CN109620955A - A kind of biodegradable meso-porous nanometer magnetic material and preparation method thereof - Google Patents

A kind of biodegradable meso-porous nanometer magnetic material and preparation method thereof Download PDF

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CN109620955A
CN109620955A CN201811284788.8A CN201811284788A CN109620955A CN 109620955 A CN109620955 A CN 109620955A CN 201811284788 A CN201811284788 A CN 201811284788A CN 109620955 A CN109620955 A CN 109620955A
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calcium
aqueous solution
phosphate
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王璞琳
马铭
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Beijing Sai Zhi Technology Co Ltd
Dongguan University of Technology
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Dongguan University of Technology
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Abstract

The present invention provides a kind of biodegradable meso-porous nanometer magnetic materials and preparation method thereof.The present invention is using coprecipitation in situ, by a certain amount of calcic, the salt of phosphate radical and carbonate dissolves in aqueous solution, constant temperature stirs at a certain temperature, then a certain amount of soluble iron is added, cobalt, the salt such as nickel, continue constant temperature and stirs 10s-120h, product filtering, ethanol washing 2 times, 600-1200 DEG C of calcining 2-12h after being dried in air, product is placed in the citric acid-sodium hydroxide buffer that pH is 4.5-7.4, 30min-24h is continuously stirred under certain temperature, product deionized water is washed 2 times, ethanol washing 2 times, 50-60 DEG C of drying, obtain the mesoporous nano magnetic material in skeleton containing nano magnetic material.The meso-porous nanometer magnetic material of the method for the present invention synthesis can be used as magnetic target material, kill for tumour, the orientation of cancerous tissue, and have biodegradability, and can gradually degrade discharge in vivo, avoid the accumulation enrichment of nanoparticle in vivo.

Description

A kind of biodegradable meso-porous nanometer magnetic material and preparation method thereof
Technical field
The invention belongs to biomaterial preparation fields, and in particular to a kind of biodegradable meso-porous nanometer magnetic material and its Preparation method.
Background technique
The method of traditional treatment cancer is radiotherapy (radiotherapy) and chemotherapy (chemotherapy), and maximum difficult point is to kill The regeneration and function of normal cell, tissue, no specificity in treatment are difficult to ensure while dead tumour cell.Last century 70 Age, Widder et al. propose magnetic control targeted drug delivery system concept, and magnetic nano-particle anticancer therapy has become at present One emphasis direction of domestic and international anticancer drug target controlling and releasing system research.For magnetic drug targeting, developed The variety carriers materials such as magnetic albumin, magnetic liposome, magnetic medical macromolecular materials, micron order magnetic target therapy vector Easily cause thrombus sample blood vessel embolism, when reducing carrier dimensions to nanoscale, particle specific surface area increases, and the drug of carrying increases Add, blood viscosity can be overcome to fast move and separate under external magnetic field, is easier to improve curative effect of medication.Magnetic nanoparticle is used It is easy to be enriched in cancer, tumor locus in oncotherapy, under external magnetic field, embolism is easily caused in tumor tissues, is blocked swollen The blood supply of tumor tissue, eventually leads to death of neoplastic cells, and in alternating magnetic field, local temperature caused by magnetic hysteresis is excessively high can also To kill tumor tissues, can be administered by approach such as vein, arterial duct, oral or injections.
Meso-porous nanometer magnetic material mainly uses shell structurre in terms of drug targeting transmission at present, and magnetic material is wrapped up In core position, it is substrate that shell mesoporous material, which mostly uses nano silica,.Chinese patent CN101625919A uses colloidal sol Gel combination hydro-thermal method has obtained the magnetism of the mesoporous nano in silicon dioxide skeleton and mesopore orbit containing nano magnetic material Material, preparation method use hydrothermal method, and preparation condition requires height, and process is uncontrollable, and collosol and gel product is nano-scale, Solid-liquid is not readily separated, and main carriers nano silica is not biodegradable in vivo, can be enriched in people with blood migration everywhere Body normal tissue, there are biosafety issues.
Summary of the invention
The present invention aiming at the shortcomings in the prior art, provides a kind of biodegradable meso-porous nanometer magnetic material and its preparation Method.The meso-porous nanometer magnetic material of the method for the present invention synthesis can be used as magnetic target material, determine for tumour, cancerous tissue To killing, and there is biodegradability, can gradually degrade discharge in vivo, avoid nanoparticle in vivo Accumulation enrichment.
It is an object of the present invention to provide a kind of material, the material includes magnetic nano crystal and inorganic nano-crystal Body；The chemical composition of the magnetic nano crystal includes metal oxide；The chemical composition packet of the inorganic nanocrystal Include the substance of tool biocompatibility and/or biodegradability；The material further includes meso-hole structure.
At least one of specifically, the material further includes following 1) -8) described:
1) average grain diameter of the particle of the material is 20nm-800nm；Specifically, the average grain of the particle of the material Diameter is 800nm, 20nm, 50nm, 650nm or 350nm；
2) specific surface area of the material includes 80-120m2/g；Specifically, the specific surface area of the material is 80m2/g、 120m2/g、115m2/g、90m2/ g or 95m2/g；
3) in the material, the mass percentage of the magnetic nano crystal is 20%-30%；Specifically, the magnetic Property nanocrystal mass percentage be 20%, 30% or 25%；
4) in the material, the mass percentage of the inorganic nanocrystal is 70%-80%；Specifically, the nothing The mass percentage of machine nanocrystal is 80%, 70% or 75%；
5) material further includes anti-tumor drug；Specifically, the anti-tumor drug includes adriamycin and/or Japanese yew Alcohol；And/or in the material, the mass percentage of the anti-tumor drug is 0-10wt%；
6) chemical composition of the inorganic nanocrystal includes P elements, calcium constituent and/or carbanion；Specifically, The chemical composition of the inorganic nanocrystal includes tricalcium phosphate and/or calcium carbonate；
7) chemical composition of the magnetic nano crystal includes ferroso-ferric oxide, cobaltosic oxide and/or three oxidations Two nickel；
8) chemical composition of the material includes Fe3O4Ca4(PO4)2CO3、Co3O4Ca4(PO4)2CO3、Ni2O3Ca4(PO4)2CO3And/or Fe3O4Ca5(PO4)3CO3。
Again specifically, the preparation method of the material includes: that calcium salt, phosphate and/or carbonate are dissolved in acid water In solution, after adding reacting metal salt, adjusting pH value with lye, the reaction was continued 9.0 or more, after filtering to take solid matter calcining, It is placed in the buffer that pH is 4.5-7.4 after stirring, washing, drying to obtain the final product；Specifically, with lye adjust pH value 9.0, 10.0,11.0 and/or 9.5.
At least one of also specifically, the preparation method of the material further includes following 1) -21) described:
1) calcium salt includes calcium chloride, calcium nitrate and/or calcium phosphate；
2) phosphate include phosphoric acid, disodium-hydrogen, sodium dihydrogen phosphate, potassium phosphate,monobasic, dipotassium hydrogen phosphate and/or Potassium dihydrogen phosphate；
3) carbonate includes sodium carbonate and/or sodium bicarbonate；
4) acidic aqueous solution includes the acidic aqueous solution that pH is 1-5；Specifically, the acidic aqueous solution includes that pH is 1.0,4.2,3.2 and/or 5 acidic aqueous solution；
5) acidic aqueous solution includes the aqueous solution of hydrochloric acid, nitric acid and/or phosphoric acid；
6) metal salt includes iron chloride, ferric nitrate, cobalt chloride, cobalt nitrate, nickel chloride and/or nickel nitrate；
7) lye includes sodium hydroxide, potassium hydroxide and/or ammonium hydroxide；
8) buffer includes citric acid-sodium hydroxide buffer；
9) calcining, which is included in oxidizing atmosphere, calcines；Specifically, being included in air or O2It is calcined in atmosphere；
10) calcining includes 600-1200 DEG C of calcining；Specifically, the calcining includes 800-1000 DEG C of calcining；Have again Body is 800 DEG C or 1000 DEG C；
11) calcining includes calcining 2-12h；Specifically, the calcining is calcining 12h, 2h, 6h or 7h；
It 12) further include 0 DEG C of -100 DEG C of constant temperature stirring before adding metal salt；Specifically, further including 0 before addition metal salt DEG C, 25 DEG C and/or the stirring of 100 DEG C of constant temperature
It 13) further include continuing to stir 10s-120h after adding metal salt；Specific stirring 30min；
14) the reaction was continued the 2min-36h that includes that the reaction was continued；Specifically, the reaction was continued 2min, 36h, 2h, and/or 13h；
It is 15) described that the reaction was continued including stirring；Specifically, the stirring includes high-speed stirred；The high-speed stirred is to stir Mix 1200 turns/min or more of speed；
It 16) further include that will filter after gained solid matter deionized water and/or ethanol washing 50-60 DEG C after the filtering Drying；Specifically, the washing is to be washed with deionized 2 times, ethanol washing 2 times；And/or specifically, the drying includes 50 DEG C of drying；
17) stirring includes stirring 30min-24h；Specifically, the stirring includes stirring 30min or 6h；And/or institute Stating stirring includes 25 DEG C of constant temperature stirrings；
18) washing includes using deionized water and/or ethanol washing；Specifically, the washing is to be washed with deionized water It washs 2 times, ethanol washing 2 times；
19) drying includes 50-60 DEG C of drying；Specifically, the drying includes 50 DEG C of drying；
20) molar ratio of the metal in the calcium and metal salt in the calcium salt includes 3:1-4:1；
21) chemical composition of the material includes Fe3O4Ca4(PO4)2CO3、Co3O4Ca4(PO4)2CO3、Ni2O3Ca4(PO4)2CO3And/or Fe3O4Ca5(PO4)3CO3。
It is a further object to provide a kind of preparation method of material, the preparation method includes: by calcium salt, phosphorus Hydrochlorate and/or carbonate are dissolved in acidic aqueous solution, add reacting metal salt after, with lye adjust pH value 9.0 or more after Continuous reaction after filtering to take solid matter calcining, is placed in the buffer that pH is 4.5-7.4 after stirring, washing, drying to obtain the final product；Tool Body, pH value is adjusted 9.0,10.0,11.0 and/or 9.5 with lye.
At least one of specifically, the preparation method further includes following 1) -24) described:
1) calcium salt includes calcium chloride, calcium nitrate and/or calcium phosphate；
2) phosphate include phosphoric acid, disodium-hydrogen, sodium dihydrogen phosphate, potassium phosphate,monobasic, dipotassium hydrogen phosphate and/or Potassium dihydrogen phosphate；
3) carbonate includes sodium carbonate and/or sodium bicarbonate；
4) acidic aqueous solution includes the acidic aqueous solution that pH is 1-5；Specifically, the acidic aqueous solution includes that pH is 1.0,4.2,3.2 and/or 5 acidic aqueous solution；
5) acidic aqueous solution includes the aqueous solution of hydrochloric acid, nitric acid and/or phosphoric acid；
6) metal salt includes iron chloride, ferric nitrate, cobalt chloride, cobalt nitrate, nickel chloride and/or nickel nitrate；
7) lye includes sodium hydroxide, potassium hydroxide and/or ammonium hydroxide；
8) buffer includes citric acid-sodium hydroxide buffer；
9) calcining, which is included in oxidizing atmosphere, calcines；Specifically, being included in air or O2It is calcined in atmosphere；
10) calcining includes 600-1200 DEG C of calcining；Specifically, the calcining includes 800-1000 DEG C of calcining；Have again Body is 800 DEG C or 1000 DEG C；
11) calcining includes calcining 2-12h；Specifically, the calcining is calcining 12h, 2h, 6h or 7h；
It 12) further include constant temperature stirring at 0 DEG C -100 DEG C before adding metal salt；Specifically, further including 0 before addition metal salt DEG C, 25 DEG C and/or the stirring of 100 DEG C of constant temperature
It 13) further include continuing to stir 10s-120h after adding metal salt；Specific stirring 30min；
14) the reaction was continued the 2min-36h that includes that the reaction was continued；Specifically, the reaction was continued 2min, 36h, 2h, and/or 13h；
It is 15) described that the reaction was continued including stirring；Specifically, the stirring includes high-speed stirred；The high-speed stirred is to stir Mix 1200 turns/min or more of speed；
It 16) further include that will filter after gained solid matter deionized water and/or ethanol washing 50-60 DEG C after the filtering Drying；Specifically, the washing is to be washed with deionized 2 times, ethanol washing 2 times；And/or specifically, the drying includes 50 DEG C of drying；
17) stirring includes stirring 30min-24h；Specifically, the stirring includes stirring 30min or 6h；And/or institute Stating stirring includes 25 DEG C of constant temperature stirrings；
18) washing includes using deionized water and/or ethanol washing；Specifically, the washing is to be washed with deionized water It washs 2 times, ethanol washing 2 times；
19) drying includes 50-60 DEG C of drying；Specifically, the drying includes 50 DEG C of drying；
20) molar ratio of the metal in the calcium and metal salt in the calcium salt includes 3:1-4:1；
21) chemical composition of the material includes Fe3O4Ca4(PO4)2CO3、Co3O4Ca4(PO4)2CO3、Ni2O3Ca4(PO4)2CO3And/or Fe3O4Ca5(PO4)3CO3；
22) material further includes meso-hole structure；
23) average grain diameter of the particle of the material is 20nm-800nm；Specifically, the average grain of the particle of the material Diameter is 800nm, 20nm, 50nm, 650nm or 350nm；
24) specific surface area of the material includes 80-120m2/g；Specifically, the specific surface area of the material is 80m2/g、 120m2/g、115m2/g、90m2/ g or 95m2/g。
It is also another object of the present invention to provide the materials that any the method for the present invention is directly prepared.
It is also another object of the present invention to provide the applications of any material of the present invention.
At least one of specifically, the application includes following 1) -2) described:
1) as pharmaceutical carrier or be used to prepare tool pharmaceutical carrier function product；
2) anti-tumor drug or antitumor Related product are used to prepare.
It is also another object of the present invention to provide the applications of any the method for the present invention.
At least one of specifically, the application includes following 1) -2) described:
1) it is used to prepare pharmaceutical carrier or is used to prepare the product of tool pharmaceutical carrier function；
2) anti-tumor drug or antitumor Related product are used to prepare.
The advantages of the present invention are:
Biodegradable meso-porous nanometer magnetic material provided by the invention has stronger hydrophily, with tumor cell surface Albumen can express excellent surface compatibility.Therefore, it after targeting inputs the meso-porous nano magnetic particle, can efficiently adsorb To tumour cell surface and generate enrichment, block the nutrition of tumour cell to input to killing tumour cell.
The preparation process of biodegradable meso-porous nanometer magnetic material provided by the invention is simple, requires not experimental facilities Height, it is at low cost, pass through between nanocrystal segmentation and hydrogen ion etching, so that it may realize magnetic particle nano-scale and mesoporous hole The formation in road can be widely used for targeted drug delivery, biological magnetic to realize the magnetism and drug loading of the magnetic nanoparticle The fields such as separation.
Detailed description of the invention
The drawings described herein are used to provide a further understanding of the present application, constitutes part of this application, not Constitute the improper restriction to the application.In the accompanying drawings:
Fig. 1 is biodegradable meso-porous nanometer magnetic material Fe prepared by embodiment 13O4Ca4(PO4)2CO3Scanning electricity Sub- microscopy images figure.
Fig. 2 is biodegradable meso-porous nanometer magnetic material Fe prepared by embodiment 13O4Ca4(PO4)2CO3Biodegrade Curve graph.
Fig. 3 is biodegradable meso-porous nanometer magnetic material Co prepared by embodiment 23O4Ca4(PO4)2CO3XRD crystal Structure and Components identification result figure.
Fig. 4 is biodegradable meso-porous nanometer magnetic material Co prepared by embodiment 23O4Ca4(PO4)2CO3Cancer cell kill Hurt results of comparison figure.
Fig. 5 is biodegradable meso-porous nanometer magnetic material Fe prepared by embodiment 53O4Ca4(PO4)2CO3Cancer cell target The experimental result picture of tropism.
Specific embodiment
Made in following embodiments, experimental method is conventional method unless otherwise specified.
Material as used in the following examples etc., is commercially available unless otherwise specified.
Following embodiments and its illustrate for explanation and understanding the present invention, do not constitute to improper limit of the invention It is fixed.
Embodiment 1, biodegradable meso-porous nanometer magnetic material Fe3O4Ca4(PO4)2CO3Preparation
12g calcium nitrate, 5.77g disodium-hydrogen and 1.29g sodium carbonate are weighed, is dissolved in the hydrochloric acid solution that pH is 1.0, 0 DEG C of constant temperature stirs evenly.Suitable FeCl is added3Aqueous solution continues to stir so that the ratio between molecular number of calcium and iron is 4:1 at 0 DEG C 30min is mixed, then adjusts pH value of solution 9.0 using sodium hydroxide solution, high-speed stirred 2min filters product, deionized water Washing 2 times, ethanol washing 2 times, 50 DEG C of drying, 800 DEG C of calcining 12h, obtain desciccate in air.
It takes the above-mentioned product being prepared to be placed in the citric acid-sodium hydroxide buffer that pH is 5.5, is continuously stirred at 25 DEG C 30min is mixed, product centrifuge separation removes supernatant, and precipitating is washed with deionized 2 times, and ethanol washing 2 times, 50 DEG C of drying obtain Biodegradable meso-porous nanometer magnetic material Fe of the present invention3O4Ca4(PO4)2CO3.It is mesoporous that Fig. 1 provides the biodegradable Nano magnetic material Fe3O4Ca4(PO4)2CO3Scanning electron microscope result.
The average grain diameter of the particle of the material is 800nm, specific surface area 80m2/g；The quality hundred of magnetic nano crystal Dividing content is 20%；The mass percentage of inorganic nanocrystal is 80%.
The meso-porous nanometer magnetic material of above-mentioned preparation is placed in 37 DEG C of human body simulation body fluid, pH 7.4, it is continuous to shake 2h, 4h, 8h, 16h are swung, for 24 hours, 36h, 48h, after 72h, filtering, deionized water washing, ethanol washing, drying weighing.Fig. 2 is provided The biodegradable curve of the biodegradable meso-porous nanometer magnetic material.Fig. 2 the result shows that, the biology that the present embodiment is prepared can Meso-porous nanometer magnetic material biodegradability of degrading is good, and degradation rate is very fast in the early stage, and material surface atom can rapidly enter Simulated body fluid reaches balance after 150h, and after loading the anti-tumor drugs such as adriamycin and/or taxol, drug can with particle degradation To reach maximum value in a short time and keep sustained release, has effects that continued administration.
Embodiment 2, biodegradable meso-porous nanometer magnetic material Co3O4Ca4(PO4)2CO3Preparation
9g calcium chloride, 8.24g dipotassium hydrogen phosphate and 0.84g sodium bicarbonate are weighed, is dissolved in the hydrochloric acid solution that pH is 4.2, It is stirred evenly in 25 DEG C of constant temperature.Suitable CoCl is added3Aqueous solution so that the ratio between molecular number of calcium and cobalt be 3:1,25 DEG C after Continuous stirring 30min, then adjusts pH value of solution 10.0 using potassium hydroxide solution, and high-speed stirred 36h filters product, go from Sub- water washing 2 times, ethanol washing 2 times, 50 DEG C of drying, 800 DEG C of calcining 2h, obtain desciccate in air.
It takes the above-mentioned product being prepared to be placed in the citric acid-sodium hydroxide buffer that pH is 6.6, is continuously stirred at 25 DEG C 6h is mixed, product centrifuge separation removes supernatant, and precipitating is washed with deionized 2 times, and ethanol washing 2 times, 50 DEG C of drying obtain this The invention biodegradable meso-porous nanometer magnetic material Co3O4Ca4(PO4)2CO3.Fig. 3 provides that the biodegradable is mesoporous to be received Rice magnetic material Co3O4Ca4(PO4)2CO3XRD crystal structure result.
The average grain diameter of the particle of the material is 20nm, specific surface area 120m2/g；The quality hundred of magnetic nano crystal Dividing content is 30%；The mass percentage of inorganic nanocrystal is 70%.
By the meso-porous nanometer magnetic material ultrasonic disperse of above-mentioned preparation in DMEM cell culture fluid, magnetic nano-particle is dense Degree is 0.3mg/L.It is added in 24 porocyte culture plates for 100 microlitres with every hole, culture plate has adherent growth cell in advance SKOV3, microscopically observation cell number and form, observation result continue to train as shown in the picture for marking " before addition " in Fig. 4 After supporting for 24 hours, SKOV3 cell growth state is observed under inverted microscope, SKOV3 cell becomes the ball cell that falls off from adherent, sees Result is examined as shown in the picture for marking " after addition " in Fig. 4.Fig. 4 the result shows that, biodegradable that the present embodiment is prepared is situated between Hole nano magnetic material can effectively kill cancer cell.
Embodiment 3, biodegradable meso-porous nanometer magnetic material Ni2O3Ca4(PO4)2CO3Preparation
9g calcium chloride, 8.24g dipotassium hydrogen phosphate and 0.84g sodium bicarbonate are weighed, is dissolved in the hydrochloric acid solution that pH is 3.2, It is stirred evenly in 100 DEG C of constant temperature.Suitable NiCl is added2Aqueous solution, so that the ratio between molecular number of calcium and nickel is 4:1, at 100 DEG C Continuing to stir 30min, then adjusts pH value of solution 11.0 or more using potassium hydroxide solution, high-speed stirred 2h filters product, Deionized water is washed 2 times, and ethanol washing 2 times, 50 DEG C of drying, 800 DEG C of calcining 6h, obtain desciccate in air.
It takes the above-mentioned product being prepared to be placed in the citric acid-sodium hydroxide buffer that pH is 6.0, is continuously stirred at 25 DEG C 6h is mixed, product centrifuge separation removes supernatant, and precipitating is washed with deionized 2 times, and ethanol washing 2 times, 50 DEG C of drying obtain this The invention biodegradable meso-porous nanometer magnetic material Ni2O3Ca4(PO4)2CO3。
The average grain diameter of the particle of the material is 50nm, specific surface area 115m2/g；The quality hundred of magnetic nano crystal Dividing content is 25%；The mass percentage of inorganic nanocrystal is 75%.
Embodiment 4, biodegradable meso-porous nanometer magnetic material Fe3O4Ca5(PO4)3CO3Preparation
9g calcium chloride, 7.42g dipotassium hydrogen phosphate and 0.84g sodium bicarbonate are weighed, is dissolved in the hydrochloric acid solution that pH is 5, 100 DEG C of constant temperature stir evenly.Suitable Fe (NO is added3)3Aqueous solution, so that the ratio between molecular number of calcium and iron is 3:1, at 100 DEG C Continue stir 30min, then using potassium hydroxide solution adjust pH value of solution 9.5, high-speed stirred 13h filters product, go from Sub- water washing 2 times, ethanol washing 2 times, 50 DEG C of drying, 800 DEG C of calcining 10h, obtain desciccate in air.
It takes the above-mentioned product being prepared to be placed in the citric acid-sodium hydroxide buffer that pH is 7.4, is continuously stirred at 25 DEG C 6h is mixed, product centrifuge separation removes supernatant, and precipitating is washed with deionized 2 times, and ethanol washing 2 times, 50 DEG C of drying obtain this The invention biodegradable meso-porous nanometer magnetic material Fe3O4Ca5(PO4)3CO3。
The average grain diameter of the particle of the material is 650nm, specific surface area 90m2/g；The quality hundred of magnetic nano crystal Dividing content is 30%；The mass percentage of inorganic nanocrystal is 70%.
Embodiment 5, drug loading biodegradable meso-porous nanometer magnetic material Fe3O4Ca4(PO4)2CO3Preparation
10g calcium nitrate, 3.77g disodium-hydrogen and 0.87g sodium carbonate are weighed, is dissolved in the hydrochloric acid solution that pH is 1.0, 37 DEG C of constant temperature stir evenly.Suitable FeCl is added3Aqueous solution continues so that the ratio between molecular number of calcium and iron is 4:1 at 37 DEG C 30min is stirred, then adjusts pH value of solution 9.0 using sodium hydroxide solution, high-speed stirred 2min filters product, deionization Water washing 2 times, ethanol washing 2 times, 50 DEG C of drying, 800 DEG C of calcining 7h, obtain desciccate in air.
It takes the above-mentioned product being prepared to be placed in the citric acid-sodium hydroxide buffer that pH is 5.5, is continuously stirred at 25 DEG C 30min is mixed, product centrifuge separation removes supernatant, and precipitating is washed with deionized 2 times, and ethanol washing 2 times, 50 DEG C of drying obtain Biodegradable meso-porous nanometer magnetic material Fe of the present invention3O4Ca4(PO4)2CO3。
The average grain diameter of the particle of the material is 350nm, specific surface area 95m2/g；The quality hundred of magnetic nano crystal Dividing content is 30%；The mass percentage of inorganic nanocrystal is 70%.
In the ratio of material and drug 9:1, the adriamycin and/or taxol that weigh 10Wt% are dissolved in 37 DEG C of human body simulation In body fluid.90% above-mentioned material, after sealing continuous oscillation 48h under the conditions of 37 DEG C, filtering, deionized water washing, drying, gamma Radiation sterilization.Weighing.It is added in 24 porocyte culture plates for 100 microlitres with every hole, culture plate is having adherent growth just in advance Normal gonad cell and ovarian cancer cell SKOV3, after 2h is added, microscopically observation cell number and form observe result such as Fig. 5 Shown, in Fig. 5, normal cell indicates that normal ovarian cell, cancer cell indicate ovarian cancer cell SKOV3, Nanoparticles indicates drug loading biodegradable meso-porous nanometer magnetic material Fe3O4Ca4(PO4)2CO3.The experimental result Display carries medicine meso-porous nano magnetic particle and is enriched in cancer cell surfaces, shows that material manufactured in the present embodiment has target to cancer cell Tropism.
Embodiments of the present invention above described embodiment only expresses, the description thereof is more specific and detailed, but can not Therefore limitations on the scope of the patent of the present invention are interpreted as, as long as skill obtained in the form of equivalent substitutions or equivalent transformations Art scheme should all be fallen within the scope and spirit of the invention.

Claims (10)

1. a kind of material, which is characterized in that the material includes magnetic nano crystal and inorganic nanocrystal；The magnetic Nano The chemical composition of crystal includes metal oxide；The chemical composition of the inorganic nanocrystal includes tool biocompatibility And/or the substance of biodegradability；The material further includes meso-hole structure.
2. material according to claim 1, which is characterized in that the material further includes following 1) -8) it is described at least It is a kind of:
1) average grain diameter of the particle of the material is 20nm-800nm；
2) specific surface area of the material includes 80-120m2/g；
3) in the material, the mass percentage of the magnetic nano crystal is 20%-30%；
4) in the material, the mass percentage of the inorganic nanocrystal is 70%-80%；
5) material further includes anti-tumor drug；
6) chemical composition of the inorganic nanocrystal includes P elements, calcium constituent and/or carbanion；
7) chemical composition of the magnetic nano crystal includes ferroso-ferric oxide, cobaltosic oxide and/or nickel sesquioxide；
8) chemical composition of the material includes Fe3O4Ca4(PO4)2CO3、Co3O4Ca4(PO4)2CO3、Ni2O3Ca4(PO4)2CO3 And/or Fe3O4Ca5(PO4)3CO3。
3. according to claim 1 and/or 2 any materials, which is characterized in that the preparation method of the material include: by Calcium salt, phosphate and/or carbonate are dissolved in acidic aqueous solution, after adding reacting metal salt, adjust pH value 9.0 with lye Above the reaction was continued, after filtering to take solid matter calcining, is placed in the buffer that pH is 4.5-7.4 after stirring, washing, drying i.e. ?.
4. material according to claim 3, which is characterized in that the preparation method of the material further includes following 1) -21) institute At least one of state:
1) calcium salt includes calcium chloride, calcium nitrate and/or calcium phosphate；
2) phosphate includes phosphoric acid, disodium-hydrogen, sodium dihydrogen phosphate, potassium phosphate,monobasic, dipotassium hydrogen phosphate and/or phosphoric acid Potassium dihydrogen；
3) carbonate includes sodium carbonate and/or sodium bicarbonate；
4) acidic aqueous solution includes the acidic aqueous solution that pH is 1-5；
5) acidic aqueous solution includes the aqueous solution of hydrochloric acid, nitric acid and/or phosphoric acid；
6) metal salt includes iron chloride, ferric nitrate, cobalt chloride, cobalt nitrate, nickel chloride and/or nickel nitrate；
7) lye includes sodium hydroxide, potassium hydroxide and/or ammonium hydroxide；
8) buffer includes citric acid-sodium hydroxide buffer；
9) calcining, which is included in oxidizing atmosphere, calcines；
10) calcining includes 600-1200 DEG C of calcining；
11) calcining includes calcining 2-12h；
It 12) further include 0 DEG C of -100 DEG C of constant temperature stirring before adding metal salt；
It 13) further include continuing to stir 10s-120h after adding metal salt；
14) the reaction was continued the 2min-36h that includes that the reaction was continued；
It is 15) described that the reaction was continued including stirring；
It 16) further include 50-60 DEG C of baking after filtering gained solid matter deionized water and/or ethanol washing after the filtering It is dry；
17) stirring includes stirring 30min-24h；
18) washing includes using deionized water and/or ethanol washing；
19) drying includes 50-60 DEG C of drying；
20) molar ratio of the metal in the calcium and metal salt in the calcium salt includes 3:1-4:1；
21) chemical composition of the material includes Fe3O4Ca4(PO4)2CO3、Co3O4Ca4(PO4)2CO3、Ni2O3Ca4(PO4)2CO3 And/or Fe3O4Ca5(PO4)3CO3。
5. a kind of preparation method of material, which is characterized in that the preparation method includes: by calcium salt, phosphate and/or carbonate It is dissolved in acidic aqueous solution, after adding reacting metal salt, adjusting pH value with lye, the reaction was continued 9.0 or more, filters to take solid After the calcining of state substance, it is placed in the buffer that pH is 4.5-7.4 after stirring, washing, drying to obtain the final product.
6. according to the method described in claim 5, it is characterized in that, the preparation method further includes following 1) -24) it is described in It is at least one:
1) calcium salt includes calcium chloride, calcium nitrate and/or calcium phosphate；
2) phosphate includes phosphoric acid, disodium-hydrogen, sodium dihydrogen phosphate, potassium phosphate,monobasic, dipotassium hydrogen phosphate and/or phosphoric acid Potassium dihydrogen；
3) carbonate includes sodium carbonate and/or sodium bicarbonate；
4) acidic aqueous solution includes the acidic aqueous solution that pH is 1-5；
5) acidic aqueous solution includes the aqueous solution of hydrochloric acid, nitric acid and/or phosphoric acid；
6) metal salt includes iron chloride, ferric nitrate, cobalt chloride, cobalt nitrate, nickel chloride and/or nickel nitrate；
7) lye includes sodium hydroxide, potassium hydroxide and/or ammonium hydroxide；
8) buffer includes citric acid-sodium hydroxide buffer；
9) calcining, which is included in oxidizing atmosphere, calcines；Specifically, being included in air or O2It is calcined in atmosphere；
10) calcining includes 600-1200 DEG C of calcining；
11) calcining includes calcining 2-12h；
It 12) further include constant temperature stirring at 0 DEG C -100 DEG C before adding metal salt；
It 13) further include continuing to stir 10s-120h after adding metal salt；
14) the reaction was continued the 2min-36h that includes that the reaction was continued；
It is 15) described that the reaction was continued including stirring；
It 16) further include 50-60 DEG C of baking after filtering gained solid matter deionized water and/or ethanol washing after the filtering It is dry；
17) stirring includes stirring 30min-24h；
18) washing includes using deionized water and/or ethanol washing；
19) drying includes 50-60 DEG C of drying；
20) molar ratio of the metal in the calcium and metal salt in the calcium salt includes 3:1-4:1；
21) chemical composition of the material includes Fe3O4Ca4(PO4)2CO3、Co3O4Ca4(PO4)2CO3、Ni2O3Ca4(PO4)2CO3 And/or Fe3O4Ca5(PO4)3CO3；
22) material further includes meso-hole structure；
23) average grain diameter of the particle of the material is 20nm-800nm；
24) specific surface area of the material includes 80-120m2/g。
7. the material that claim 5 and/or 6 any the methods are directly prepared.
8. the application of claim 1,2,3,4 and/or 7 any materials.
9. application according to claim 8, which is characterized in that the application includes following 1) -2) it is described at least one Kind:
1) as pharmaceutical carrier or be used to prepare tool pharmaceutical carrier function product；
2) anti-tumor drug or antitumor Related product are used to prepare.
10. the application of claim 5 and/or 6 any the methods.
At least one of specifically, the application includes following 1) -2) described:
1) it is used to prepare pharmaceutical carrier or is used to prepare the product of tool pharmaceutical carrier function；
2) anti-tumor drug or antitumor Related product are used to prepare.
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