-hydroxy-succinamide is common in modified mesoporous silicon oxide shell layer surface
Valency grafting diethyl pentetic acid, obtains the 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 obtained in, flow back 24h at 120 DEG C, centrifuge washing, will
Product is dissolved in 10mL dimethylformamides (DMF), obtains the second dispersion liquid；Thereafter 40mg diethyl pentetic acids are dissolved in
In dimethylformamide (DMF), and add 25mg 1- (3- dimethylamino-propyls) -3- ethyl-carbodiimide hydrochlorides and 25mg
N-hydroxy-succinamide, activates under room temperature condition and is added in the second dispersion liquid after 1h, centrifugation after 24h is sufficiently stirred under room temperature and is washed
Wash, obtain the gold-Nano particles of silicon dioxide of modified double mesoporous core shell structure, in being dispersed in 10mL deionized waters,
Obtain the 3rd dispersion liquid.
(4)GdCl3In Gd3+It is coordinated with the double mesoporous gold-Nano particles of silicon dioxide of modified core shell structure,
Obtain the double mesoporous gold-gadolinium nano-hybrid materials of core shell structure：2mol/L20mL is added toward the 3rd dispersion liquid obtained in step (3)
GdCl3Solution, reacts after 5h, centrifuge washing under 120 DEG C of reflux states, obtain product be the gold of double mesoporous core shell structures-
Gadolinium nano-hybrid material.
Embodiment 4
Platinum-iron nano-hybrid material of double mesoporous core shell structure and preparation method thereof that the present embodiment is provided, material and answer
With essentially identical with embodiment 1-3, its difference is that it is comprised the following steps：
(1) with N, N- dimethyl hexadecyls base ammonium bromide sodium acetate (OTAB-Na) is surfactant, using ascorbic acid
Chloroplatinic acid is reduced, synthesising mesoporous inorganic nano platinum particle：85mg surfactants (OTAB-Na) are added into 10mL
In ionized water, 60 DEG C of dissolvings are warmed up to, are subsequently added into 2mL0.01mol/L aqueous solution of chloraurate and 2mL 0.2mol/L are fresh
Aqueous ascorbic acid, stirs 2.5h, and centrifugation, washing, product is dissolved in deionized water, forms mesoporous nano platinum particle dispersion
Liquid.
(2) with cetyl trimethylammonium bromide (CATB) as surfactant, in mesoporous inorganic nanoparticle surface bag
Mesoporous silicon oxide shell is wrapped up in, then removes CTAB, obtain the 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, formed the first mixed liquor, 0.5h is stirred at 60 DEG C, add in the first mixed liquor thereafter the NaOH of 200 μ L 30% with
2mL absolute ethyl alcohols, add 200 μ L tetraethyl orthosilicates (TEOS) after being warming up to 60 DEG C, 2.5h is reacted under reflux state, and centrifugation is washed
Wash, product is dispersed in 10mL absolute ethyl alcohols, obtain the second mixed liquor, then ammonium nitrate containing 0.5g is added in the second mixed liquor
Ammonium nitrate ethanol solution remove CTAB, react 3h under 80 DEG C of reflux states, centrifuge washing obtains double mesoporous platinum-silica
Nano-particle, in being dissolved in toluene, obtains the first dispersion liquid.
(3) aminopropyl triethoxysilane is used, by double mesoporous platinum-titanium dioxide of the silicone hydroxyl hydrolytie polycondensation to core shell structure
The mesoporous silicon oxide shell layer surface of silicon nano carry out it is amido modified, thereafter again pass through 1- (3- dimethylamino-propyls) -3-
The amido link of ethyl-carbodiimide hydrochloride and N-hydroxy-succinamide is common in modified mesoporous silicon oxide shell layer surface
Valency grafting diethyl pentetic acid, obtains the 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 obtained in, after reacting completely under 100 DEG C of reflux states,
Centrifuge washing, product is dissolved in 10mL dimethylformamides (DMF), obtains the second dispersion liquid；Thereafter by 35mg diethyl three
Triamine pentaacetic acid is dissolved in dimethylformamide (DMF), and adds 20mg 1- (3- dimethylamino-propyls) -3- ethyl carbodiimides
Hydrochloride and 20mg N-hydroxy-succinamides, activate under room temperature and are added in the second dispersion liquid after 1h, are sufficiently stirred under room temperature
Centrifuge washing after 24h, obtains the platinum-Nano particles of silicon dioxide of modified double mesoporous core shell structure, is dispersed in 10mL
In deionized water, the 3rd dispersion liquid is obtained.
(4)FeCl3In Fe3+It is coordinated with the double mesoporous platinum-Nano particles of silicon dioxide of modified core shell structure,
Obtain the double mesoporous platinum-iron nano-hybrid materials of core shell structure：2mol/L is added toward the 3rd dispersion liquid obtained in step (3)
20mLFeCl3Solution, reacts after 4h, centrifuge washing under 100 DEG C of reflux states, obtains product and is double mesoporous core shell structures
Platinum-iron nano-hybrid material.
Embodiment 5
Platinum-manganese nano-hybrid material of double mesoporous core shell structure and preparation method thereof that the present embodiment is provided, material and answer
With essentially identical with embodiment 1-4, its difference is that it is comprised the following steps：
(1) with N, N- dimethyl hexadecyls base ammonium bromide sodium acetate (OTAB-Na) is surfactant, using ascorbic acid
Chloroplatinic acid is reduced, synthesising mesoporous inorganic platinum particles：95mg surfactants (OTAB-Na) are added into 10mL deionizations
In water, 80 DEG C of dissolvings are warmed up to, are subsequently added into the fresh Vitamin C of 2mL0.01mol/L aqueous solution of chloraurate and 2mL0.2mol/L
Aqueous acid, stirs 3h, and centrifugation, washing, product is dissolved in deionized water, forms mesoporous nano platinum particle dispersion liquid.
(2) with cetyl trimethylammonium bromide (CATB) as surfactant, in mesoporous inorganic nanoparticle surface bag
Mesoporous silicon oxide shell is wrapped up in, then removes CTAB, obtain the 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, formed the first mixed liquor, 1h is stirred at 70 DEG C, add in the first mixed liquor thereafter the NaOH of 200 μ L 30% with
4mL absolute ethyl alcohols, add 200 μ L tetraethyl orthosilicates (TEOS) after being warming up to 70 DEG C, react 2h under reflux state, centrifuge washing,
Product is dispersed in 10mL absolute ethyl alcohols, the second mixed liquor is obtained, then is added containing 0.5g ammonium nitrate in 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, in being dissolved in toluene, obtains the first dispersion liquid.
(3) aminopropyl triethoxysilane is used, by double mesoporous platinum-titanium dioxide of the silicone hydroxyl hydrolytie polycondensation to core shell structure
The mesoporous silicon oxide shell layer surface of silicon nano carry out it is amido modified, thereafter again pass through 1- (3- dimethylamino-propyls) -3-
The amido link of ethyl-carbodiimide hydrochloride and N-hydroxy-succinamide is common in modified mesoporous silicon oxide shell layer surface
Valency grafting diethyl pentetic acid, obtains the 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 obtained in, flow back 24h at 100 DEG C, centrifuge washing, will
Product is dissolved in 10mL dimethylformamides (DMF), obtains the second dispersion liquid；Thereafter 40mg diethyl pentetic acids are dissolved in
In dimethylformamide (DMF), and add 1- (3- the dimethylamino-propyls) -3- ethyl-carbodiimide hydrochlorides and 30mg of 30mg
N-hydroxy-succinamide, activates under room temperature and is added in the second dispersion liquid after 1h, and centrifuge washing after 24h is sufficiently stirred under room temperature,
The double mesoporous platinum-Nano particles of silicon dioxide of modified core shell structure is obtained, in being dispersed in 10mL deionized waters, is obtained
3rd dispersion liquid.
(4)MnCl2In Mn2+It is coordinated with the double mesoporous platinum-Nano particles of silicon dioxide of modified core shell structure,
Obtain the double mesoporous platinum-manganese nano-hybrid materials of core shell structure：2mol/ is added toward the 3rd dispersion liquid obtained in step (3)
L20mLMnCl2Solution, reacts after 6h, centrifuge washing under 100 DEG C of reflux states, obtains product and 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 application by double mesoporous core shell structures obtained in embodiment 1
In the method for light heat test, comprise the following steps：
(1) the double mesoporous platinum-gadolinium nano-hybrid materials of core-shell of the deionized water with 0～400 μ g/mL；
(2) it is 1.5w/cm with power density2808nm 5～15min of laser illumination；
(3) temperature change of different time points sample is recorded.
As shown in Fig. 2 after the irradiation of 808nm laser, as sample concentration increases, the temperature of sample gradually rises, most full-page proof
High-temperature is risen under product concentration conditions and can reach 30 DEG C or so, the platinum-gadolinium nano-hybrid material of double mesoporous core shell structures has well
Photo-thermal effect, photo-thermal conversion efficiency is high, and photostability is high.
Embodiment 7
The present embodiment provides a kind of platinum-gadolinium nano-hybrid material application by double mesoporous core shell structures obtained in embodiment 1
In the method for live body magnetic resonance imaging, comprise the following steps：
(1) platinum-gadolinium nano-hybrid material phosphate buffer (PBS) of the double mesoporous core shell structure for preparing is configured to
The dispersion liquid of 1～2mg/mL；
(2) entered in Kunming mouse body by tail vein injection, respectively the Magnetic Resonance Imaging after different time sections.
As shown in figure 3, (a) is the magnetic resonance imaging for injecting mouse after the double mesoporous platinum-gadolinium nano-hybrid materials of core shell structure
Anterior view, (b) be inject the magnetic resonance figure in mouse liver section after the double mesoporous platinum-gadolinium nano-hybrid material of core shell structure,.Can be with
Find out, inject has the signal of obvious magnetic resonance in mouse liver after the double mesoporous platinum-gadolinium nano-hybrid materials of core shell structure, and
At 2 hours, signal reached maximum, was injecting 24 hours signal decreases afterwards, illustrated that the double mesoporous platinum-gadolinium nanometers of core shell structure are miscellaneous
The nano-hybrid material has relatively long cycle period relative to other materials to change material, and does not exist long-term stagnant in vivo
The problem stayed.
Embodiment 8
The present embodiment provides a kind of platinum-gadolinium nano-hybrid material application by double mesoporous core shell structures obtained in embodiment 1
In the method for live body hypodermic tumour thermal imaging experiment, comprise the following steps：
(1) platinum-gadolinium nano-hybrid material PBS of the double mesoporous core shell structure for preparing is configured into dividing for 1～2mg/mL
Dispersion liquid；
(2) nude mice by subcutaneous intra-tumor is entered by intratumor injection and is used as experimental group, inject the conduct control of PBS cushioning liquid
Group, with 808nm laser 5min is irradiated, and by thermal imaging system the temperature change of tumor locus is observed.
As shown in figure 4, after the irradiation of 808nm laser, nano-hybrid material is significantly improved in tumor locus temperature,
Jing can reach the temperature needed for tumor thermal therapy.
The present invention's focuses on, by unique component and simplified preparation technology, can the double mesoporous cores of mass preparation
The inorganic-inorganic nano-hybrid material of shell structure, and easy to operate, process is easily-controllable, Stability Analysis of Structures, it is repeatable high, it is easy to produce
Industry；The nano-hybrid material size uniformity of its synthesis, significantly improves its photostability, photothermal conversion rate, magnetic resonance imaging
Resolution ratio, while the material meets the demand of clinical diagnosis and treatment, can be widely applied to diagnosis and treatment of tumour etc. raw
Thing medical domain.
As described in the above embodiment the present invention, it is used to synthesize double Jie using other obtained by same or similarity method
The method of the nano-hybrid material of hole core-shell, such as by change reactant prepare different mesoporous inorganic nano-particles or
By the amount of change reactant to regulate and control mesoporous silicon oxide shell thickness, by silicone hydroxyl hydrolytie polycondensation in mesoporous silicon oxide
Shell layer surface modifies different functional groups so as to connect different metal complex, in the scope of the present invention.
Claims (10)
1. a kind of preparation method of the inorganic-inorganic nano-hybrid material of double mesoporous core shell structure, it is characterised in that including following
Step：
(1) with N, N- dimethyl hexadecyls base ammonium bromide sodium acetate (OTAB-Na) be surfactant, ascorbic acid, slaine
For raw material, slaine is reduced using ascorbic acid, synthesising mesoporous inorganic nano-particle；
(2) with cetyl trimethylammonium bromide (CATB) as surfactant, NaOH, absolute ethyl alcohol, tetraethyl orthosilicate
(TEOS) and step (1) synthesis mesoporous inorganic nano-particle be raw material, mesoporous inorganic nanoparticle surface wrap up mesoporous two
Silica shell, reuses ammonium nitrate ethanol solution and removes CTAB, obtains double mesoporous inorganic-silica nanometers of core shell structure
Particle；
(3) double mesoporous inorganic-Nano particles of silicon dioxide, the aminopropyl-triethoxy silicon of the core shell structure synthesized with step (2)
Alkane, diethyl pentetic acid, 1- (3- dimethylamino-propyls) -3- ethyl-carbodiimide hydrochlorides and N- hydroxysuccinimidyls acyl are sub-
Amine is raw material, first with aminopropyl triethoxysilane, by double mesoporous inorganic-dioxies of the silicone hydroxyl hydrolytie polycondensation to core shell structure
The mesoporous silicon oxide shell layer surface of SiClx nano-particle carries out amido modified, passes through-(3- dimethylamino-propyls) -3- again thereafter
The amido link of ethyl-carbodiimide hydrochloride and N-hydroxy-succinamide is common in modified mesoporous silicon oxide shell layer surface
Valency grafting diethyl pentetic acid, obtains double mesoporous inorganic-Nano particles of silicon dioxide of modified core shell structure；
(4) with double mesoporous inorganic-Nano particles of silicon dioxide of modified core shell structure and metal chlorination salt as raw material, metal
Metal ion in chlorate is coordinated with double mesoporous inorganic-Nano particles of silicon dioxide of modified core shell structure, is obtained
To the inorganic-inorganic nano-hybrid material of double mesoporous core shell structures.
2. the preparation method of the inorganic-inorganic nano-hybrid material of mesoporous core shell structures as claimed in claim 1 double, its feature
It is that the step (1) is specially：N, N- dimethyl hexadecyl base ammonium bromide sodium acetate (OTAB-Na) aqueous solution are warming up to
50-100 DEG C, aqueous metal salt and fresh aqueous ascorbic acid are added, stir 1～3h, centrifugation after washing, is obtained
Product is mesoporous inorganic nano-particle.
3. the preparation method of the inorganic-inorganic nano-hybrid material of mesoporous core shell structures as claimed in claim 1 double, its feature
It is that the step (2) is specially：First mesoporous inorganic nano-particle is dissolved in deionized water, mesoporous inorganic nanoparticle is obtained
Sub- dispersion liquid, it is mixed with CTAB, forms the first mixed liquor, and 0.5-1h is stirred under the conditions of 50-80 DEG C, thereafter in the first mixing
NaOH and absolute ethyl alcohol are added in liquid, is added after being warming up to 50-80 DEG C and 2-4h is reacted under TEOS, reflux state, centrifugation is washed
Wash, product is disperseed in ethanol, to obtain the second mixed liquor, then ammonium nitrate ethanol solution is added in 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 mesoporous core shell structures as claimed in claim 1 double, its feature
It is that the step (3) is specially：During double mesoporous inorganic-Nano particles of silicon dioxide are dissolved in into ethanol or toluene, first is obtained
Dispersion liquid, in the first dispersion liquid aminopropyl triethoxysilane is added, and flow back 24h under the conditions of 80-120 DEG C, centrifuge washing,
Product is dissolved in dimethylformamide, the second dispersion liquid is obtained；Thereafter diethyl pentetic acid is dissolved in into dimethyl formyl
In amine, and 1- (3- dimethylamino-propyls) -3- ethyl-carbodiimide hydrochlorides and N-hydroxy-succinamide are added, it is living under room temperature
Change and added in the second dispersion liquid after 1h, centrifuge washing after 24h is stirred under room temperature, obtain the double mesoporous nothing of modified core shell structure
Machine-Nano particles of silicon dioxide.
5. the preparation method of the inorganic-inorganic nano-hybrid material of mesoporous core shell structures as claimed in claim 1 double, its feature
It is that the step (4) is specially：Double mesoporous inorganic-Nano particles of silicon dioxide of modified core shell structure are dispersed in
In deionized water, the 3rd dispersion liquid is obtained, chlorination metal salt solution is added toward the 3rd dispersion liquid, flowed back at 100-120 DEG C
After reaction 3-6h, centrifuge washing obtains the inorganic-inorganic nano-hybrid material that product is double mesoporous core shell structures.
6. the preparation method of the inorganic-inorganic nano-hybrid material of mesoporous core shell structures as claimed in claim 1 double, its feature
It is that the slaine in the step (1) is the one kind in chloroplatinic acid, palladium bichloride, gold chloride, the metal in the step (4)
Chlorate is the one kind in gadolinium chloride, iron chloride, manganese chloride.
7. the inorganic-inorganic of double mesoporous core shell structures is received obtained in a kind of preparation method by described in any one of claim 1～6
Rice hybrid material, it is characterised in that it is core shell structure, kernel is mesoporous inorganic nano-particle, and shell is mesoporous silicon oxide
Shell, and the mesoporous silicon oxide shell layer surface is through inorganic metal hybrid modification.
8. the inorganic-inorganic nano-hybrid material of mesoporous core shell structures as claimed in claim 7 double, it is characterised in that described
Mesoporous inorganic nano-particle is the one kind in mesoporous nano platinum particle, mesoporous Pd nano particle and mesoporous golden nanometer particle, described
A kind of hydridization modification in gadolinium, iron and manganese of mesoporous silicon oxide shell layer surface.
9. a kind of application of the inorganic-inorganic nano-hybrid material of double mesoporous core shell structures as claimed in claim 7, its feature
It is the photothermal reagent for being used as near infrared light photo-thermal therapy.
10. a kind of application of the inorganic-inorganic nano-hybrid material of double mesoporous core shell structures as claimed in claim 7, it is special
Levy and be, be used as the contrast preparation of magnetic resonance imaging.
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| CN107812200A (en) * | 2017-10-21 | 2018-03-20 | 天津大学 | BSA-gadolinium ionic complex-coated hollow gold nanosheet and preparation method thereof |
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| CN109651851A (en) * | 2019-01-15 | 2019-04-19 | 上海崇明木棉花开手工社 | The inorganic-organic hybridization nano pigment and preparation method of natural botanical source and application |
| CN114433029A (en) * | 2022-01-27 | 2022-05-06 | 江苏大学 | Preparation method of double-mesoporous core-shell type magnetic nano stirring rod and application of adsorption separation palladium |
| CN114433029B (en) * | 2022-01-27 | 2023-11-03 | 大城县荷丰有色金属有限公司 | Preparation method of double mesoporous core-shell magnetic nano stirring rod and application of adsorption separation palladium |
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