CN104306969A - Method for preparing target release-controlled inorganic selenium medicine - Google Patents
Method for preparing target release-controlled inorganic selenium medicine Download PDFInfo
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- CN104306969A CN104306969A CN201410464117.5A CN201410464117A CN104306969A CN 104306969 A CN104306969 A CN 104306969A CN 201410464117 A CN201410464117 A CN 201410464117A CN 104306969 A CN104306969 A CN 104306969A
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Abstract
The invention discloses a method for preparing a target release-controlled inorganic selenium medicine. The preparation process includes the three steps that a magnetic Fe3O4 kernel for loading the inorganic selenium medicine is prepared; the magnetic inorganic selenium medicine is wrapped by nanosilicon dioxide; biocompatibility processing is carried out on the inorganic selenium medicine. According to the method for preparing the target release-controlled inorganic selenium medicine, coprecipitation of the inorganic selenium medicine and porous magnetic Fe3O4 is adopted, the inorganic selenium medicine is attracted to the surface and the interior of the magnetic Fe3O4, and therefore the release speed of the inorganic selenium medicine is decreased; the inorganic selenium medicine is wrapped by the porous nanosilicon dioxide, so that target long-acting slow release and controllable release of the inorganic selenium medicine are achieved; the surface of the inorganic selenium medicine is processed with polyvinylpyrrolidone macromolecule sol, and therefore the biocompatibility of the inorganic selenium medicine is improved. The method solves the problem that an existing inorganic selenium medicine is unstable in release speed is solved; the aims of conducting targeted medicine delivery, reducing side effects of the medicine and improving the treatment efficiency are achieved.
Description
Technical field
The present invention relates to a kind of preparation method of targeting controllable release inorganic selenium medicine, particularly one porous nano silica is housing, the magnetic ferroferric oxide core of coated absorption inorganic selenium, the preparation method of inorganic selenium targeting long-acting slow-releasing medicine can be realized, belong to fine chemistry industry and field of nanometer technology.
Background technology
Selenium is the indispensable a kind of trace element of body vital movement, and human body tens kinds of diseases such as it and anemia, coronary heart disease, arthritis, acquired immune deficiency syndrome (AIDS), diabetes are closely related.In addition; selenium and the development of selenium compound to Tumor suppression have protective effect; and produce antitumaous effect by number of mechanisms; it is the regulatory factor of oncogene expression; can inducing cancer cell programmed cell death; and can affect immunization of cell, many development models of tumor cell accept selenium compound regulation and control all directly or indirectly.
Inorganic selenium medicine adopts selenium dioxide, sodium selenite, sodium selenate, selenium sulfide, selenium sulfide etc. to be selenium source mostly, and wherein maximum with the investigation and application of sodium selenite, its anticancer effect is also remarkable.
In an adult human body, normal selenium content is 4-10mg, and the selenium be absorbed in body is discharged by excrement, urine or expiration.The selenium optimised quantity that every day is taken in is 55 μ g, and adult is no more than at most 400 μ g every day, and the selenium of excess intake may cause acute and chronic poisoning, and the toxicity of selenium is that restriction is containing one of most important factor of selenium drug development.Inorganic selenium medicine is used for mankind's Orally taken selenium-replenishing, and everyone every day, conventional selenium supplement amount was 50-100 μ g, and treatment selenium supplement amount is 100-300 μ g, divides three inferior to taking half an hour after meal.
Chinese patent CN1401329(2003-03-12) to disclose a kind of take bimetallic oxide as the oral Selenium supplement agent of carrier and system is each and using method, oral Selenium supplement agent is a kind of bimetallic oxide containing active selenium, and the content of selenium in bimetallic oxide is 0.01%-0.5%.Utilize the character of bimetallic oxide adsorpting anion, by selenate radical, its lattice of selenite radical implanted ions, make solid state powder finally by drying and grinding or spraying dry, or be pressed into tablet.There is provided required trace element-selenium by slow releasing function for human or animal, alleviate and directly take the side effect such as gastrointestinal reaction that inorganic selenium sterling brings, add the absorbance of selenium.During this invention practical application, elemental selenium sustained-release dosage is difficult to accurate control, easily occurs that selenium is excessive or not enough.
Chinese patent CN1911239(2007-02-14) disclose a kind of Selenium supplement agent and preparation method and purposes, it is a kind of anion exchange resin containing commutative selenate radical or selenite radical ion, by weight percentage, the content of selenium in anion exchange resin is 0.1%-1.0%.Its preparation method utilizes anion exchange resin can play the feature of exchange interaction with anion, selenate radical or selenite radical loaded in anion exchange resin.Due to the control slow-released carrier that ion exchange resin is a kind of function admirable, to the selenium of institute's load, there is control slow releasing function, thus substantially increase the absorption rate of selenium.Selenium supplement agent of the present invention has low toxicity, efficiently feature, can be used as selenium-supplementing feed additive; Also can be used for health product and the medicine preparing mankind's Orally taken selenium-replenishing and treated human diseases by the selenium of drug treatment.During this invention practical application, selenium can not discharge from anion exchange resin Linear, and selenium concentration controls not accurate enough.
Chinese patent CN102078324(2011-06-01) disclose a kind of can the medicine of Hepatoma therapy, provide chitosan monohydrate selenium dioxide ester be prepared in a kind of can application in the medicine of Hepatoma therapy.Chitosan monohydrate selenium dioxide ester selenate radical is adsorbed in chitosan monomer 2-NH
2with the low-molecular-weight organic selenium that 6-0H is prepared into, there is stronger antitumor action, and toxic and side effects is also much smaller.In this invention, chitosan monomer is very weak to the combination of selenium, is difficult to play controllable sustained-release effect to the selenium of institute's load.
Often need larger dose for serious disease treatment, inorganic selenium drug use dosage control plays curative effect and falls hypotoxic key.Experiment proves that inorganic selenium has cumulative toxicity and mutagenic action, and during practical application, dosage is difficult to accurate control.Magnetic Nano coated with silica inorganic selenium medicine is adopted to be a kind ofly realize the most simple and easy to do mode of inorganic selenium targeting controllable release.
Summary of the invention
The rate of release of targeting controllable release inorganic selenium medicine is determined jointly by the performance of porous nano silica housing with the magnetic ferroferric oxide core of absorption inorganic selenium medicine.Prepare magnetic Nano SiO at present
2method comprise: (1) adds surfactant and Fe in aqueous
3o
4magnetic powder makes template agent, thereon clad nano SiO
2presoma, hydrolysis forms nucleocapsid structure porous nano silica; (2) coated magnetic Fe on porous nano silica
3o
4colloidal sol, (3) prepare Nano-meter SiO_2
2and nanometer Fe
3o
4mixed sols, obtains magnetic medicine carrier after gel.If inorganic selenium pharmaceutical carrier has magnetic, inorganic selenium medicine just can arrive destination organization under the guiding in magnetic field, realizes target administration, avoids other organs of drug damages and improves therapeutic efficiency.
The present invention is directed to the problem of existing magnetic Nano silicon dioxide as the not easily stability contorting of rate of release during inorganic selenium pharmaceutical carrier, adopt inorganic selenium medicine and porous magnetic Fe
3o
4co-precipitation, by inorganic selenium Drug absorbability in magnetic Fe
3o
4surperficial and inner, delay its rate of release; Carry out coated with porous nano silica to inorganic selenium medicine again, thus realize arsenical prolonged drug slow release and controllable release, go back available polyethylene ketopyrrolidine polymeric sol and its biocompatibility is improved to the process of inorganic selenium medical surfaces.The technical scheme that the present invention takes comprises carrying inorganic selenium medicine magnetic Fe
3o
4the preparation of core, nano silicon coated magnetic inorganic selenium medicine with surface treatment three steps of inorganic selenium medicine, concrete implementation step is.
(1) add trivalent iron salt, divalent iron salt and selenite in deionized water, control material molar ratio: Fe
3+: Fe
2+: Se=1:1:0.1-0.5, the strong aqua ammonia adding mass percentage concentration 25% under vigorous stirring regulates solution to make pH be greater than 11, generates the magnetic Fe of carrying inorganic selenium medicine
3o
4core, with the black precipitate that attraction is insoluble, with deionized water wash precipitation 2-3 time, drying precipitated at 105 DEG C, obtain the nano-magnetic Fe of carrying inorganic selenium medicine
3o
4core.
(2) surfactant is added in deionized water, the nano-magnetic Fe of carrying inorganic selenium medicine
3o
4core, the strong aqua ammonia adding mass percentage concentration 25% again regulates pH value of solution to be greater than 11, be heated to 60-80 DEG C, add silester under vigorous stirring, isothermal reaction 0.5-2h, to silester complete hydrolysis, the black precipitate that cooling, filtration are formed, with deionized water wash 2-3 time, obtains the magnetic inorganic selenium medicine that nano silicon is coated, described surfactant is quaternary ammonium salts surfactant, in the solution mass percentage concentration 0.1%-1.0%; Described silester mass percentage concentration 0.5%-5.0% in the solution, material molar ratio: Si:Fe: Se=10-20:1:0.05-0.25.
(3) polyvinylpyrrolidone is dissolved in the clear solution that dehydrated alcohol forms mass percentage concentration 1.0%-5.0%, by magnetic inorganic selenium medicine coated for the nano silicon prepared above dipping wherein, stir or supersound process 0.5-1h, nano silicon is made to be that polyvinylpyrrolidone is coated, macromolecule layer thickness 5-20nm, isolated by filtration precipitates, natural drying obtains magnetic controllable release inorganic selenium medicine, the magnetic inorganic selenium medicine mass percentage concentration 0.5%-5.0% in the solution that described nano silicon is coated.In simulated body fluid, in medicine, inorganic selenium are at 24h release rate 30%-45%, at the release rate 50%-70% of 48h.
The nano-magnetic Fe of carrying inorganic selenium medicine
3o
4the preferred 20-100nm of nuclear diameter, if magnetic core diameter is less than 20nm, then magnetic is too weak too little with drug load; If the diameter of magnetic core is greater than 100nm, then nano effect weakens and to be difficult to drug release behavior control.On silica shell, aperture is preferably 5-20nm, when the aperture on silica shell is less than 5nm, there is drug releasing rate too slow; When the aperture of silica shell is greater than 20nm, then there is drug release efficiency and be difficult to control.The thickness of magnetic core-shell nano silicon shell is preferably 10-50 nm, if the thickness of silica shell is less than 10nm, then drug loading stability reduces; If the thickness of silica shell is greater than 50 nm, then drug releasing rate slowly, and the thickness of silica shell and aperture can be passed through reaction density, time and surfactant concentration and control.The diameter of carrying inorganic selenium medicine magnetic core-shell nano silicon dioxide is preferably 100-300nm.
The selenous total amount of inorganic selenium assay, adopt seleno reagent colour developing colorimetry, i.e. tetravalence selenium and seleno reagent (3 in slightly acidic solution, 3-diaminobenzidine tetrahydrochloride) effect formation yellow complex, in High-pH solution can extract by organic solvents such as benzene, the interference EDTA of ferrum eliminates, its absorbance is surveyed at 420nm place with spectrophotometer, with the standard selenium solution of a series of variable concentrations, working curve is done to absorbance under the same conditions, can inorganic selenium content in calculation sample according to the slope of curve.
The beneficial effect that the present invention obtains is:
(1) the invention solves the problem of existing inorganic selenium drug releasing rate instability, realize long-acting slow-release and controllable release;
(2) inorganic selenium medicine of the present invention has magnetic, can arrive destination organization under the guiding in magnetic field, realizes target administration and improves therapeutic efficiency, can realize facilitating medication and reducing drug side effect.
Detailed description of the invention
Embodiment 1
Take 0.54 gram of ferric chloride [FeC1
36H
2o], 0.78 gram of Ferrous ammonium sulfate [(NH
4)
2fe (SO
4)
2.6H
2o] and 0.17 gram of sodium selenite [NaSeO
3], be dissolved in 50 ml deionized waters, adding 5 ml concentration under strong agitation is the ammonia of 25%, reacts 15 minutes, isolate the magnetic Fe of black by attraction in 50 DEG C of water-baths
3o
4solid, by washed with de-ionized water 3-5 time, drying precipitated at 105 DEG C, obtain the nano-magnetic Fe that particle diameter is the carrying inorganic selenium medicine of 50nm
3o
4core.
Measure 120mL deionized water and be heated to 80 DEG C, under vigorous stirring, add the above nano-magnetic Fe preparing carrying inorganic selenium medicine
3o
4core and 0.6g quaternary ammonium salts surfactant, namely obtain Fe in ultrasonic 10 minutes
3o
4nano sol, adds strong aqua ammonia 3ml and regulates pH value of solution to be greater than 11, add 10mL silester, isothermal reaction 2h at 80 DEG C, to complete hydrolysis, and then cold filtration precipitation, and with deionized water wash, obtain the magnetic inorganic selenium medicine that nano silicon is coated.
1.0g polyvinylpyrrolidone is dissolved in 100ml dehydrated alcohol and forms clear solution, by magnetic arsenic agent medicine coated for the nano silicon secondary prepared above dipping wherein, supersound process 0.5h, be polyvinylpyrrolidone coated, macromolecule layer thickness 10nm, isolated by filtration, natural drying obtains magnetic controllable release inorganic selenium medicine.In simulated body fluid, in medicine, inorganic selenium are at the release rate 45% of 24h, at the release rate 70% of 48h.
Embodiment 2
Take 0.54 gram of ferric chloride [FeC1
36H
2o], 0.78 gram of Ferrous ammonium sulfate [(NH
4)
2fe (SO
4)
2.6H
2o] and 0.04 gram of sodium selenite [NaSeO
3], be dissolved in 50 ml deionized waters, adding 5 ml concentration under strong agitation is the ammonia of 25%, reacts 15 minutes, isolate the Fe of black by attraction in 50 DEG C of water-baths
3o
4solid, by washed with de-ionized water 3-5 time, drying precipitated at 105 DEG C, obtain the nano-magnetic Fe that particle diameter is the carrying inorganic selenium medicine of 50nm
3o
4core.
Measure 120mL deionized water and be heated to 60 DEG C, under vigorous stirring, add the nano-magnetic Fe of the carrying inorganic selenium medicine of above preparation
3o
4core and 0.6g quaternary ammonium salts surfactant, namely obtain Fe in ultrasonic 10 minutes
3o
4nano sol, adds strong aqua ammonia 3ml and regulates pH value of solution to be greater than 11, add 10mL silester, isothermal reaction 2h at 60 DEG C, to complete hydrolysis, then cold filtration precipitation, and with deionized water wash, obtain the magnetic inorganic selenium medicine that nano silicon secondary is coated.
1.0g polyvinylpyrrolidone is dissolved in 100ml dehydrated alcohol and forms clear solution, by magnetic inorganic selenium medicine coated for the nano silicon secondary prepared above dipping wherein, supersound process 0.5h, be polyvinylpyrrolidone secondary coated, macromolecule layer thickness 10nm, isolated by filtration, natural drying obtains magnetic controllable release inorganic selenium medicine.In simulated body fluid, in medicine, inorganic selenium are at 24h release rate 30%, at the release rate 50% of 48h.
Claims (4)
1. a preparation method for targeting controllable release inorganic selenium medicine, is characterized in that preparation process comprises the magnetic Fe of carrying inorganic selenium medicine
3o
4biocompatibility process three steps of the preparation of core, nano silicon coated magnetic inorganic selenium medicine and inorganic selenium medicine.
2. the preparation method of targeting controllable release inorganic selenium medicine according to claim 1, is characterized in that carrying inorganic selenium medicine magnetic Fe
3o
4the preparation process of core is:
(1) add trivalent iron salt, divalent iron salt and selenite in deionized water, control material molar ratio: Fe
3+: Fe
2+: Se=1:1:0.1-0.5;
(2) strong aqua ammonia adding mass percentage concentration 25% under vigorous stirring regulates solution to make pH be greater than 11, generates the magnetic Fe of carrying inorganic selenium medicine
3o
4core;
(3) with the black precipitate that attraction is insoluble, with deionized water wash 2-3 time, drying precipitated at 105 DEG C, obtain the nano-magnetic Fe of carrying inorganic selenium medicine
3o
4core, Fe
3o
4the preferred 20-100nm of nuclear diameter.
3. the preparation method of targeting controllable release inorganic selenium medicine according to claim 1, is characterized in that the step of nano silicon coated magnetic inorganic selenium medicine is:
(1) surfactant is added in deionized water, the nano-magnetic Fe of carrying inorganic selenium medicine
3o
4core, the strong aqua ammonia adding mass percentage concentration 25% again regulates pH value of solution to be greater than 11, be heated to 60-80 DEG C, add silester under vigorous stirring, isothermal reaction 0.5-2h, to silester complete hydrolysis, described surfactant is quaternary ammonium salts surfactant, in the solution mass percentage concentration 0.1%-1.0%; Described silester mass percentage concentration 0.5%-5.0% in the solution, material molar ratio: Si:Fe: Se=10-20:1:0.05-0.25;
(2) cool, filter the black precipitate formed, with deionized water wash 2-3 time, obtain the magnetic inorganic selenium medicine that nano silicon is coated, drug particle diameter is preferably 100-300nm.
4. the preparation method of targeting controllable release inorganic selenium medicine according to claim 1, is characterized in that the biocompatibility treatment step of inorganic selenium medicine is:
(1) magnetic inorganic selenium medicine coated for nano silicon is immersed in the polyvinylpyrrolidone alcoholic solution of mass percentage concentration 1.0%-5.0%, the magnetic inorganic selenium medicine mass percentage concentration 0.5%-5.0% in the solution that nano silicon is coated, stir or supersound process 0.5-1h, nano silicon is made to be that polyvinylpyrrolidone is coated, macromolecule layer thickness 5-20nm;
(2) isolated by filtration precipitation, natural drying, obtains magnetic controllable release inorganic selenium medicine, and in simulated body fluid, in medicine, inorganic selenium are at 24h release rate 30%-45%, at the release rate 50%-70% of 48h.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105079027A (en) * | 2015-08-13 | 2015-11-25 | 上海工程技术大学 | Porous Se-SiO2 nanoparticle as well as preparation method and application thereof |
| CN105850991A (en) * | 2016-01-29 | 2016-08-17 | 华电电力科学研究院 | Preparation method for amino composite magnetic nano bacteria remover |
| CN109908172A (en) * | 2019-03-13 | 2019-06-21 | 常州大学 | A kind of magnetic iron oxide and elemental selenium Nano Composite Particles and its preparation method and application |
| CN111213789A (en) * | 2020-01-09 | 2020-06-02 | 四川吉隆达生物科技集团有限公司 | Nano selenium feed additive and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101693011A (en) * | 2009-08-13 | 2010-04-14 | 苏州纳米技术与纳米仿生研究所 | Preparation method of magnetic medicine-carrying nano-particle |
-
2014
- 2014-09-14 CN CN201410464117.5A patent/CN104306969A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101693011A (en) * | 2009-08-13 | 2010-04-14 | 苏州纳米技术与纳米仿生研究所 | Preparation method of magnetic medicine-carrying nano-particle |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105079027A (en) * | 2015-08-13 | 2015-11-25 | 上海工程技术大学 | Porous Se-SiO2 nanoparticle as well as preparation method and application thereof |
| CN105079027B (en) * | 2015-08-13 | 2017-12-29 | 上海工程技术大学 | A kind of porous Se SiO2Nano-particle and its preparation method and application |
| CN105850991A (en) * | 2016-01-29 | 2016-08-17 | 华电电力科学研究院 | Preparation method for amino composite magnetic nano bacteria remover |
| CN109908172A (en) * | 2019-03-13 | 2019-06-21 | 常州大学 | A kind of magnetic iron oxide and elemental selenium Nano Composite Particles and its preparation method and application |
| CN111213789A (en) * | 2020-01-09 | 2020-06-02 | 四川吉隆达生物科技集团有限公司 | Nano selenium feed additive and preparation method thereof |
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