CN105125499B - A kind of preparation process of interventional treatment magnetic steering pharmaceutical carrier - Google Patents
A kind of preparation process of interventional treatment magnetic steering pharmaceutical carrier Download PDFInfo
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- CN105125499B CN105125499B CN201510615368.3A CN201510615368A CN105125499B CN 105125499 B CN105125499 B CN 105125499B CN 201510615368 A CN201510615368 A CN 201510615368A CN 105125499 B CN105125499 B CN 105125499B
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Abstract
The invention discloses a kind of preparation processes of interventional treatment magnetic steering pharmaceutical carrier, belong to a kind of interventional treatment carrier, it is characterised in that：NaOH、FeCl3·6H2O、FeCl2·4H2O molar ratios are OH‑：Fe3+：Fe2+=8.0：1.0~1.8：1.0, it first takes sodium hydroxide starch gelatinization to mix, mixing ferrous solution is then added dropwise in being gelatinized mixed liquor, is reacted in pyroreaction kettle under inert atmosphere, 180~240 DEG C, keeps the temperature 6~10h, is washed after Temperature fall, is dried to obtain carbon coating type ferroso-ferric oxide.Compared with prior art, the present invention solves the defects of traditional targeted therapy is complicated with magnetic-particle carrier cladding process, and production cost is high, and product property is unstable.
Description
Technical field
The present invention relates to interventional treatment carriers, especially a kind of preparation side for interventional treatment magnetic steering pharmaceutical carrier
Method.
Background technology
Interventional treatment is the main method of non-operative treatment primary carcinoma of liver, includes mainly transcatheter arterial chemoembolization
(TACE).Current TACE operations are mostly that the mixed emulsion of chemotherapeutics and lipiodol is directly injected into the confession of tumour by conduit
Blood is intravascular, and while blood supply, the induced tumor necrosis for blocking tumour, the chemotherapeutics slow release in suppository continues
Kill tumour to property.With the continuous improvement of " neoplasm targeted therapy " technology, " medicine microspheres embolism " progresses into clinical practice
In, it is more complete to the embolism of tumour capillary network after medicine microspheres inject supply artery of the tumor by arterial cannulation, and it is normal
Rule suppository, which is compared, to be less susceptible to form offshoot circulation, and cancerous tissue necrosis is more thorough, embolism effect can be both generated, but also as anticancer
The carrier of drug makes the drug of tumor area maintain higher concentration level for a long time.But merely by interventional method for " medicine
The guiding of object microballoon ", complicated for operation, grasp is constant, in recent years, and puts forward intervention cooperation magnetic steering and increases drug targeting performance
Therapeutic scheme, i.e., injected near tumor area by intervening magnetic nanoparticle volume is small, with superparamagnetism, then
Outer introduction by magnetic field (such as：Nuclear magnetic resonance) under, it will be oriented to and limit with drug or without the magnetic nanoparticle of drug
To tumor area capillary network, magnetic thermotherapy, targeted chemotherapy, radiotherapy and thermochemotherapy, hot radiotherapy etc. further can be achieved, play treatment
Maximum effect and reduce side effect.
It is more extensive to the research of ferromagnetic material in numerous magnetic materials, and with four oxygen of nanometer in ferromagnetic material
Change three-iron (Fe3O4) research is most universal, biocompatibility is good, without spies such as hemolytic activity, genetoxic and superparamagnetism
Property, it is a kind of good interventional treatment magnetic steering pharmaceutical carrier.But in practical application, generally require magnetic nanoparticle ruler
It is very little it is uniform, chemical property is stable, biocompatibility and good dispersion.Due to the special construction of magnetic ferroferric oxide nano-particles
It determines that its own dispersibility is poor, is easy to happen reunion, it is difficult to long-time stable suspends in the solution, and in air
The defect that cannot be stabilized in recent years, advocate to carry out cladding processing more.Carbon geochemistry property is stablized, the nanometer under carbon coating
Grain has bioaffinity and unique spectral characteristic, is acknowledged as ideal covering material.Since carbon shell can be in very little
Space confine metallics, can avoid influence of the environment to nano material, reduce interparticle interaction, therefore solve
The problem of magnetic ferroferric oxide nano-particles are easily reunited and cannot be stabilized in air.Additionally, due to depositing for carbon coating layer
, the compatibility between magnetic ferroferric oxide and organism is improved, thus carbon-coated magnetic ferriferrous oxide nanometer material exists
It has broad application prospects in terms of medicine.
The carbon coating Fe that domestic and foreign literature is reported at present3O4The synthetic method of magnetic microsphere is essentially all using two steps
Or multistep processes synthesis, it is substantially all including two steps：I.e. first synthesizing magnetic microballoon, then uses carbon-coated magnetic microballoon.And
Fe3O4Among magnetic microsphere preparation process, in order to control microballoon size, if it has to abandon simple direct synthesis method, and adopt
With the methods of pyrolysismethod, reversed coprecipitation, such as《The preparation method of magnetic carbon-coated ferroferric oxide nano-composite material》(Shen
Please number：201110303081.9) disclosed in：Granular size is controlled by adjusting reaction temperature and addition surfactant.
The mechanism of addition surfactant (SAA) is using SAA components in the amphipathic by one end functional group of interface (surface)
" bridge " is formed between absorption or reaction and CNTs, between CNTs microparticle surfaces, between CNTs particles and other materials, plays coupling
With the effect of increase-volume.After SAA surface modification treatments, CNTs shows dispersibility and machinability well, above-mentioned, but in base
Because of therapy field in use, needing drug and high molecular material to combine, the Fe being modified using SAA3O4Magnetic microsphere, 1. its is right
There is negative effect in the viscosity of polymer, is unfavorable for the combination and attachment of drug；2. whether to verify SAA and pharmaceutical activity repeatedly
Conflict, Fe modified same SAA3O4Magnetic microsphere can not be used for all pharmaceutical carriers；3. fully to assess surface-active
The toxicity in vivo of agent makes scrupulous selection；4. it is higher that SAA is modified cost.To sum up, step it is more, cannot safety reduction synthesized
" particle aggregation " in journey is the maximum disadvantage of current synthetic method.
Invention content
The technical assignment of the present invention is to be directed to the above the deficiencies in the prior art, provide it is a kind of it is easy to operate, production cost is low
Interventional treatment magnetic steering pharmaceutical carrier preparation process.
The present invention the technical solution to solve the technical problem is that：A kind of preparation work of interventional treatment magnetic steering pharmaceutical carrier
Skill, it is characterised in that：Preparation method comprises the following steps that：
(1) starch will be added in the NaOH solution of 1.0~1.3mol/L of molar concentration, stirring forms mixed liquor to being gelatinized；
Mixed liquor is added in reaction kettle, reaction kettle is sealed, reaction kettle is purged by intake valve using high pure nitrogen, is discharged internal empty
Gas；
(2) according to molar ratio OH-：Fe3+：Fe2+=8.0：1.0~1.8：1.0, weigh FeCl3·6H2O、FeCl2·4H2O
It is dissolved in deoxidation pure water respectively, and is uniformly mixed to obtain mixed liquor；
(3) gained is mixed in sodium hydroxide starch gelatinization mixed liquor a dropping step (2) obtained by as inlet valve into step (1)
Close liquid；Reaction kettle is warming up to 180~240 DEG C, keeps the temperature 6~10h, after Temperature fall, is washed, it is dry, obtain carbon-coated nano
Magnetic ferroferric oxide.Starch addition in above-mentioned steps (1) is that 10.0~20.0g of starch is added per moles of NaOH.
Compared with prior art, the present invention has advantageous effect following prominent：
1, using method of the present invention production carbon-coated nano Fe3O4Material, by carbon coating process conformity in Fe3O4Generation
Cheng Zhong, rather than in Fe3O4Generating process after, simplify technological process, save time and cost.
2, NaOH and starch mixed solution are subjected to gelatinization processing first, increase solution viscosity, adds iron ion, ferrous iron
Solion, iron ion, ferrous ion are wrapped up by gelatinization solution environmental, OH—It reacts and slows down with iron ion, ferrous ion, most
The particle size (＜ 100nm) and agglomeration for generating ferroso-ferric oxide are inhibited eventually, improves the dispersibility of final product, are reduced
Final product particle size improves the performance of material.
3, impurity F e2O3Content is small, and finished product stable quality effect is good.
4, carbon coating temperature is low, and high degree reduces production cost.
Description of the drawings
Fig. 1 is carbon coating of embodiment of the present invention Fe3O4Scanning electron microscopic picture.
Specific implementation mode
With reference to the accompanying drawings of the specification with specific implementation mode to the present invention into explanation.
Comparative example：
(1) 0.2 mole of FeCl is weighed respectively first3·6H2O, 0.1 mole of FeCl2·4H2O is dissolved in 0.3L deoxidation pure water,
It stirs and evenly mixs, forms the solution of mixing.
(2) solution made from step (1) is added in reaction kettle, seals reaction kettle, passes through air inlet using high pure nitrogen
Valve purges reaction kettle, and inner air is discharged.
(3) 0.8 moles of NaOH is weighed again, is dissolved in the solution that deoxidation pure water forms 1.0mol/L, and stirring and dissolving passes through charging
Sodium hydroxide solution is added dropwise into iron-containing liquor for valve.The proportioning that substance is wherein added is molar ratio Fe3+：Fe2+：OH—=2.0：
1.0：8.0, reaction kettle is warming up to 150 DEG C, keeps the temperature 6h, after Temperature fall, is washed, it is dry, obtain initial product.
(4) again by initial product and 23g glucose mixings, under the conditions of nitrogen protection, 500 DEG C of heat preservation 6h are to get to carbon packet
Cover ferroso-ferric oxide.
Embodiment 1：
(1) 8 moles of NaOH are weighed, is dissolved in deoxidation pure water, forms the solution of 1.3mol/L, 110g water solubilitys are added and form sediment
Powder stirs at 25 DEG C to being completely dissolved；Form mixed liquor；Mixed liquor is added in reaction kettle, reaction kettle is sealed, use is high-purity
Nitrogen purges reaction kettle by intake valve, and inner air is discharged；Occur since soluble starch is added in the NaOH solution of heat
Gelatinization reaction, intragranular starch molecule to all directions stretch spread, dissolve out granule outside, spread come starch molecule between
It can mutually be linked, wind, form one and netted contain hydrocolloid.It is molten when starch enters the particle disintegration stage of gelatinization reaction
Fluid viscosity is maximum, and starch molecule is enable to be coated on around NaOH, it is suppressed that NaOH reacts speed with iron ion, ferrous ion
Degree, and the Fe for inhibiting the two to generate3O4Particle size and agglomeration, improve the dispersibility of final product, reduce final
Product particle size；
(2) 1.8 moles of FeCl are weighed3·6H2O, 1 mole of FeCl2·4H2O is dissolved in deoxidation pure water and forms mixed solution；Its
Contain 1.8mol Fe in a concentration of every liter of solution3+With 1.0mol Fe2+。
(3) mixed as obtained by inlet valve a dropping step (2) into sodium hydroxide starch gelatinization solution obtained by step (1)
Close liquid.The raw material proportioning being wherein added is molar ratio OH—：Fe3+：Fe2+=8：1.8：1, reaction kettle is warming up to 210 DEG C, heat preservation
7h after Temperature fall, is washed, dry, obtains carbon-coated nano magnetic Fe3O4。
Conventional preparation techniques mostly use OH-：Fe3+：Fe2+=8：2：1 this equation ideal theory ratio, but existing
In real technique, Fe2+Property is unstable, is easy to be oxidized to Fe3+。Fe3+：Fe2+=2：When 1, impurity F e often will produce2O3, influence
Finished product quality.
Large viscosity after being gelatinized due to soluble starch aqueous solution, it is suppressed that the Fe that NaOH is generated with iron3O4Particle size with
And agglomeration, Fe3O4Granularity it is smaller.And the starch solution being gelatinized is in Fe3O4Generating process in complete carbon coating, simplify
Technological process saves time and cost, more energy saving.
The iron chloride of processing step (2), or other trivalent ferrous solutions, such as ferric nitrate, ferric sulfate, it is therein
Frerrous chloride, or other ferrous solutions, such as ferrous nitrate, ferrous sulfate.
In the present embodiment, use water soluble starch, so-called water soluble starch and soluble starch difference lies in,
Water soluble starch can be dissolved in cold water and be gelatinized, i.e., can dissolve between 15 DEG C to 25 DEG C, but in actually groping, energy at 25 DEG C
Enough obtain better pasting effect.
Embodiment 2：
(1) 2 moles of NaOH are weighed, is dissolved in deoxidation pure water, is formed the solution of 1.0mol/L, after being heated to 60 DEG C, add
Enter 40g soluble starches, stirring forms mixed liquor to complete gelatinization；Mixed liquor is added in reaction kettle, reaction kettle is sealed,
Reaction kettle is purged by intake valve using high pure nitrogen, inner air is discharged；
(2) 0.25 mole of FeCl is weighed3·6H2O, 0.25 mole of FeCl2·4H2It is molten that O is dissolved in deoxidation pure water formation mixing
Liquid；Contain 1.0mol Fe in its a concentration of every liter of solution3+With 1.0mol Fe2+。
(3) gained in the sodium hydroxide starch gelatinization solution a dropping step (2) obtained by as inlet valve into step (1)
Mixed liquor.It is molar ratio OH that raw material proportioning, which is wherein added,—：Fe3+：Fe2+=8.0：1.0：1.0, reaction kettle is warming up to 180 DEG C,
10h is kept the temperature, after Temperature fall, is washed, it is dry, obtain carbon-coated nano magnetic Fe3O4。
In the present embodiment, the soluble starch used, soluble starch is not soluble in water at normal temperatures, but when water temperature is to 53 DEG C
When above, soluble starch swelling, division form homogeneous paste solution.53 DEG C of theoretical gelatinization points for starch, but due to
The difference of initial starch material, gelatinization point are varied from, and aqueous solution gelatinization point is between 53~72 DEG C, described in technique
Soluble starch be dissolved in the NaOH solution of 1.0mol/L, high alkalinity causes gelatinization point to decline, and corn forms sediment at 60 DEG C
Powder, tapioca, potato starch, sweet potato starch, wheaten starch, polished rice starch, barley starch, glutinous rice starch, buckwheat starch,
Sweet potato starch can be gelatinized completely, prevent from, due to excessive temperature, causing that reaction is caused to add in subsequently synthesizing since temperature is excessively high
Speed, agglutination accelerate.
Embodiment 3：
(1) 8 moles of NaOH are weighed first, are dissolved in deoxidation pure water, are formed the solution of 1.2mol/L, be added at 40 DEG C
80g pre-gelatinized starches, stirring is to being completely dissolved；Ultrasonic mixing, ultrasound make the air being present in mixed liquor under 200Hz frequencies
Bubble shakes under sound wave effect, and growth occurs when reaching certain limit and cavitation is played in collapse, is turned into using ultrasonic air
With making NaOH be uniformly mixed with starch molecule in solution and control starch granules size, be evenly distributed.Mixed liquor is added to
In reaction kettle, reaction kettle is sealed, reaction kettle is purged by intake valve using high pure nitrogen, inner air is discharged；
(2) 1.5 moles of FeCl are weighed3·6H2O, 1 mole of FeCl2·4H2O is dissolved in deoxidation pure water and forms mixed liquor；Its is dense
Degree is to contain 1.5mol Fe in every liter of solution3+With 1.0mol Fe2+。
(3) as inlet valve to the mixing obtained by the sodium hydroxide starch gelatinization solution a dropping step (2) obtained by step (1)
Liquid.It is molar ratio OH that raw material proportioning, which is wherein added,—：Fe3+：Fe2+=8：1.5：1, reaction kettle is warming up to 240 DEG C, keeps the temperature 6h,
After Temperature fall, wash, it is dry, obtain carbon-coated nano magnetic Fe3O4。
Pre-gelatinized starch is a kind of converted starch, as long as being tuned into paste with cold water when application, eliminates the trouble of Heat Gelatinization.
But in actually groping, better pasting effect can be obtained at 40 DEG C, and be superimposed more preferably with ultrasonic effect at such a temperature.
Comparative example, embodiment 1, embodiment 2,3 test result of embodiment show comparative example, embodiment 1,2,3 product
Yield is respectively 40.78%, 67.23%, 68.27%, 73.42%, and the yield of each embodiment is can be seen that from product yield
It is apparently higher than the yield using the carbon-coated comparative example of high temperature after reversed coprecipitation；1000 DEG C of simultaneous thermal analysis results of final temperature are aobvious
Show：Comparative example, 1,2,3 residuals content of embodiment are respectively 20.25%, 28.31%, 27.24%, 30.12%, 1000 DEG C of heat
Residual product is Fe after weightlessness2O3, Fe is gone out by Fe mass balance calculations3O4Content is respectively：Comparative example 29.36%；Embodiment
1 is 41.05%；Embodiment 2 is 39.50%；Embodiment 3 is 43.67%；The content balance that carbon is calculated is carried out by yield
Example, embodiment 1,2,3 are respectively 11.42%, 26.18%, 28.77%, 29.77%, it can be seen that embodiment 1,2,3 is pure
Degree is big, content is high, carbon coating effect is better than comparative example.
Fig. 1 is the scanning electron microscopic picture of this programme embodiment 2, as seen from the figure carbon obtained through the embodiment of the present invention
Coat nanometer Fe3O4Particle soilless sticking, pattern is uniform, even particle size distribution<100nm.
It should be noted that the present invention particular embodiment to the present invention have been described in detail, for ability
For the technical staff in domain, its various of progress is obviously changed without departing from the spirit and scope of the present invention
Become all within protection scope of the present invention.
Claims (4)
1. a kind of preparation process of interventional treatment magnetic steering pharmaceutical carrier, it is characterised in that：Preparation method includes following technique
Step：
(1) starch will be added in the NaOH solution of 1.0~1.3mol/L of molar concentration, stirring forms mixed liquor to being gelatinized；It will mix
It closes liquid to be added in reaction kettle, seals reaction kettle, reaction kettle is purged by intake valve using high pure nitrogen, inner air is discharged；
(2) according to molar ratio OH-：Fe3+：Fe2+=8.0：1.0~1.8：1.0, weigh FeCl3·6H2O、FeCl2·4H2O distinguishes
It is dissolved in deoxidation pure water, and is uniformly mixed to obtain mixed liquor；
(3) gained mixing in sodium hydroxide starch gelatinization mixed liquor a dropping step (2) obtained by as inlet valve into step (1)
Liquid；Reaction kettle is warming up to 180~240 DEG C, keeps the temperature 6~10h, after Temperature fall, is washed, it is dry, obtain carbon-coated nano magnetic
Property ferroso-ferric oxide.
2. a kind of preparation process of interventional treatment magnetic steering pharmaceutical carrier according to claim 1, it is characterised in that：It is described
Starch addition in step (1) is that 10.0~20.0g of starch is added per moles of NaOH.
3. a kind of preparation process of interventional treatment magnetic steering pharmaceutical carrier according to claim 1, it is characterised in that：It is described
Trivalent iron salt in step (2) is one kind in ferric sulfate, ferric nitrate or iron chloride.
4. a kind of preparation process of interventional treatment magnetic steering pharmaceutical carrier according to claim 1, it is characterised in that：It is described
Divalent iron salt in step (2) is one kind in ferrous sulfate, ferrous nitrate, iron ammonium sulfate or frerrous chloride.
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| CN201810505207.2A CN108653235B (en) | 2015-09-24 | 2015-09-24 | Preparation process of carbon-coated magnetic guiding drug carrier |
| CN201510615368.3A CN105125499B (en) | 2015-09-24 | 2015-09-24 | A kind of preparation process of interventional treatment magnetic steering pharmaceutical carrier |
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| CN201510615368.3A CN105125499B (en) | 2015-09-24 | 2015-09-24 | A kind of preparation process of interventional treatment magnetic steering pharmaceutical carrier |
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| CN108815566A (en) * | 2018-09-20 | 2018-11-16 | 黄旭东 | A kind of preparation method of porous hemostatic starch |
| CN110212192A (en) * | 2019-06-25 | 2019-09-06 | 河南大学 | A kind of adjustable nano ferriferrous oxide composite material and preparation method of cladding carbon layers having thicknesses and application |
| CN110931751B (en) * | 2019-12-06 | 2022-03-18 | 怀化学院 | Carbon-ferroferric oxide composite material and preparation method and application thereof |
Citations (4)
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|---|---|---|---|---|
| CN1554727A (en) * | 2003-12-21 | 2004-12-15 | 大连理工大学 | Method for preparing carbon coated nano metal material using biological material-starch as substrate |
| CN102323311A (en) * | 2011-09-01 | 2012-01-18 | 聊城大学 | Guanine derivative possessing magnetism by taking graphene as carrier, its synthetic method and its application |
| CN102786097A (en) * | 2012-07-26 | 2012-11-21 | 天津大学 | Hydrothermal preparation method for carbon cladded nanometer ferriferrous oxide particles |
| CN103606654A (en) * | 2012-12-21 | 2014-02-26 | 燕山大学 | Method for preparing carbon-coated manganite composite material |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| KR100637275B1 (en) * | 2005-01-28 | 2006-10-23 | 한국지질자원연구원 | Preparation of nano size Iron oxide for MRI contrast agent by ultrasonic and manufaturing method thereof and manufaturing method of MRI contrast agent using Iron oxide nano particle and MRI contrast agent thereof |
| CN104001474A (en) * | 2014-05-20 | 2014-08-27 | 江苏大学 | Carbon-coated ferroferric oxide core-shell nano particle and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1554727A (en) * | 2003-12-21 | 2004-12-15 | 大连理工大学 | Method for preparing carbon coated nano metal material using biological material-starch as substrate |
| CN102323311A (en) * | 2011-09-01 | 2012-01-18 | 聊城大学 | Guanine derivative possessing magnetism by taking graphene as carrier, its synthetic method and its application |
| CN102786097A (en) * | 2012-07-26 | 2012-11-21 | 天津大学 | Hydrothermal preparation method for carbon cladded nanometer ferriferrous oxide particles |
| CN103606654A (en) * | 2012-12-21 | 2014-02-26 | 燕山大学 | Method for preparing carbon-coated manganite composite material |
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