CN104030296A - Method for preparing tiny mesoporous silica drug sustained-release material - Google Patents
Method for preparing tiny mesoporous silica drug sustained-release material Download PDFInfo
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Abstract
The invention provides a method for preparing a tiny mesoporous silica drug sustained-release material and a tiny mesoporous hollow tubular silicon dioxide material obtained through the method. The drug loading capacity, calculated through a TG method, of the tiny mesoporous hollow tubular silicon dioxide material for aspirin model drugs is 15%, the sustained-release stage is the time of six hours of the initial stage of an experiment, and the drug releasing rate is high; after six hours, the stage of release balancing is achieved, and the amount of balanced release is 73.6%.
Description
Technical field
The present invention relates to a kind of micro-mesoporous silicon oxide Thermosensitive Material Used for Controlled Releasing of Medicine, belong to material processing field.
Background technology
Occurring in nature exists many porous masses.The definition of pure according to the world in applied chemistry federation (IUPAC), porous material (porous material) is divided three classes according to pore diameter range: being less than 2nm is micropore (micropore); 2 to 50nm is mesoporous (mesopore); Being greater than 50 nanometers is macropore (macropore).Sometimes also the micropore that is less than 0.7nm is called to ultramicropore, the macropore that is greater than 1mm is called grand hole.From Mobil company in 1992, develop and take after the material that M41S is representative, ordered mesoporous material just real a kind of novel material of conduct is climbed up stage.Ordered mesoporous material also carries out deep research because its unique structure, character and potential application performance have attracted the scholar of various different research fields to it.
By chemical constitution classification, mesoporous material can be divided into the large class of silica-based and non-silica-based composition two, and the main component of silicon-based mesoporous material skeleton is silicon-dioxide, comprises pure silicon dioxide and other element two class mesoporous materials of doping; Non-silicon-based mesoporous material be skeleton consist of non-silicon comprise carbon, transition metal oxide, phosphoric acid salt and sulfide etc.The variable valence state that they have, or metal properties, will make them have application prospect widely.But they are with respect to silicon-based mesoporous material, and thermostability is poor, and during calcining, duct easily caves in, its preparation method is still a stern challenge.
The feature of mesoporous material has: 1. have high-specific surface area and 2. have orderly pore passage structure, pore size distribution is narrower, and size is adjustable; 3. or aftertreatment synthetic through condition optimizing, has good thermostability; 4. particle has regular morphology.
Mesoporous hollow silica material is because of its orderly mesopore orbit structure, higher surface-area, and density is low, and Thermodynamically stable has overcome traditional Si O2 because density is large, specific surface area is little, the deficiency that application is restricted.And inner hollow structure expanded the volume of material especially, can fix or load large active compound.Material is being loaded, and adsorbing domain has higher using value.
The method of synthesizing mesoporous silicon dioxide material is a lot, as hydrothermal method, and low temperature synthesis method, solid reaction process, template synthesis method, microemulsion method, spray reaction etc.And the method for preparing mesoporous hollow silica material is mainly template.Select nano-grade matter that a kind of specified shape maybe can form specified shape intermediate as reaction template, by some householder methods, in template, wrap up layer of silicon dioxide housing, then with calcining, dissolve, the method for cleaning is removed template and is made silicon-dioxide housing keep mesoporous hollow structure.According to the character of template, be generally divided into soft template and hard template method.According to shell formation mechanism difference, be divided into again sol-gel method and self-assembly method layer by layer.
Mesoporous hollow silica material, as a kind of new nanostructure, except having orderly pore passage structure, also has very large internal space, makes it can load guest species, and object and environment are separated completely, until suitable location discharges.Therefore it can be used as the carrier of medicament slow release and controlled release, the carrier of catalyzer, gas and noble metal particle sorbent material, the immobilized carrier of bio-identification, enzyme.In recent years, there is increasing scholar that the loading of the medicine of inorganic mesoporous hollow material is discharged and studied with control.Its good biocompatibility makes material aspect medicine controlled releasing, have good application potential; Its inner hollow structure makes it than common mesoporous material, aspect loading, more have superiority; It,, in size, pattern, controlled surface-functionalized, more has superiority as carrier than biological organic nano materials such as liposomes, artificial macromole, degradable high polymers.
Botterhuis etc. have synthesized diameter Distribution scope narrower (0.6-1.2 μ m) 40 ℃ of low temperature, and wall thickness is consistent, has the hollow nanometer material of vermiform pore passage structure, and have studied dye molecule at encapsulation release characteristics wherein.Liu etc. be take golden nanometer particle as template, and the 3-aminopropyl trimethoxy silane of take has been prepared diameter at 45-60nm as silicon source, and wall thickness is the mesoporous hollow silica nanometer spheroid of 3-10 nanometer.With sodium cyanide, dissolve " core " and obtain hollow structure.They take fluorescein isothiocyanate and have studied the slow release characteristic of mesoporous hollow material as drug model.Chen etc. are usingd soft template method (CTAB is as template), and the TEOS of take has synthesized diameter as 900nm as silicon source, the mesoporous hollow silica microsphere that wall thickness is 100nm.And take this water-insoluble drug of the Carbamazepine slow release characteristic of mesoporous material that has been model research.Zhu etc. have synthesized mesoporous hollow silica microsphere, and studied its surface with and without N-TES, NN-TES, the impact on ibuprofen pharmaceutical controlled release during NNN-TES modification.
For the research great majority of mesoporous hollow silica material medicament slow release characteristic, concentrate in recent years spherically, improve drug loading, and control time three aspects that discharge.For other shapes understatement as fresh in tubulose road.Aspect raising drug loading, be generally that expectation is controlled at 1 μ m left and right by material diameter.Suitable effects on surface modification is also significant to improving drug loading, control to discharge.Current mesoporous hollow material is also unrealized industrialization in the application of medicament slow release, but its good biocompatibility, internal capacity is large, and pore passage structure is beneficial to slowly-releasing, encapsulated drug safety in iuntercellular transmission etc., a little invariably show that it has huge development potentiality aspect Thermosensitive Material Used for Controlled Releasing of Medicine.
Electrostatic spinning technique is a kind of special methods of preparing nano/submicron level material.Formals by the U.S. proposed in 1934.This technology, by polymers soln or melt are applied to electric field, makes it be drawn into solid jet state, and forming diameter is the spinning of nano-micrometre level, and is collected on receiving screen.Method of electrostatic spinning is being subject to extensive concern because it is convenient, flexible, simple to operate aspect preparation submicron/nanometer level material.
Electric spinning device is minute three parts generally: high-voltage power supply, kapillary and metal receiving trap.High-voltage power voltage is at 1-50kV; Capillary is generally ined succession and is contained polymers soln syringe, and syringe is contained on syringe pump; Receiving trap adopts tinsel or wire netting.Electrical spinning method is all suitable for a variety of materials, as superpolymer, and matrix material, semiconductor material, stupalith etc.In order to obtain the nanofiber of specific modality, many scientists study and improve on device for spinning.As 1. improved receiving trap, comprise that cylinder receives, parallel pole receives, and rotational line drum receives, and rotating disk receives, bath of liquid reception etc.; 2. operation improving electrode, is included in spinning nozzle and places a metal ring that adds positive electricity; 3. improve spinning nozzle, comprise coaxial spray silk, air-casing spinning, bi-component spray silk.
During spinning, be generally that the syringe that syringe pump promotes to be equipped with polymers soln advances, make it at kapillary spinning nozzle, form the drop that can not drip, solution is connected with power supply high-voltage positive electrode by metal electrode, and now polymers soln is subject to the effect of surface tension and electrical forces at capillary exit; Increase along with strength of electric field, charge generation electric field in solution causes drop deformation, the solution of end gradually becomes taper by semisphere, be called Taylor cone, when critical electric field power reaches certain value, charged liquid stream goes out from Taylor vertex of a cone end-fire, solvent volatilizees rapidly, jet is subject to stretching action, makes tensile fiber elongated to diameter to nano level filament shape, is finally mapped to brokenly on the receiving trap that is connected to negative voltage.Voltage, receiving screen and kapillary distance, the concentration of polymers soln, the character of solvent and kind are all the factors that determine spinning diameter.In general, voltage is larger, and polymer concentration is lower, and receiving screen and kapillary distance are far away, and spinning diameter is less.
Up to the present, electrostatic spinning technique is unique effective way that realizes fiber nanometer materials continuous production.Functional materials prepared by method of electrostatic spinning has great potential in carrier, biomedicine, thin film fabrication, sensitive material application aspect.
Lignocellulose mainly comprises xylogen, hemicellulose, cellulose iii part, increasing people's research application Electrospinning is prepared minor diameter in recent years lignocellulose, xylogen, hemicellulose, Mierocrystalline cellulose and derivatived cellulose.
It is raw material that this patent adopts cellulose acetate exactly, and Electrospun obtains hundreds of nanometers to the fiber of micron diameter; Then as template, with TEOS, be silicon source, application solgel reaction obtains silicon-dioxide cellulose acetate nucleocapsid mixture; In high-temperature calcination in retort furnace to remove cellulose acetate template and to obtain having micro-mesoporous silicon dioxide tube; Finally with 3-aminopropyl trimethoxy silane, micro-mesoporous silicon dioxide tube is carried out to amination modification, obtain having the micro-meso-porous titanium dioxide silicone tube of amination of drug slow release function.
Summary of the invention
The object of the present invention is to provide a kind of silicon-dioxide tubulose material with drug slow release function, the method environmental friendliness, cost is low, technique is simple.
Object of the present invention is achieved through the following technical solutions:
A method of preparing micro-mesoporous silicon oxide Thermosensitive Material Used for Controlled Releasing of Medicine, is characterized in that comprising the steps:
Step (1): employing cellulose acetate is raw material;
Step (2): cellulose acetate is dissolved in to acetone/water mixing solutions, and cellulose acetate concentration is 9-18wt%;
Step (3): cellulose acetate solution prepared by step (2) carries out electrostatic spinning, and Electrospun condition is: voltage 10-30kV, syringe needle and collecting board spacing 10-30cm, feed liquor amount 1-5mL/h;
Step (4): collect electrostatic spinning cellulose acetate, then it is template, take cetyl trimethylammonium bromide as bridging agent, tetraethoxy is silicon source, adopts sol-gel method, prepares the core-shell material of silicon-dioxide/cellulose acetate, its reaction conditions is: reaction medium is the mixture of water and ethanol, the addition of cetyl trimethylammonium bromide is 0.5-5mmol/L in addition, tetraethoxy addition 1-10mL/L, ammoniacal liquor 2-15mL/L;
Step (5): the core-shell material high-temperature calcination of silicon-dioxide/cellulose acetate prepared by step (4), remove organic template, obtain having micro-mesoporous silicon dioxide tube;
Step (6): micro-mesoporous silicon-dioxide tube material prepared by step (5) is placed in container, add reaction medium toluene, then add 3-aminopropyl trimethoxy silane, and ultrasonic dispersion, again container is placed in to 120 ℃ of oil bath pan reflux, reaction finishes use toluene centrifuge washing afterwards, then uses ethanol centrifuge washing, and last vacuum-drying is for the amidized micro-meso-porous titanium dioxide silicone tube that obtains having drug slow release function.
The micro-mesoporous hollow tubular earth silicon material that the method obtains, this micro-mesoporous hollow tubular earth silicon material calculates drug loading to acetylsalicylic acid model drug by TG method and reaches 15%, and 6 hours experiment initial stages were the slowly-releasing stage, and rate of release is very fast; After 6 hours, reach release balance, balance burst size is 73.6%.
Accompanying drawing explanation
Accompanying drawing 1: cellulose acetate (concentration 18wt%) Electrospun
The silicon dioxide tube of accompanying drawing 2: embodiment 1 preparation
Accompanying drawing 3. cellulose acetates (concentration 14wt%) Electrospun
The silicon dioxide tube of accompanying drawing 4. embodiment 2 preparations
Accompanying drawing 5. cellulose acetates (concentration 9wt%) Electrospun
The silicon dioxide tube of accompanying drawing 6: embodiment 3 preparations
The amination silicon dioxide tube (SiO2-APTES) of accompanying drawing 7: embodiment 3 preparations, the thermogravimetric curve of the amination silicon dioxide tube (SiO2-APTES-ASP) of loading acetylsalicylic acid and pure acetylsalicylic acid (ASP)
Accompanying drawing 8. acetylsalicylic acid are loaded in the release profiles of embodiment 3 materials
Embodiment
Take the cellulose acetate (CA) of certain mass, be dissolved in acetone and water (v: v=9: in mixing solutions 1), be uniformly dissolved stand for standby use completely with magnetic stirrer to cellulose acetate.Above-mentioned solution is packed in the syringe of being furnished with metal needle.The positive electrode of high-voltage power supply is connected with syringe needle, and ground-electrode is connected with the aluminium film on collecting board.The electrostatic spinning parameters such as regulating voltage, syringe needle and collecting board spacing, feed liquor speed, prepare the acetic acid micron/submicron silk (CAMF) of different diameter.
At room temperature take a certain amount of cellulose acetate Electrospun, add deionized water and the dehydrated alcohol of certain volume, then add a certain proportion of CTAB, adding the ammoniacal liquor of certain volume as catalyzer.Above-mentioned mixing solutions is disperseed 30 minutes with ultrasonic separating apparatus, CTAB and ammoniacal liquor are evenly distributed in system.Within standing 10 minutes, make CTAB and CAMF reach adsorption equilibrium again.Then slowly add a certain amount of TEOS disperseing with dehydrated alcohol.Under 30 ± 1 ℃ of water-baths, be incubated 2-3 hour.Reaction finishes rear washing with alcohol.Air-dry under natural condition, obtain CAMF-SiO2 core-shell material.
By the 600 ℃ of high-temperature calcinations 6 hours in retort furnace of above-mentioned core-shell material, remove template CAMF and CTAB, obtain micro-mesoporous hollow silica tubular material.
The powder sample that takes a certain amount of dried micro-mesoporous silicon oxide tubular material, is placed in Florence flask, adds toluene and 3-aminopropyl trimethoxy silane (APTES), ultrasonic dispersion.Florence flask is placed in to 120 ℃ of oil bath pan reflux 6h.Reaction finishes rear toluene centrifuge washing 2 times of using, ethanol centrifuge washing 3 times, and vacuum-drying is for obtaining amidized silicon dioxide tube, and this material can be used for follow-up medicament slow release research.
Below in conjunction with embodiment, the present invention is described in further detail, but embodiments of the present invention are not limited to this.
Embodiment 1
The cellulose acetate solution of preparation 18wt%.Above-mentioned solution is packed in the syringe of being furnished with metal needle.The positive electrode of high-voltage power supply is connected with syringe needle, and ground-electrode is connected with the aluminium film on collecting board.Regulating voltage 20kV, syringe needle and collecting board spacing 20cm, feed liquor speed 5mL/h etc., prepare diameter at the cellulose acetate Electrospun of several microns, sees accompanying drawing 1.
At room temperature take 0.1g cellulose acetate Electrospun, add 45mL deionized water and 15mL dehydrated alcohol, then add cetyl trimethylammonium bromide 0.03mmol, then add the ammoniacal liquor of 0.12mL as catalyzer.Above-mentioned mixing solutions is disperseed 30 minutes with ultrasonic separating apparatus.Within standing 10 minutes, make CTAB and CAMF reach adsorption equilibrium again.Then slowly add the TEOS that 0.6mL disperses with dehydrated alcohol.Under 30 ± 1 ℃ of water-baths, be incubated 3 hours.Reaction finishes rear washing with alcohol.Air-dry under natural condition, obtain CAMF-SiO2 core-shell material.
By the 600 ℃ of high-temperature calcinations 6 hours in retort furnace of above-mentioned core-shell material, remove template CAMF and CTAB, obtain micro-mesoporous hollow silica tubular material, its SEM figure is shown in accompanying drawing 2.It is 240m that BET method is measured specific surface area
2/ g.
The powder sample 0.2g that takes dried micro-mesoporous silicon oxide tubular material, is placed in 150mL Florence flask, adds 40mL toluene and 5mLAPTES, ultrasonic dispersion.Florence flask is placed in to 120 ℃ of oil bath pan reflux 6h.Reaction finishes rear toluene centrifuge washing 2 times of using, ethanol centrifuge washing 3 times, and vacuum-drying is for obtaining amidized silicon dioxide tube, and this material can be used for follow-up medicament slow release research.
Embodiment 2
The cellulose acetate solution of preparation 14wt%.Above-mentioned solution is packed in the syringe of being furnished with metal needle.The positive electrode of high-voltage power supply is connected with syringe needle, and ground-electrode is connected with the aluminium film on collecting board.Regulating voltage 10kV, syringe needle and collecting board spacing 10cm, feed liquor speed 1mL/h etc., prepare diameter at the cellulose acetate Electrospun of hundreds of nanometers, sees accompanying drawing 3.
At room temperature take 0.1g cellulose acetate Electrospun, add 30mL deionized water and 30mL dehydrated alcohol, then add cetyl trimethylammonium bromide 0.3mmol, then add the ammoniacal liquor of 0.9mL as catalyzer.Above-mentioned mixing solutions is disperseed 30 minutes with ultrasonic separating apparatus.Within standing 10 minutes, make CTAB and CAMF reach adsorption equilibrium again.Then slowly add the TEOS that 0.06mL disperses with dehydrated alcohol.Under 30 ± 1 ℃ of water-baths, be incubated 2 hours.Reaction finishes rear washing with alcohol.Air-dry under natural condition, obtain CAMF-SiO2 core-shell material.
By the 600 ℃ of high-temperature calcinations 6 hours in retort furnace of above-mentioned core-shell material, remove template CAMF and CTAB, obtain micro-mesoporous hollow silica tubular material, its SEM figure is shown in accompanying drawing 4.It is 450m that BET method is measured specific surface area
2/ g.
The powder sample 0.2g that takes dried micro-mesoporous silicon oxide tubular material, is placed in 150mL Florence flask, adds 40mL toluene and 5mLAPTES, ultrasonic dispersion.Florence flask is placed in to 120 ℃ of oil bath pan reflux 6h.Reaction finishes rear toluene centrifuge washing 2 times of using, ethanol centrifuge washing 3 times, and vacuum-drying is for obtaining amidized silicon dioxide tube, and this material can be used for follow-up medicament slow release research.
Embodiment 3
The cellulose acetate solution of preparation 9wt%.Above-mentioned solution is packed in the syringe of being furnished with metal needle.The positive electrode of high-voltage power supply is connected with syringe needle, and ground-electrode is connected with the aluminium film on collecting board.Regulating voltage 30kV, syringe needle and collecting board spacing 15cm, feed liquor speed 2mL/h etc., prepare diameter at the cellulose acetate Electrospun of submicron, sees accompanying drawing 5.
At room temperature take 0.1g cellulose acetate Electrospun, add 15mL deionized water and 45mL dehydrated alcohol, then add cetyl trimethylammonium bromide 0.01mmol, then add the ammoniacal liquor of 0.09mL as catalyzer.Above-mentioned mixing solutions is disperseed 30 minutes with ultrasonic separating apparatus.Within standing 10 minutes, make CTAB and CAMF reach adsorption equilibrium again.Then slowly add the TEOS that 0.2mL disperses with dehydrated alcohol.Under 30 ± 1 ℃ of water-baths, be incubated 3 hours.Reaction finishes rear washing with alcohol.Air-dry under natural condition, obtain CAMF-SiO2 core-shell material.
By the 600 ℃ of high-temperature calcinations 6 hours in retort furnace of above-mentioned core-shell material, remove template CAMF and CTAB, obtain micro-mesoporous hollow silica tubular material, its SEM figure is shown in accompanying drawing 6.It is 760m that BET method is measured specific surface area
2/ g.It is that the pore volume in the hole of 1.7nm-300nm is 0.41cm that BJH model calculates pore diameter range
3/ g, the pore volume that is wherein less than 67nm is 0.46cm
3/ g, mesoporous aperture concentrates on 4.60nm; It is 0.18cm that Horvath-Kawazoe model calculates Micropore volume
3/ g, diameter concentrates on 0.7nm left and right.
The powder sample 0.2g that takes dried micro-mesoporous silicon oxide tubular material, is placed in 150mL Florence flask, adds 40mL toluene and 5mLAPTES, ultrasonic dispersion.Florence flask is placed in to 120 ℃ of oil bath pan reflux 6h.Reaction finishes rear toluene centrifuge washing 2 times of using, ethanol centrifuge washing 3 times, and vacuum-drying is for obtaining amidized silicon dioxide tube, and this material can be used for follow-up medicament slow release research.
Technique effect
The present invention be take cellulose acetate Electrospun and is prepared the earth silicon material of tubulose as template, then the surfaces externally and internally of its pipe of amination obtains having the material of drug slow release function.Finally we are medicine loading capacity and the slow release effect that model drug is assessed this material with acetylsalicylic acid.
It is as follows that medicine loads experiment: take the amination silicon dioxide tube of 0.15g after 40 ℃ of vacuum-drying, be placed in the ethanolic soln that 18mL aspirin content is 20mg/mL, at room temperature magnetic agitation 24h carries out medicine loading, centrifugation, and 40 ℃ of vacuum-dryings are standby.Finally utilize thermogravimetric analyzer (TG) to calculate medicine loading capacity.
Drug release: the PBS damping fluid of configuration simulation human body environment, compound method is as follows: by 0.24g KH2PO4,3.63g Na2HPO412H2O, 8gNaCl and 0.2gKCl are dissolved in 900mL deionized water, regulate pH=7.4, add deionized water and are settled to 1L.
Utilize the PBS measured in solution ultraviolet absorptivity of the acetylsalicylic acid of concentration known, draw the typical curve of the relation of the absorbancy of acetylsalicylic acid in PBS damping fluid and concentration.Take the SiO2-APTES-ASP after 0.12g vacuum-drying, be placed in Erlenmeyer flask, add 120mL PBS damping fluid, be placed in low temperature shaking table, temperature setting is set to 37 ℃, rotating speed 200rpm/min.At certain time interval: 10min, 20min, 40min, 1h, 1.5h, 2h, 3h, 4h, 6h, 8h, 10h, 12h, 24h, 36h, 48h, 72h pipettes 2 * 1.8mL solution with liquid-transfering gun, centrifugation under rotating speed 11000rpm, gets supernatant liquid and utilizes ultraviolet spectrophotometer to measure absorbancy, calculates release amount of medicine.
The acetylsalicylic acid loading capacity of the amination silicon dioxide tube in embodiment 1 is 6%, and the medicament slow release time is 2 hours.
The acetylsalicylic acid loading capacity of the amination silicon dioxide tube in embodiment 2 is 10%, and the medicament slow release time is 4 hours.
The acetylsalicylic acid loading capacity of the amination silicon dioxide tube in embodiment 3 is 15%, and the medicament slow release time is 6 hours, and its balance burst size is 73.6%.The laden TG figure of medicine of embodiment 3 is shown in accompanying drawing 7, and its medicament slow release curve is shown in accompanying drawing 8.
Statement in addition, it in embodiment, is only preferred embodiment of the present invention, not the present invention is done to any pro forma restriction, although the present invention discloses as above with preferred embodiment, yet not in order to limit the present invention, any those skilled in the art, within not departing from the scope of technical solution of the present invention, when can utilizing the technology contents of above-mentioned announcement to make a little change or being modified to the equivalent embodiment of equivalent variations, in every case be not depart from technical solution of the present invention content, any simple modification of above embodiment being done according to technical spirit of the present invention, equivalent variations and modification, all still belong in the scope of technical solution of the present invention.
Claims (2)
1. a method of preparing micro-mesoporous silicon oxide Thermosensitive Material Used for Controlled Releasing of Medicine, is characterized in that comprising the steps:
Step (1): employing cellulose acetate is raw material;
Step (2): cellulose acetate is dissolved in to acetone/water mixing solutions, and cellulose acetate concentration is 9-18wt%;
Step (3): cellulose acetate solution prepared by step (2) carries out electrostatic spinning, and Electrospun condition is: voltage 10-30kV, syringe needle and collecting board spacing 10-30cm, feed liquor amount 1-5mL/h;
Step (4): collect electrostatic spinning cellulose acetate, then it is template, take cetyl trimethylammonium bromide as bridging agent, tetraethoxy is silicon source, adopts sol-gel method, prepares the core-shell material of silicon-dioxide/cellulose acetate, its reaction conditions is: reaction medium is the mixture of water and ethanol, the addition of cetyl trimethylammonium bromide is 0.5-5mmol/L in addition, tetraethoxy addition 1-10mL/L, ammoniacal liquor 2-15mL/L;
Step (5): the core-shell material high-temperature calcination of silicon-dioxide/cellulose acetate prepared by step (4), remove organic template, obtain having micro-mesoporous silicon dioxide tube;
Step (6): micro-mesoporous silicon-dioxide tube material prepared by step (5) is placed in container, add reaction medium toluene, then add 3-aminopropyl trimethoxy silane, and ultrasonic dispersion, again container is placed in to 120 ℃ of oil bath pan reflux, reaction finishes use toluene centrifuge washing afterwards, then uses ethanol centrifuge washing, and last vacuum-drying is for the amidized micro-meso-porous titanium dioxide silicone tube that obtains having drug slow release function.
2. the micro-mesoporous hollow tubular earth silicon material that method according to claim 1 obtains, this micro-mesoporous hollow tubular earth silicon material calculates drug loading to acetylsalicylic acid model drug by TG method and reaches 15%, 6 hours experiment initial stages were the slowly-releasing stage, and rate of release is very fast; After 6 hours, reach release balance, balance burst size is 73.6%.
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| CN106395838A (en) * | 2016-02-26 | 2017-02-15 | 厦门大学 | Method for preparing mesoporous silica gel |
| CN111333458A (en) * | 2020-05-07 | 2020-06-26 | 安徽肥地肥业有限责任公司 | Method for preparing organic fertilizer containing nicotine |
| CN111821463A (en) * | 2020-07-21 | 2020-10-27 | 中国矿业大学 | Preparation method of drug-loaded polycaprolactone-chitosan-silicon dioxide hybrid fiber |
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| CN105271268A (en) * | 2015-11-13 | 2016-01-27 | 上海联锴日用化工有限公司 | Monodisperse mesoporous silica microsphere powder and preparation method thereof |
| CN105648657A (en) * | 2015-12-30 | 2016-06-08 | 中国人民解放军国防科学技术大学 | Amination mesoporous silica fiber and preparation method and application thereof |
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| CN106395838A (en) * | 2016-02-26 | 2017-02-15 | 厦门大学 | Method for preparing mesoporous silica gel |
| CN111333458A (en) * | 2020-05-07 | 2020-06-26 | 安徽肥地肥业有限责任公司 | Method for preparing organic fertilizer containing nicotine |
| CN111821463B (en) * | 2020-07-21 | 2021-10-15 | 中国矿业大学 | Preparation method of drug-loaded polycaprolactone-chitosan-silicon dioxide hybrid fiber |
| CN111821463A (en) * | 2020-07-21 | 2020-10-27 | 中国矿业大学 | Preparation method of drug-loaded polycaprolactone-chitosan-silicon dioxide hybrid fiber |
| CN111939852A (en) * | 2020-07-28 | 2020-11-17 | 华陆工程科技有限责任公司 | Preparation method of aerogel microspheres with adsorption catalysis function |
| CN112456501A (en) * | 2020-11-30 | 2021-03-09 | 石河子大学 | Mesoporous silica nanosphere with ultrahigh specific surface area and preparation method thereof |
| CN113575575A (en) * | 2021-08-09 | 2021-11-02 | 华南农业大学 | Film-coated drug-loaded microsphere, drug-sustained-release insect-expelling pet collar and preparation method thereof |
| CN113575575B (en) * | 2021-08-09 | 2022-01-28 | 华南农业大学 | Film-coated drug-loaded microsphere, drug-sustained-release insect-expelling pet collar and preparation method thereof |
| CN114883567A (en) * | 2022-06-30 | 2022-08-09 | 河南科隆新能源股份有限公司 | Lithium ion battery cathode material with hollow tubular structure and preparation method and application thereof |
| CN114883567B (en) * | 2022-06-30 | 2022-09-30 | 河南科隆新能源股份有限公司 | Lithium ion battery cathode material with hollow tubular structure and preparation method and application thereof |
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