CN104587489A - Halloysite nanotube drug sustained-release material and preparation method thereof - Google Patents
Halloysite nanotube drug sustained-release material and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a halloysite nanotube drug sustained-release material and a preparation method thereof. The drug sustained-release material is prepared by the following steps: performing acid corrosion to a halloysite nanotube to obtain a dilated nanotube, loading the drug into an inner cavity of the halloysite nanotube, and coating an organosilane polymerized hydrophobic layer onto the surface of the drug-carried halloysite nanotube, wherein the during the coating of the organosilane polymerized hydrophobic layer, organosilane I is firstly used for modifying the outer surface of the halloysite nanotube, and then organosilane II is added to form the organosilane polymerized hydrophobic layer on the surface of the nanotube. Compared with the prior art, the sustained release material has universality on a hydrophobic drug and a hydrophile drug, the drug release time can be effectively prolonged, the encapsulation efficiency is high, and the administration safety of the drug can be improved.
Description
Technical field
The invention belongs to Thermosensitive Material Used for Controlled Releasing of Medicine field, be specifically related to a kind of halloysite nanotubes Thermosensitive Material Used for Controlled Releasing of Medicine and preparation method thereof.
Background technology
In recent years, China's slow releasing pharmaceutical used and presented steady-state growth situation always.Release/controlled release preparation is one of clinical commonly used drug dosage form, because slow releasing preparation has the compliance that can reduce and take number of times, improve patient, blood concentration fluctuation is less, route of administration variation, the advantages such as zest is little and curative effect lasting, safety, so a lot of medicine is all attempted to be developed to slow releasing preparation, make it to become the research project that pharmacy corporation has very large practical value.Slow-release material is conducive to improving curative effect of medication, reducing toxic and side effects, can alleviate the misery of patient's repeatedly medication, is significant for raising clinical application level.
Bio-pharmaceutical slow release macromolecular material mainly natural polymer, semi-synthetic macromolecule, the synthesis macromolecule of " printing during chemical industry " (2013,27 (9): 5-8) exploitation at present.Wherein CNT, chitosan, sodium alginate and polylactic acid etc. are current more materials of applying in drug controlled release system, have in report and utilize water soluble polymer sodium alginate to modify the CNT of encapsulating oxaliplatin to improve the biocompatibility of CNT, obtain oxaliplatin-sodium alginate-multi-walled carbon nano-tubes complex, result proves to play good medicament slow release effect." Jiangsu's agriculture science " (2013,41 (7): 299-302) reporting with oxaliplatin is the feasibility of model drug research multi-walled carbon nano-tubes as slow-released carrier, by water soluble polymer moditied processing carboxylic carbon nano-tube (MWCNT COOH), improve its surface nature, result shows the oxaliplatin-chitin-sodium alginate-multi-walled carbon nano-tubes complex obtained, and slow release effect is good." chemistry and biological engineering " (2014,31 (2): 35-37) employing emulsion-solvent evaporation method is reported, with Biodegradable material polylactic acid for carrier, add pharmaceutical grade azithromycin and a certain amount of nano ferriferrous oxide wherein to prepare polylactic acid/nano ferroso-ferric oxide and carry Azithromycin slow-release microsphere, result shows that microsphere has obvious medicament slow release effect.But although above-mentioned complex all can play certain slow release effect, it only can be used in the slow release of certain specific medicine, does not have universality.
In addition, although current more existing slow releasing pharmaceutical products, its still exist envelop rate lower, absorb the problems such as limited, the quality of the pharmaceutical preparations is unstable, the more difficult control of dosage.And its cost prepared is high, the complicated operation of preparation process.
Summary of the invention
The object of the present invention is to provide a kind of for hydrophobic drug and hydrophilic medicament have universality, can effective high, the halloysite nanotubes Thermosensitive Material Used for Controlled Releasing of Medicine that improves drug administration safety of prolong drug release time, envelop rate.
Another object of the present invention is to provide a kind of preparation method of simple to operate, above-mentioned slow-release material that cost is low.
Technical scheme of the present invention:
A kind of halloysite nanotubes Thermosensitive Material Used for Controlled Releasing of Medicine, this Thermosensitive Material Used for Controlled Releasing of Medicine is by carrying out acid corrosion with after the nanotube obtaining dilatation by halloysite nanotubes, by drug loading in halloysite nanotubes inner chamber, the halloysite nanotubes Surface coating organosilan polymerization hydrophobic layer after medicine carrying obtains; Wherein, in coated organic polymerizable silane hydrophobic layer process, organo silane coupling agent I pair of halloysite nanotubes outer surface is first used to modify, add organo silane coupling agent II again, thus form organic polymerizable silane hydrophobic layer at halloysite nanotubes Surface coating, organo silane coupling agent I is tetraethoxysilane, and organo silane coupling agent II is selected from one or more in n-octytriethoxysilane, hexadecyl, VTES.
The organosilan polymerization hydrophobic layer thickness of above-mentioned formation is 20 ~ 50nm.
The preparation method of above-mentioned slow-release material, comprises the following steps:
(1) corrosion of halloysite nanotubes
Galapectite powder dilute acid soln corrodes, and washing, drying, obtain the dilatation halloysite nanotubes of inner wall section corrosion;
(2) drug loading
To treat that the medicine dissolution of load is in solvent, be then soaked in above-mentioned solution by the halloysite nanotubes of dilatation, guarantee system is in vacuum environment, and cleaning, drying obtain medicine carrying halloysite nanotubes;
(3) hydrophobic layer is modified
A, medicine carrying halloysite nanotubes solvent to be dissolved, add organo silane coupling agent I and at 30 ~ 70 DEG C, halloysite nanotubes outer surface is modified;
B, by modify after halloysite nanotubes be scattered in solvent, add organo silane coupling agent II and form organic polymerizable silane hydrophobic layer in halloysite nanotubes Surface coating at 90 ~ 130 DEG C;
Wherein, organo silane coupling agent I is tetraethoxysilane, and organo silane coupling agent II is selected from one or more in n-octytriethoxysilane, hexadecyl, VTES.
In (3) step, the mass ratio of medicine carrying halloysite nanotubes and organo silane coupling agent I is 1:2.0 ~ 5.0.
In (3) step, in every 1g medicine carrying halloysite nanotubes, add 5 ~ 20mL ammonia.
In (3) step, the mass ratio of the halloysite nanotubes after modification and organo silane coupling agent II is 1:2.5 ~ 7.0.
In (2) step, the mass ratio of halloysite nanotubes and medicine is 1:0.5 ~ 5.
Medicine of the present invention preferably includes as ibuprofen, diclofenac sodium or ofloxacin.
Acid in acid corrosion of the present invention is dilute acid soln, and concentration is preferably 1.0 ~ 5.0mol/L.
Olefin(e) acid solution is preferably dilution heat of sulfuric acid.
The medicine carrying time of halloysite nanotubes is that 24 ~ 48h is advisable.
One or more in described solvent preferred alcohol, isopropyl alcohol, toluene or cyclohexane extraction.
Beneficial effect of the present invention
The present inventor is low for the universality for the slow-release material in medicine in prior art, cost is high, the present situation of the not good grade of slow release effect, provide a kind of, for hydrophobic drug and hydrophilic medicament, there is universality, cost is low, envelop rate is high, the quality of the pharmaceutical preparations is stablized, dosage easily controls, can effectively prolong drug release time, improve the halloysite nanotubes Thermosensitive Material Used for Controlled Releasing of Medicine of coated organic polymerizable silane hydrophobic layer of drug administration safety.Concrete, slow-release material of the present invention is raw material by choosing halloysite nanotubes, first carries out acid corrosion to obtain the nanotube of dilatation to halloysite nanotubes, is loaded among inner chamber afterwards by medicine, obviously increases drug loading to reach more high-drug-effect; Secondly by first using specific organosilan I pair of halloysite nanotubes outer surface to modify, add specific organosilan II again and form organic polymerizable silane hydrophobic layer in nanotube surface, control the thickness degree of hydrophobic layer, reach desirable sustained drug release effect.
The present invention selects the galapectite after corrosion as slow releasing carrier material, also carries out hydrophobic layer modification, is combined by hydrophobic layer and jointly applies to slow release, obtain good slow release effect with galapectite.By corroding the nano material of the dilatation inner chamber obtained, improve envelop rate.As can be seen from the TEM figure of Fig. 1, in a figure, the cavity inside diameter of original halloysite nanotubes is that the galapectite obtained after corrosion in 10-15nm, b figure carries out medicine carrying, and internal diameter expands as 25-35nm.Visible, the galapectite material after corrosion can improve entrapment efficiency really.
Using modification galapectite material as nano drug-carrying material in the present invention, not only can make the route of administration of medicine and administering mode variation, thus provide more selection for the preparation in future.And nano drug-carrying material of the present invention has the absorption increasing medicine, improve the advantage of the bioavailability of medicine, pharmaceutically-active time lengthening can be made, be conducive to increasing medicine and absorption site biofilm contact area, obviously increase and improve absorption and the bioavailability of medicine.For the treatment of some disease, general drug metabolism is fast, the repeated multiple times administration of need, and increases complication odds, and the present invention solves this difficult problem effectively.The present invention, by forming the environment comparatively closed, enhances the stability of medicine factor to external world.The biological stability of medicine is enhanced, and medicine can keep the integrity of its structure before arriving site of action, thus improves the biological activity of medicine.
When drug level of the present invention is 50mg/ml, drug loading can reach 150mg/g.
And preparation method of the present invention is simple, cost is low, the excellent performance of the slow-release material prepared.
Accompanying drawing explanation
Fig. 1 is the transmission electron microscope picture after the halloysite nanotube medicine carrying that obtains of embodiment 1 and surface modification are modified.Wherein, the halloysite nanotubes that Fig. 1 (a) is cavity, Fig. 1 (b) is the halloysite nanotubes after medicine carrying, and Fig. 1 (c) is for being covered with the halloysite nanotubes material of organosilan polymerization hydrophobic layer; Can find out from a, b figure, medicine is successfully loaded in halloysite nanotube inner chamber, and the obvious internal diameter expansion of the halloysite nanotube after corrosion improves drug loading; As can be seen from c figure, after organosilan polymerization hydrophobic layer is successfully coated on medicine carrying, halloysite nanotubes is surperficial.
Fig. 2 is the medicament slow release performance figure of the halloysite nanotubes material that embodiment 4 obtains.
Fig. 3 is the medicament slow release performance figure of the halloysite nanotubes material that embodiment 1 obtains.
Fig. 4 is the medicament slow release performance comparison diagram of the halloysite nanotubes material that embodiment 1 and comparative example 3 obtain.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is described in detail.
Embodiment 1
(1) corrosion of halloysite nanotubes (HNTs)
Get 4g galapectite powder dispersion in the dilution heat of sulfuric acid of 200mL 3mol/L, after ultrasonic disperse, magnetic agitation 12h in 70 DEG C of water-baths, with a large amount of distilled water wash to neutral, vacuum 60 DEG C of dryings, obtain the dilatation halloysite nanotubes of inner wall section corrosion.
(2) load of ibuprofen (IBU)
Get 1g Ibuprofen samples and be placed in conical flask, dissolved completely with the ethanol of 40mL, then add the halloysite nanotubes ultrasonic disperse of the dilatation of 1g, and guarantee system is in vacuum environment, constant temperature oscillation 24h is to reach the object of drug loading, complete with the cleaning of second alcohol and water, vacuum drying obtains HNTs-IBU.
(3) hydrophobic layer is modified
A, the solvent (ethanol: water=4:1) of the HNTs-IBU 200mL of 0.5g is carried out ultrasonic dissolution, 8.335mL ammonia is added after a while half an hour in 45 DEG C of magnetic agitation, later add 1.75g tetraethoxysilane (TEOS), whole reaction system is in 45 DEG C of water-bath 12h.After having reacted, extremely neutral with the cleaning of second alcohol and water respectively, centrifugal, vacuum drying obtains HNTs-IBU TEOS.
B, get 0.5g HNTs-IBU@TEOS ultrasonic disperse in the dry toluene of 25mL, add n-octytriethoxysilane (OTES) back flow reaction 24h in 90 DEG C of oil baths of 2.32g.After having reacted, respectively by ethanol and toluene cleaning extremely neutrality, centrifugal, vacuum drying obtains HNTs-IBU@TEOS@OTES.Such organosilan polymerization hydrophobic layer is just formed at halloysite nanotubes surface.
(4) external sustained release performance
The external slow release behavior of HNTs-IBU@TEOS@OTES nano-tube support material is carried out in dissolving-out tester, the nano material of 0.4g is infiltrated in the pH 7.4PBS buffer solution of 500mL, 100rpm/min, 37 DEG C, in a certain time interval, get the release liquid of 1.0mL respectively, and fill into the fresh pH 7.4PBS buffer solution of 1.0mL, the solution taken out is passed through the nylon leaching film of 0.45 μm, then by its concentration of ultraviolet determination.
Comparative example 1
In embodiment 1, (3) step hydrophobic layer is modified and is only selected single organosilan to carry out modification to halloysite nanotubes, operate as follows: get 0.5g HNTs-IBU ultrasonic disperse in the dry toluene of 25mL, add n-octytriethoxysilane (OTES) back flow reaction 24h in 90 DEG C of oil baths of 2.32g.
The nano-particle obtained after bearing reaction completes aggregates into the large bulk of viscosity.
Comparative example 2
In embodiment 1, (3) step hydrophobic layer is modified in a step and the temperature 45 C of use is changed to 20 DEG C, it is as follows that all the other modes according to a step carry out operation: get and the solvent of the HNTs-IBU 200mL of 0.5g (ethanol: water=4:1) is carried out ultrasonic dissolution, 8.335mL ammonia is added after a while half an hour in 20 DEG C of magnetic agitation, later add 1.75g tetraethoxysilane (TEOS), whole reaction system is in 20 DEG C of water-bath 12h.Having reacted rear discovery product sticks on bottle wall mostly, and centre is milky solvent, cannot clean.
Comparative example 3
In being modified by (3) step hydrophobic layer in embodiment 1, the portfolio ratio of organosilan is changed to m (OTES): m (HNTs-IBU@TEOS)=8 to obtain the organosilan polymerization hydrophobic layer of different-thickness, remaining operates according to the mode of embodiment 1, operates as follows:
A, the solvent (ethanol: water=4:1) of the HNTs-IBU 200mL of 0.5g is carried out ultrasonic dissolution, 8.335mL ammonia is added after a while half an hour in 45 DEG C of magnetic agitation, later add 1.75g tetraethoxysilane (TEOS), whole reaction system is in 45 DEG C of water-bath 12h.After having reacted, extremely neutral with the cleaning of second alcohol and water respectively, centrifugal, vacuum drying obtains HNTs-IBU TEOS.
B, get 0.5g HNTs-IBU@TEOS ultrasonic disperse in the dry toluene of 25mL, add n-octytriethoxysilane (OTES) back flow reaction 24h in 90 DEG C of oil baths of 4g.After having reacted, respectively by ethanol and toluene cleaning extremely neutrality, centrifugal, vacuum drying obtains HNTs-IBU@TEOS@OTES.
The material slow-release effect obtained is as Fig. 4, and as can be seen from the figure, medicine is difficult to discharge from material, affects drug absorption process and curative effect.
Embodiment 2
(1) corrosion of halloysite nanotubes
Get 4g galapectite powder dispersion in the dilution heat of sulfuric acid of 200mL 5mol/L, after ultrasonic disperse, magnetic agitation 12h in 80 DEG C of water-baths, with a large amount of distilled water wash to neutral, vacuum 70 DEG C of dryings, obtain the dilatation halloysite nanotubes of inner wall section corrosion.
(2) load of ofloxacin (OFL)
Get 1g ofloxacin sample and be placed in conical flask, dissolved completely with the dilute acetic acid solution of 30mL pH 3.0, then add the halloysite nanotubes ultrasonic disperse of the dilatation of 2g, and guarantee system is in vacuum environment, constant temperature oscillation 48h is to reach the object of drug loading, complete with the cleaning of dilute acetic acid solution water, vacuum drying obtains HNTs-OFL.
(3) hydrophobic layer is modified
A, the solvent (isopropyl alcohol: water=5:1) of the HNTs-OFL 200mL of 0.5g is carried out ultrasonic dissolution, 8.335mL ammonia is added after a while in 45 DEG C of magnetic agitation, later add 1.75g tetraethoxysilane (TEOS), whole reaction system is in 60 DEG C of water-bath 12h.After having reacted, extremely neutral with the cleaning of second alcohol and water respectively, centrifugal, vacuum drying obtains HNTs-OFL TEOS.
B, get 0.5g HNTs-OFL@TEOS ultrasonic disperse in the dry toluene of 25mL, add n-octytriethoxysilane (OTES) back flow reaction 24h in 100 DEG C of oil baths of 2.32g.After having reacted, respectively by ethanol and toluene cleaning extremely neutrality, centrifugal, vacuum drying obtains HNTs-OFL@TEOS@OTES.Such organosilan polymerization hydrophobic layer is just formed at halloysite nanotubes surface.
(4) external sustained release performance
The external slow release behavior of HNTs-OFL@TEOS@OTES nano-tube support material is carried out in dissolving-out tester, the nano material of 0.5g is infiltrated in the pH 7.4PBS buffer solution of 500mL, 100rpm/min, 37 DEG C, in a certain time interval, get the release liquid of 5.0mL respectively, and fill into the fresh pH 7.4PBS buffer solution of 5.0mL, the solution taken out is passed through the nylon leaching film of 0.45 μm, then by its concentration of ultraviolet determination.
Embodiment 3
(1) corrosion of halloysite nanotubes
Get 4g galapectite powder dispersion in the dilution heat of sulfuric acid of 200mL 4mol/L, after ultrasonic disperse, magnetic agitation 12h in 80 DEG C of water-baths, with a large amount of distilled water wash to neutral, vacuum 70 DEG C of dryings, obtain the dilatation halloysite nanotubes of inner wall section corrosion.
(2) load of ibuprofen (IBU)
Get 2g Ibuprofen samples and be placed in conical flask, dissolved completely with the ethanol of 50mL, then add the halloysite nanotubes ultrasonic disperse of the dilatation of 2g, and guarantee system is in vacuum environment, constant temperature oscillation 24h is to reach the object of drug loading, complete with the cleaning of second alcohol and water, vacuum drying obtains HNTs-IBU.
(3) hydrophobic layer is modified
A, the solvent (ethanol: water=5:1) of the HNTs-IBU 200mL of 0.5g is carried out ultrasonic dissolution, 8.335mL ammonia is added after a while in 60 DEG C of magnetic agitation, later add 2.25g tetraethoxysilane (TEOS), whole reaction system is in 60 DEG C of water-bath 12h.After having reacted, extremely neutral with the cleaning of second alcohol and water respectively, centrifugal, vacuum drying obtains HNTs-IBU TEOS.
B, get 0.5g HNTs-IBU@TEOS ultrasonic disperse in the dry toluene of 25mL, add n-octytriethoxysilane (OTES) back flow reaction 24h in 120 DEG C of oil baths of 3g.After having reacted, respectively by ethanol and toluene cleaning extremely neutrality, centrifugal, vacuum drying obtains HNTs-IBU@TEOS@OTES.Such organosilan polymerization hydrophobic layer is just formed at halloysite nanotubes surface.
(4) external sustained release performance
The external slow release behavior of HNTs-IBU@TEOS@OTES nano-tube support material is carried out in dissolving-out tester, the nano material of 0.5g is infiltrated in the pH 7.4PBS buffer solution of 500mL, 100rpm/min, 37 DEG C, in a certain time interval, get the release liquid of 5.0mL respectively, and fill into the fresh pH 7.4PBS buffer solution of 5.0mL, the solution taken out is passed through the nylon leaching film of 0.45 μm, then by its concentration of ultraviolet determination.
Embodiment 4
(1) corrosion of halloysite nanotubes
Get 4g galapectite powder dispersion in the dilution heat of sulfuric acid of 200mL 5mol/L, after ultrasonic disperse, magnetic agitation 12h in 75 DEG C of water-baths, with a large amount of distilled water wash to neutral, vacuum 70 DEG C of dryings, obtain the dilatation halloysite nanotubes of inner wall section corrosion.
(2) load of diclofenac sodium (DS)
Get 2g diclofenac sodium sample and be placed in conical flask, dissolved completely with the ethanol of 40mL, then add the halloysite nanotubes ultrasonic disperse of the dilatation of 1g, and guarantee system is in vacuum environment, constant temperature oscillation 24h is to reach the object of drug loading, complete with the cleaning of second alcohol and water, vacuum drying obtains HNTs-DS.
(3) hydrophobic layer is modified
A, the solvent (isopropyl alcohol: water=3:1) of the HNTs-DS 200mL of 0.5g is carried out ultrasonic dissolution, 8.335mL ammonia is added after a while in 50 DEG C of magnetic agitation, later add 2.25g tetraethoxysilane (TEOS), whole reaction system is in 45 DEG C of water-bath 12h.After having reacted, extremely neutral with the cleaning of second alcohol and water respectively, centrifugal, vacuum drying obtains HNTs-DS TEOS.
B, get 0.5g HNTs-DS@TEOS ultrasonic disperse in the dry toluene of 25mL, add n-octytriethoxysilane (OTES) back flow reaction 24h in 120 DEG C of oil baths of 3g.After having reacted, respectively by ethanol and toluene cleaning extremely neutrality, centrifugal, vacuum drying obtains HNTs-DS@TEOS@OTES.Such organosilan polymerization hydrophobic layer is just formed at halloysite nanotubes surface.
(4) external sustained release performance
The external slow release behavior of HNTs-DS@TEOS@OTES nano-tube support material is carried out in dissolving-out tester, the nano material of 0.3g is infiltrated in the pH 7.4PBS buffer solution of 500mL, 100rpm/min, 37 DEG C, in a certain time interval, get the release liquid of 3.0mL respectively, and fill into the fresh pH 7.4PBS buffer solution of 3.0mL, the solution taken out is passed through the nylon leaching film of 0.45 μm, then by its concentration of ultraviolet determination.
Claims (10)
1. a halloysite nanotubes Thermosensitive Material Used for Controlled Releasing of Medicine, it is characterized in that, this Thermosensitive Material Used for Controlled Releasing of Medicine is by carrying out acid corrosion with after the nanotube obtaining dilatation by halloysite nanotubes, by drug loading in halloysite nanotubes inner chamber, the halloysite nanotubes Surface coating organosilan polymerization hydrophobic layer after medicine carrying obtains; Wherein, in the process of coated organic polymerizable silane hydrophobic layer, organo silane coupling agent I pair of halloysite nanotubes outer surface is first used to modify, add organo silane coupling agent II again, thus form organic polymerizable silane hydrophobic layer at halloysite nanotubes Surface coating, organo silane coupling agent I is tetraethoxysilane, and organo silane coupling agent II is selected from one or more in n-octytriethoxysilane, hexadecyl, VTES.
2. slow-release material according to claim 1, is characterized in that, the organosilan polymerization hydrophobic layer thickness of formation is 20 ~ 50nm.
3. slow-release material according to claim 1, is characterized in that, described medicine is ibuprofen, diclofenac sodium or ofloxacin.
4. the preparation method of the slow-release material described in any one of claim 1-3, is characterized in that, comprises the following steps:
(1) corrosion of halloysite nanotubes
Galapectite powder dilute acid soln corrodes, and washing, drying, obtain the dilatation halloysite nanotubes of inner wall section corrosion;
(2) drug loading
To treat that the medicine dissolution of load is in solvent, be then soaked in above-mentioned solution by the halloysite nanotubes of dilatation, guarantee system is in vacuum environment, and cleaning, drying obtain medicine carrying halloysite nanotubes;
(3) hydrophobic layer is modified
A, medicine carrying halloysite nanotubes solvent to be dissolved, add ammonia, then add organo silane coupling agent I and at 30 ~ 70 DEG C, halloysite nanotubes outer surface is modified;
B, by modify after halloysite nanotubes be scattered in solvent, add organo silane coupling agent II at 90 ~ 130 DEG C in the organic polymerizable silane hydrophobic layer of the coated formation of nanotube surface;
Wherein, organosilan I is tetraethoxysilane, and organosilan II is selected from one or more in n-octytriethoxysilane, hexadecyl, VTES.
5. preparation method according to claim 4, is characterized in that, in (3) step, the mass ratio of medicine carrying halloysite nanotubes and organo silane coupling agent I is 1:2.0 ~ 5.0.
6. the preparation method according to claim 4 or 5, is characterized in that, in (3) step, adds 5 ~ 20mL ammonia in every 1g medicine carrying halloysite nanotubes.
7. preparation method according to claim 4, is characterized in that, in (3) step, the mass ratio of the halloysite nanotubes after modification and organo silane coupling agent II is 1:2.5 ~ 7.0.
8. the preparation method according to claim 4 or 7, is characterized in that, in (2) step, the mass ratio of halloysite nanotubes and medicine is 1:0.5 ~ 5.
9. preparation method according to claim 4, is characterized in that, the concentration of described dilute acid soln is 1.0 ~ 5.0mol/L.
10. preparation method according to claim 4, is characterized in that, one or more in described solvent selected from ethanol, isopropyl alcohol, toluene or cyclohexane extraction.
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