CN105770904A - Composite nano medicament-loading material for treating cancer and preparation method thereof - Google Patents
Composite nano medicament-loading material for treating cancer and preparation method thereof Download PDFInfo
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- CN105770904A CN105770904A CN201610149183.2A CN201610149183A CN105770904A CN 105770904 A CN105770904 A CN 105770904A CN 201610149183 A CN201610149183 A CN 201610149183A CN 105770904 A CN105770904 A CN 105770904A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 238000011068 loading method Methods 0.000 title claims abstract description 9
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- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 description 2
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- 239000004115 Sodium Silicate Substances 0.000 description 2
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 2
- 229940009456 adriamycin Drugs 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
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- 229910052911 sodium silicate Inorganic materials 0.000 description 2
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- 239000004094 surface-active agent Substances 0.000 description 2
- BFFQFGGITJXTFP-UHFFFAOYSA-N 3-methyldioxetane Chemical compound CC1COO1 BFFQFGGITJXTFP-UHFFFAOYSA-N 0.000 description 1
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- 229930012538 Paclitaxel Natural products 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- BSJGASKRWFKGMV-UHFFFAOYSA-L ammonia dichloroplatinum(2+) Chemical compound N.N.Cl[Pt+2]Cl BSJGASKRWFKGMV-UHFFFAOYSA-L 0.000 description 1
- 229940124650 anti-cancer therapies Drugs 0.000 description 1
- 238000011319 anticancer therapy Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
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- 238000006731 degradation reaction Methods 0.000 description 1
- 229960004679 doxorubicin Drugs 0.000 description 1
- VJJPUSNTGOMMGY-MRVIYFEKSA-N etoposide Chemical compound COC1=C(O)C(OC)=CC([C@@H]2C3=CC=4OCOC=4C=C3[C@@H](O[C@H]3[C@@H]([C@@H](O)[C@@H]4O[C@H](C)OC[C@H]4O3)O)[C@@H]3[C@@H]2C(OC3)=O)=C1 VJJPUSNTGOMMGY-MRVIYFEKSA-N 0.000 description 1
- 229960005420 etoposide Drugs 0.000 description 1
- 229960002949 fluorouracil Drugs 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229940088013 hycamtin Drugs 0.000 description 1
- 229940093474 manganese carbonate Drugs 0.000 description 1
- 235000006748 manganese carbonate Nutrition 0.000 description 1
- IPJKJLXEVHOKSE-UHFFFAOYSA-L manganese dihydroxide Chemical compound [OH-].[OH-].[Mn+2] IPJKJLXEVHOKSE-UHFFFAOYSA-L 0.000 description 1
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
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- 229960001756 oxaliplatin Drugs 0.000 description 1
- DWAFYCQODLXJNR-BNTLRKBRSA-L oxaliplatin Chemical compound O1C(=O)C(=O)O[Pt]11N[C@@H]2CCCC[C@H]2N1 DWAFYCQODLXJNR-BNTLRKBRSA-L 0.000 description 1
- 229960001592 paclitaxel Drugs 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 235000019795 sodium metasilicate Nutrition 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- RCINICONZNJXQF-MZXODVADSA-N taxol Chemical compound O([C@@H]1[C@@]2(C[C@@H](C(C)=C(C2(C)C)[C@H](C([C@]2(C)[C@@H](O)C[C@H]3OC[C@]3([C@H]21)OC(C)=O)=O)OC(=O)C)OC(=O)[C@H](O)[C@@H](NC(=O)C=1C=CC=CC=1)C=1C=CC=CC=1)O)C(=O)C1=CC=CC=C1 RCINICONZNJXQF-MZXODVADSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- UCFGDBYHRUNTLO-QHCPKHFHSA-N topotecan Chemical compound C1=C(O)C(CN(C)C)=C2C=C(CN3C4=CC5=C(C3=O)COC(=O)[C@]5(O)CC)C4=NC2=C1 UCFGDBYHRUNTLO-QHCPKHFHSA-N 0.000 description 1
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Classifications
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K45/00—Medicinal preparations containing active ingredients not provided for in groups A61K31/00 - A61K41/00
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K47/00—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient
- A61K47/02—Inorganic compounds
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K47/00—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient
- A61K47/30—Macromolecular organic or inorganic compounds, e.g. inorganic polyphosphates
- A61K47/42—Proteins; Polypeptides; Degradation products thereof; Derivatives thereof, e.g. albumin, gelatin or zein
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K49/00—Preparations for testing in vivo
- A61K49/001—Preparation for luminescence or biological staining
- A61K49/0013—Luminescence
- A61K49/0017—Fluorescence in vivo
- A61K49/0019—Fluorescence in vivo characterised by the fluorescent group, e.g. oligomeric, polymeric or dendritic molecules
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K49/00—Preparations for testing in vivo
- A61K49/001—Preparation for luminescence or biological staining
- A61K49/0013—Luminescence
- A61K49/0017—Fluorescence in vivo
- A61K49/005—Fluorescence in vivo characterised by the carrier molecule carrying the fluorescent agent
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K49/00—Preparations for testing in vivo
- A61K49/06—Nuclear magnetic resonance [NMR] contrast preparations; Magnetic resonance imaging [MRI] contrast preparations
- A61K49/08—Nuclear magnetic resonance [NMR] contrast preparations; Magnetic resonance imaging [MRI] contrast preparations characterised by the carrier
Abstract
The invention discloses a composite nano medicament-loading material for treating cancer and a preparation method thereof. The composite nano medicament-loading material takes UCNPs as a core; a layer of porous material covers the surface of the core; an anti-cancer medicament is loaded in pores; a layer of alkaline manganese compound is deposited on the surface of the porous material; the surface of the alkaline manganese compound is marked with one or more capture molecules or identification molecules. According to the composite nano medicament-loading material for treating cancer and the preparation method thereof, a common antigen antibody identification technology is utilized, and the characteristic that tumour cells can dissolve the alkaline manganese compound is utilized, and the anti-cancer medicament can be released to play a role only after the alkaline manganese compound is dissolved. The alkaline manganese compound in normal cells is hardly dissolved; the anti-cancer medicament is not released or is released slowly, so that the damage to the normal cells caused by the medicament can be greatly reduced; the side effect is low. In addition, an up-conversion luminescence fluorescence imaging technology and a nuclear magnetic resonance technology are combined, so that a double-function imaging mode of a tumour tissue is realized; the identification accuracy rate of the tumour tissue is improved; a treatment effect is observed accurately at any time.
Description
Technical field
The present invention relates to field of medicaments, particularly relate to a kind of for composite Nano medicine carrying material treating cancer and preparation method thereof.
Background technology
Cancer is to threaten the first killer of human health.Chemotherapeutics can high efficiency control and the cancer cell killed in tissue, be a kind of important anti-cancer therapies.
But, existing chemotherapeutics is poor due to targeting, inevitably to normal cell damage, causes patient body resistance degradation, thus reduces the survival rate of patient.According to statistics, after early-stage cancer patient's regular treatment, 5 years survival rates are 70% 95%, and 5 years survival rates after end-stage patients' regular treatment only have 10% 30%.Meanwhile, observing result for the treatment of needs by using corresponding imaging device to check after absorption of human body preparation again, and this there is also preparation targeting problem, and cannot follow the trail of the problems such as medication effect in time.
Therefore, prior art has yet to be improved and developed.
Summary of the invention
In view of above-mentioned the deficiencies in the prior art, it is an object of the invention to provide a kind of for composite Nano medicine carrying material treating cancer and preparation method thereof, it is intended to solve the problem that existing medicine carrying material targeting is poor, big to normal cell side effect and cannot follow the trail of medication effect in time.
Technical scheme is as follows:
A kind of composite Nano medicine carrying material for treating cancer, wherein, described composite Nano medicine carrying material is with UCNPs as core, core surface covers one layer of porous material, cancer therapy drug is loaded in hole, porous material surface one layer of alkaline manganese compound of deposition, alkaline manganese compound surface marks one or more capture molecules or identifies molecule.
The described composite Nano medicine carrying material for treating cancer, wherein, described porous material is the one in porous silica material, meso pore silicon oxide material, mesoporous TiO 2, meso-porous carbon material.
The described composite Nano medicine carrying material for treating cancer, wherein, described alkaline manganese compound is MnO2、Mn(OH)2Or MnCO3。
The composite Nano medicine carrying material of described treatment cancer, wherein, described cancer therapy drug is broad-spectrum anti-cancer drug.
The described composite Nano medicine carrying material for treating cancer, wherein, described capture molecule or identification molecule are one or more in antigen, antibody and specific proteins.
A kind of preparation method of arbitrary described composite Nano medicine carrying material for treating cancer, wherein, including step:
A, employing hydro-thermal method prepare UCNPs；
B, with UCNPs as core, core surface cover one layer of porous material, obtain cover porous material p-UCNPs；
C, p-UCNPs is immersed cancer therapy drug solution, soak absorption 1 ~ 96h, be dried, obtain loading the mp-UCNPs of cancer therapy drug；
D, mp-UCNPs surface deposit one layer of alkaline manganese compound, obtain the mmp-UCNPs that alkaline manganese compound is shell；
E, mmp-UCNPs alkaline manganese compound surface mark capturing molecule or identify molecule, obtain composite Nano medicine carrying material.
The preparation method of the described composite Nano medicine carrying material for treating cancer, wherein, when described porous material is porous silica material, described step B specifically includes: by waterglass in crucible in 120-500 DEG C of roasting 1-24h, obtain pressed powder；Described pressed powder is washed, is put into after drying in the CTAB solution of 0.03mol/L, the stirred in water bath of 30-80 DEG C, be simultaneously introduced UCNPs particle, stir 1-8h, be cooled to room temperature, the HCl of dropping 0.1-6mol/L, the pH value of solution is adjusted to 6-9；Filtering, washing, be dried, the sample obtained is incubated 1-8h at 300-600 DEG C, i.e. obtains covering the p-UCNPs of porous silica material.
The preparation method of the described composite Nano medicine carrying material for treating cancer, wherein, described alkaline manganese compound is MnO2Time, described step D specifically includes: the mp-UCNPs of load cancer therapy drug is pipetted 250 μ L and is added in the centrifuge tube of 2mL, add the 2-(N-morpholino of 250 μ L 0.1mol/L pH=6) ethyl sulfonic acid cushioning liquid, add 250 μ L 10 mmol/L KMnO4Mix；Become Blang's colloid after solution 30min, through centrifugation, clean by deionized water, remove supernatant, i.e. obtain MnO2Mmp-UCNPs for shell.
The preparation method of the described composite Nano medicine carrying material for treating cancer, wherein, described alkaline manganese compound is Mn (OH)2Time, described step D specifically includes: the mp-UCNPs of load cancer therapy drug is pipetted 250 μ L and is added in the centrifuge tube of 2mL, add the PBS of 250 μ L 0.1mol/L pH=8.0, add 250 μ L 10mmol/L KMnO4Mix；Through centrifugation after 30min, clean by deionized water, remove supernatant, i.e. obtain Mn (OH)2Mmp-UCNPs for shell.
The preparation method of the described composite Nano medicine carrying material for treating cancer, wherein, described alkaline manganese compound is MnCO3Time, described step D specifically includes: the mp-UCNPs of load cancer therapy drug is pipetted 1mL and is added in the centrifuge tube of 5mL, add 500 μ L 0.1mol/L MnCl2Solution, is added dropwise over 1mL 0.1mol/L Na the most under agitation2CO3Solution, through centrifugation after 30min, cleans by deionized water, removes supernatant, i.e. obtain MnCO3Mmp-UCNPs for shell.
Beneficial effect: after the composite Nano medicine carrying material of the present invention is injected in vivo, the capture molecule fixing on its surface or identify under molecular action, can be combined with cancer cell and be swallowed by cancer cell.After entering cancer cell, owing to the acidity in cancer cell is strong, alkaline manganese compound is decomposed by acid, and the cancer therapy drug being enclosed in porous material is released, and kills cancer cell.It addition, after alkaline manganese compound dissolves, the manganese ion that dissociates is Magnetic resonance imaging agent, can be organized by Magnetic resonance imaging positioning tumor in time；The UCNPs covering porous material can carry out up-conversion luminescence positioning tumor tissue by infrared laser irradiation.Wherein up-converting phosphor technology can avoid the background fluorescence of biological tissue, highly sensitive.
Detailed description of the invention
The present invention provides a kind of for composite Nano medicine carrying material treating cancer and preparation method thereof, and for making the purpose of the present invention, technical scheme and effect clearer, clear and definite, the present invention is described in more detail below.Should be appreciated that specific embodiment described herein, only in order to explain the present invention, is not intended to limit the present invention.
The present invention provides a kind of for composite Nano medicine carrying material treating cancer and preparation method thereof, wherein, described composite Nano medicine carrying material is with UCNPs as core, core surface covers one layer of porous material, cancer therapy drug is loaded in hole, porous material surface one layer of alkaline manganese compound of deposition, alkaline manganese compound surface marks one or more capture molecules or identifies molecule.The present invention with rare earth upconversion nano material (UCNPs) as core, surface covers one layer of porous material, load cancer therapy drug (such as adriamycin) in hole, then deposit one layer of alkaline manganese compound (such as manganese dioxide, manganous hydroxide or manganese carbonate) at porous material surface, to close cancer therapy drug.Alkaline manganese compound surface marks one or more capture molecules or identifies molecule (such as antigen, antibody or specific proteins), and its effect is can be with one or more cancer cells such as specific recognition lung cancer, liver cancer, cancer of the stomach, the cancer of the esophagus, the carcinoma of the rectum, colon cancer, breast cancer, cancer of pancreas, osteocarcinoma, prostate cancer, carcinoma of urinary bladder, cutaneum carcinomas.After composite Nano medicine carrying material of the present invention is injected in vivo, under specific antigen, antibody or specific proteins effect that its surface is fixing, can be combined with cancer cell and be swallowed by cancer cell.After entering cell, due to the sour environment in cancer cell, alkaline manganese compound dissolves, and the cancer therapy drug being enclosed in porous material is released, and kills cancer cell.Generally, due to specific the most not the 100% of specific antigen, antibody or specific proteins, always have a small amount of nanoparticle and enter in normal cell, cause injury of human.The composite Nano medicine carrying material of the present invention, owing to normal cell inner acidic is more weak, alkaline manganese compound is difficult to dissolve, thus cancer therapy drug does not discharges or discharge slowly, is substantially reduced the injury (side effect is little) of agents on normal cells.After alkaline manganese compound dissolves, the manganese ion that dissociates is Magnetic resonance imaging agent, can be organized by Magnetic resonance imaging positioning tumor.The UCNPs covering porous material can carry out up-conversion luminescence positioning tumor tissue by infrared laser irradiation.Wherein up-converting phosphor technology can avoid the background fluorescence of biological tissue, highly sensitive.The composite Nano medicine carrying material of the present invention, while medicine carrying kills cancer cell, moreover it is possible to leave Magnetic resonance imaging agent and up-conversion fluorescence preparation in the cancer cell of apoptosis, conveniently follows the tracks of medication effect in time.The composite Nano medicine carrying material of the present invention, combines specific recognition and the pattern of two kinds of tumor cells of Chemical recognition, and targeting is high, is substantially reduced cancer therapy drug to Normocellular toxic action, thus the toxic and side effect of chemotherapy is preferably minimized.Meanwhile, after medicine effect, also having and have Magnetic resonance imaging agent and infrared up conversion fluorescence imaging agent simultaneously in tumour cell, convenient follow the tracks of result for the treatment of is observed, and adjusts in time or maintaining treatment scheme.
The composite Nano medicine carrying material of the present invention can identify multiple kinds of tumor cell and kill they (lung cancer, liver cancer, cancer of the stomach, the cancer of the esophagus, the carcinoma of the rectum, colon cancer, breast cancer, cancer of pancreas, osteocarcinoma, prostate cancer, carcinoma of urinary bladder, cutaneum carcinoma etc.), and can reduce Normocellular toxicity, targeting is good, have up-conversion fluorescence identification function and NMR imaging function concurrently, it is simple to follow the trail of medication effect simultaneously comprehensively.Can be suitable for killing early, middle and late each phase cancer cell.
Further, the particle diameter of described rare earth upconversion nano material is 20-60nm.Preferable particle size the most of the present invention be the UCNPs of 20-60nm be core, to improve the identification function of UCNPs.
Further, the one during described porous material is the materials such as porous silica material, meso pore silicon oxide material, mesoporous TiO 2, mesoporous carbon.The i.e. present invention preferably covers one layer of porous silica material, meso pore silicon oxide material, mesoporous TiO 2 or meso-porous carbon material, preferably to load cancer therapy drug on UCNPs core surface.
Further, described cancer therapy drug is broad-spectrum anti-cancer drug, such as, broad-spectrum anti-cancer drug can be one or more combinations in adriamycin, Etoposide, endoxan and fluorouracil, Hycamtin, taxol, oxaliplatin, neoplatin, Doxorubicin etc..Cancer cell all can effectively be killed by above-mentioned cancer therapy drug.
Further, described alkaline manganese compound is MnO2、Mn(OH)2Or MnCO3.Due to the sour environment of cancer cell, after the present invention above-mentioned alkaline manganese compound enters cancer cell, so that the cancer therapy drug being enclosed in porous material is released, cancer cell can be killed by carcinolysis.And normal cell inner acidic is more weak, above-mentioned alkaline manganese compound is difficult to dissolve, thus cancer therapy drug does not discharges or discharge slowly, is substantially reduced cancer therapy drug to Normocellular injury.
Further, described capture molecule or identification molecule are one or more in antigen, antibody and specific proteins.This specific antigen of the present invention, antibody or specific proteins can be with one or more cancer cells such as specific recognition lung cancer, liver cancer, cancer of the stomach, the cancer of the esophagus, the carcinoma of the rectum, colon cancer, breast cancer, cancer of pancreas, osteocarcinoma, prostate cancer, carcinoma of urinary bladder, cutaneum carcinomas, it is possible to swallowed by cancer cell.
Based on above-mentioned composite Nano medicine carrying material, the present invention also provides for the preparation method of arbitrary a kind of described composite Nano medicine carrying material for treating cancer, wherein, including step:
A, employing hydro-thermal method prepare UCNPs；
B, with UCNPs as core, core surface cover one layer of porous material, obtain cover porous material p-UCNPs, be designated as p-UCNPs；
C, p-UCNPs is immersed cancer therapy drug solution, soak absorption 1 ~ 96h, be dried, obtain loading the p-UCNPs of cancer therapy drug, be designated as mp-UCNPs；
D, mp-UCNPs surface deposit one layer of alkaline manganese compound, obtain the mp-UCNPs that alkaline manganese compound is shell, be designated as mmp-UCNPs；
E, mmp-UCNPs alkaline manganese compound surface mark capturing molecule or identify molecule, obtain composite Nano medicine carrying material.
The composite Nano medicine carrying material prepared by said method, while medicine carrying kills cancer cell, moreover it is possible to leave Magnetic resonance imaging agent and up-conversion fluorescence preparation in the cancer cell of apoptosis, conveniently follows the tracks of medication effect in time.
The composite Nano medicine carrying material of the present invention, even if there being a small amount of mark unsuccessful, enter in normal cell, owing to normal cell inner acidic is more weak, alkaline manganese compound is difficult to decompose, thus cancer therapy drug does not discharges or discharge slowly, it is substantially reduced the injury of agents on normal cells, reduces the toxic and side effect of chemotherapy.Owing to alkaline manganese compound does not decomposes, or decompose slowly, it is impossible to enough MRI contrast agent Mn are provided2+, also will not discharge switching core material on fluorescence, even if so nano combined medicine carrying material identification mistake, entering into normal cell, also will not be identified as tumour cell in MRI imaging, up-conversion fluorescence imaging process, being substantially reduced the risk of over-treatment.
The composite Nano medicine carrying material of the present invention, combines specific recognition and the pattern of two kinds of tumor cells of Chemical recognition, and targeting is high, is substantially reduced cancer therapy drug to Normocellular toxic action, thus the toxic and side effect of chemotherapy is preferably minimized.Meanwhile, after medicine effect, also having and have Magnetic resonance imaging agent and infrared up conversion fluorescence imaging agent simultaneously in tumour cell, convenient follow the tracks of result for the treatment of is observed, and adjusts in time or maintaining treatment scheme.
Specifically, described step A is, uses hydro-thermal method to prepare rare earth upconversion nano material (UCNPs), it is preferable that use hydro-thermal method to prepare rare earth upconversion nano material (UCNPs) that particle diameter is 20-60nm.Prior art has recorded the detailed preparation method of rare earth upconversion nano material, does not repeats at this.
In step B, porous material of the present invention can be but be not limited to porous silica material, meso pore silicon oxide material, mesoporous TiO 2 (TiO2), one in the material such as mesoporous carbon.Specifically, when described porous material is porous silica material, described step B specifically includes: by waterglass in crucible in 120-500 DEG C of roasting 1-24h, obtain pressed powder；Described pressed powder is washed, is put into after drying in the CTAB solution of 0.03mol/L, the stirred in water bath of 30-80 DEG C, be simultaneously introduced UCNPs particle, stir 1-8h, be cooled to room temperature, the HCl of dropping 0.1-6mol/L, the pH value of solution is adjusted to 6-9；Filter, washing, be dried, obtain sample and be incubated 1-8h at 300-600 DEG C, i.e. obtain covering the p-UCNPs of porous silica material.
Specifically, when described porous material is porous silica material, described step B can also specifically include: Pluronic F-127 ether polymer surfactant is dissolved in N, in the mixed solution of dinethylformamide (DMF) and HCl/water solution, it is subsequently adding under UCNPs particle, stirring condition and adds a certain amount of tetraethyl orthosilicate (TEOS), at 20-90 DEG C after stirring reaction 1-48h, centrifugal, it is dried, obtains white solid product and be the p-UCNPs covering porous silica material.
Specifically, when described porous material is meso pore silicon oxide material, described step B specifically includes: with surfactant and in the presence of ethylene glycol or the polyalcohol such as glycerine or butanediol, add UCNPs particle, adding sodium silicate solution under stirring condition, synthesis covers the p-UCNPs of meso pore silicon oxide material.
Specifically, when described porous material is meso pore silicon oxide material, described step B specifically includes: in the sodium metasilicate being completely dissolved and cationic surfactant solution, adds UCNPs particle, and under stirring condition, synthesis covers the p-UCNPs of meso pore silicon oxide material.
Specifically, described porous material is mesoporous TiO2During material, described step B specifically includes: with tetrabutyl titanate as presoma, isopropanol, ethylene glycol or glycerine or butanediol etc. are solvent, cetyl trimethylammonium bromide (CTAB) or sodium cetanesulfonate or Pluronic F-127 ether, polycyclic oxypropylene ether are template, cover mesoporous TiO by sol-gel process synthesis2P-UCNPs.
Specifically, described step C is, the p-UCNPs covering porous material is immersed cancer therapy drug solution, soaks absorption 1 ~ 96h, be dried, and obtains loading the mp-UCNPs of cancer therapy drug.
In step D, described alkaline manganese compound is MnO2、Mn(OH)2Or MnCO3.Specifically, described alkaline manganese compound is MnO2Time, described step D specifically includes: be 1mg/mL by the mp-UCNPs(concentration of load cancer therapy drug) pipette 250 μ L and be added in the centrifuge tube of 2mL, add the 2-(N-morpholino of 250 μ L 0.1mol/L pH=6) ethyl sulfonic acid cushioning liquid, add 250 μ L 10mmol/L KMnO4Mix；Become Blang's colloid after solution 30min, through centrifugation, clean by deionized water, remove supernatant, i.e. obtain MnO2Mmp-UCNPs for shell.
Specifically, described alkaline manganese compound is Mn (OH)2Time, described step D specifically includes: be 1mg/mL by the mp-UCNPs(concentration of load cancer therapy drug) pipette 250 μ L and be added in the centrifuge tube of 2mL, add the PBS of 250 μ L 0.1mol/L pH=8.0, add 250 μ L 10 mmol/L KMnO4Mix；Through centrifugation after 30min, clean by deionized water, remove supernatant, i.e. obtain Mn (OH)2Mmp-UCNPs for shell.
Specifically, described alkaline manganese compound is MnCO3Time, described step D specifically includes: by load cancer therapy drug mp-UCNPs(concentration be 2mg/mL) pipette in the centrifuge tube that 1mL is added to 5 mL, add 500 μ L 0.1mol/L MnCl2Solution, is added dropwise over 1mL 0.1 mol/L Na the most under agitation2CO3Solution, through centrifugation after 30min, cleans by deionized water, removes supernatant, i.e. obtain MnCO3Mmp-UCNPs for shell.
Step E is, at alkaline manganese compound surface mark capturing molecule or the identification molecule of mmp-UCNPs, obtains composite Nano medicine carrying material.I.e. mark specific antigen, antibody or specific proteins at alkaline manganese compound surface, with specific recognition multiple kinds of tumor cell and kill they (lung cancer, liver cancer, cancer of the stomach, the cancer of the esophagus, the carcinoma of the rectum, colon cancer, breast cancer, cancer of pancreas, osteocarcinoma, prostate cancer, carcinoma of urinary bladder, cutaneum carcinoma etc.).
Compared with prior art, the present invention significantly improved 2 points:
A. at specific recognition technical elements, utilizing common antigen-antibody identification technology, recycling tumour cell can dissolve the characteristic of alkaline manganese compound, after only alkaline manganese compound is dissolved, cancer therapy drug just can discharge and play a role.Normal cell neutral and alkali manganese compound dissolves hardly, and cancer therapy drug does not discharges or discharges slowly, can be substantially reduced the injury of agents on normal cells, and side effect is little.
B. combine up-conversion luminescence Imaging-PAM and nuclear magnetic resonance technique, it is achieved the difunctional imaging pattern to tumor tissues, improve the recognition accuracy to tumor tissues, accurate observation result for the treatment of at any time.
In sum, it is a kind of for composite Nano medicine carrying material treating cancer and preparation method thereof that the present invention provides, wherein, described composite Nano medicine carrying material is with UCNPs as core, core surface covers one layer of porous material, loading cancer therapy drug, porous material surface one layer of alkaline manganese compound of deposition in hole, alkaline manganese compound surface marks one or more capture molecules or identifies molecule.The present invention utilizes common antigen-antibody identification technology, recycling tumour cell can dissolve the characteristic of alkaline manganese compound, and after only alkaline manganese compound is dissolved, cancer therapy drug just can discharge and play a role.Normal cell neutral and alkali manganese compound dissolves hardly, and cancer therapy drug does not discharges or discharges slowly, can be substantially reduced the injury of agents on normal cells, and side effect is little.It addition, the present invention combines up-conversion luminescence Imaging-PAM and nuclear magnetic resonance technique, it is achieved the difunctional imaging pattern to tumor tissues, improve the recognition accuracy to tumor tissues, accurate observation result for the treatment of at any time.
It should be appreciated that the application of the present invention is not limited to above-mentioned citing, for those of ordinary skills, can be improved according to the above description or convert, all these modifications and variations all should belong to the protection domain of claims of the present invention.
Claims (10)
1. the composite Nano medicine carrying material being used for treating cancer, it is characterized in that, described composite Nano medicine carrying material is with UCNPs as core, core surface covers one layer of porous material, cancer therapy drug is loaded in hole, porous material surface one layer of alkaline manganese compound of deposition, alkaline manganese compound surface marks one or more capture molecules or identifies molecule.
Composite Nano medicine carrying material for treating cancer the most according to claim 1, it is characterised in that described porous material is the one in porous silica material, meso pore silicon oxide material, mesoporous TiO 2, meso-porous carbon material.
Composite Nano medicine carrying material for treating cancer the most according to claim 1, it is characterised in that described alkaline manganese compound is MnO2、Mn(OH)2Or MnCO3。
The composite Nano medicine carrying material for the treatment of cancer the most according to claim 1, it is characterised in that described cancer therapy drug is broad-spectrum anti-cancer drug.
Composite Nano medicine carrying material for treating cancer the most according to claim 1, it is characterised in that described capture molecule or identification molecule are one or more in antigen, antibody and specific proteins.
6. the preparation method of composite Nano medicine carrying material for treating cancer as described in claim 1 ~ 5 is arbitrary, it is characterised in that include step:
A, employing hydro-thermal method prepare UCNPs；
B, with UCNPs as core, core surface cover one layer of porous material, obtain cover porous material p-UCNPs；
C, p-UCNPs is immersed cancer therapy drug solution, soak absorption 1 ~ 96h, be dried, obtain loading the mp-UCNPs of cancer therapy drug；
D, mp-UCNPs surface deposit one layer of alkaline manganese compound, obtain the mmp-UCNPs that alkaline manganese compound is shell；
E, mmp-UCNPs alkaline manganese compound surface mark capturing molecule or identify molecule, obtain composite Nano medicine carrying material.
The preparation method of the composite Nano medicine carrying material for treating cancer the most according to claim 6, it is characterized in that, when described porous material is porous silica material, described step B specifically includes: by waterglass in crucible in 120-500 DEG C of roasting 1-24h, obtain pressed powder；Described pressed powder is washed, is put into after drying in the CTAB solution of 0.03mol/L, the stirred in water bath of 30-80 DEG C, be simultaneously introduced UCNPs particle, stir 1-8h, be cooled to room temperature, the HCl of dropping 0.1-6mol/L, the pH value of solution is adjusted to 6-9；Filtering, washing, be dried, the sample obtained is incubated 1-8h at 300-600 DEG C, i.e. obtains covering the p-UCNPs of porous silica material.
The preparation method of the composite Nano medicine carrying material for treating cancer the most according to claim 6, it is characterised in that described alkaline manganese compound is MnO2Time, described step D specifically includes: the mp-UCNPs of load cancer therapy drug is pipetted 250 μ L and is added in the centrifuge tube of 2mL, add the 2-(N-morpholino of 250 μ L 0.1mol/L pH=6) ethyl sulfonic acid cushioning liquid, add 250 μ L 10 mmol/L KMnO4Mix；Become Blang's colloid after solution 30min, through centrifugation, clean by deionized water, remove supernatant, i.e. obtain MnO2Mmp-UCNPs for shell.
The preparation method of the composite Nano medicine carrying material for treating cancer the most according to claim 6, it is characterised in that described alkaline manganese compound is Mn (OH)2Time, described step D specifically includes: the mp-UCNPs of load cancer therapy drug is pipetted 250 μ L and is added in the centrifuge tube of 2mL, add the PBS of 250 μ L 0.1mol/L pH=8.0, add 250 μ L 10mmol/L KMnO4Mix；Through centrifugation after 30min, clean by deionized water, remove supernatant, i.e. obtain Mn (OH)2Mmp-UCNPs for shell.
The preparation method of the composite Nano medicine carrying material for treating cancer the most according to claim 6, it is characterised in that described alkaline manganese compound is MnCO3Time, described step D specifically includes: the mp-UCNPs of load cancer therapy drug is pipetted 1mL and is added in the centrifuge tube of 5mL, add 500 μ L 0.1mol/L MnCl2Solution, is added dropwise over 1mL 0.1mol/L Na the most under agitation2CO3Solution, through centrifugation after 30min, cleans by deionized water, removes supernatant, i.e. obtain MnCO3Mmp-UCNPs for shell.
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