CN101766816B - Dipolar molecule-modified mesoporous silicon material, preparation and application thereof - Google Patents

Dipolar molecule-modified mesoporous silicon material, preparation and application thereof Download PDF

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CN101766816B
CN101766816B CN2009102477298A CN200910247729A CN101766816B CN 101766816 B CN101766816 B CN 101766816B CN 2009102477298 A CN2009102477298 A CN 2009102477298A CN 200910247729 A CN200910247729 A CN 200910247729A CN 101766816 B CN101766816 B CN 101766816B
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mesoporous silicon
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butyl
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祝迎春
李芳�
阮启超
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Jiangsu Institute of advanced inorganic materials
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Shanghai Institute of Ceramics of CAS
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    • A—HUMAN NECESSITIES
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Abstract

The invention relates to a dipolar molecule-modified mesoporous silicon material, preparation and application thereof. The dipolar molecule-modified mesoporous silicon material is prepared by coupling a dipolar molecule with silane end group graft and mesoporous silicon with a pore structure through a silicon-oxygen bond. A drug control and release system prepared by taking the dipolar molecule-modified mesoporous silicon material as a carrier can realize continuous control and release of guest molecules in the system through adjusting the applied electric field. The dielectrical property test shows that the drug control and release system has excellent electric field responsiveness and can be recycled through simple cleaning treatment after drug release.

Description

A kind of dipolar molecule-modified mesoporous silicon material and preparation and application
Technical field
The present invention relates to medicine controlled releasing architectural study field, be specifically related to mesoporous silicon decorative material, more specifically relate to the preparation of the dipolar molecule-modified mesoporous silicon material of function and as the application of electric field response control delivery system.
Background technology
At present; The exploitation of the diagnosis that develops into modern disease of nanotechnology, treatment, novel pharmaceutical formulation provides new technological means with innovation; Improve timing, constant speed and the directed controllability that discharges of medicine greatly, but still be difficult to realize real timing as required, constant speed and directed complete controlled release.
Inorganic nano pore structure material (like mesoporous silicon) is because it has the pore passage structure of homogeneous, big pore volume and specific surface area and the surface is easy to excellent performances such as chemical modification, can realize the control fully of the storage of medicine and timing, constant speed and the orientation of release through the functionalization assembling to its inner hole structure.This pharmaceutical carrier induction system based on the molecule nano technology makes artificial control drug release become real: photocontrol molecular switch [Mal, the N.K. of the mesoporous oral areas that take the lead in being loaded in Nature magazine report delegation such as Fujiwara in 2003; Fujiwara, M.; Tanaka, Y., Nature; 2003,421,350]; Utilize the closure of the variation gauge tap of outside light field, thereby control the storage and the release of mesoporous interior guest species effectively, this technology is having great importance aspect the development of novel local drug-delivery preparation and target medicine carrier.Patent applicant and Fujiwara seminar through the assembling of nano-pore functionalization, have successfully realized function [Zhu, the Y.C. of the mesoporous interior drug release rates of any down regulation and control of outer field action through joint study more than 3 years; Fujiwara, M., Angew.Chem.Int.Ed, 2007,46,2241.].
The material that can be used for mesoporous built-in function modification generally has response characteristics such as light, pH, heat and electricity, but the variation of recurring structure or conformation etc. realizes complete controllable release [Park, C. to guest molecule in mesoporous under environmental stimuli; Lee, K.; Kim, C.Angew.Chem., Int.Ed.2009,48,1275-1278; Aznar, E.; Marcos, M.D.; Martinez-Manez, R.; Sancenon, F.; Soto, J.; Amoros, P.; Guillem, C.J.Am.Chem.Soc.2009,131,6833-6843; Bernardos, A.; Aznar, E.; Marcos, M.D.; Martinez-Manez, R.; Sancenon, F.; Soto, J.; Barat, J.M.; Amoros, P.Angew.Chem., Int.Ed.2009,48,5884-5887.].But be based on the response control delivery of the signal of telecommunication because that electrochemical reaction etc. possibly take place is former thereby study less.
Summary of the invention
The object of the present invention is to provide a kind of dipolar molecule-modified mesoporous silicon material and preparation method thereof, and this dipolar molecule-modified mesoporous silicon material is as the application of carrier loaded medicine.
Technical scheme of the present invention is following:
A kind of dipolar molecule-modified mesoporous silicon material; Process through the siliconoxygen bond coupling with mesoporous silicon by having the grafted dipole molecule of silane end group with pore passage structure; At first with dipole molecule grafted silane end group, thereby the hydroxyl that will be connected with grafted dipole molecule of silane end group and mesoporous silicon material duct inwall again reacts and obtains dipolar molecule-modified mesoporous silicon material of the present invention.
Reaction equation is following:
Figure G2009102477298D00021
Said have 0.05wt%～50wt% that the grafted dipole molecule of silane end group accounts for mesoporous silicon gross mass, is preferably 0.05wt%～20wt%.
It is said that to have the grafted dipole molecule of silane end group be to make after dipole molecule and the grafting of silane end group; Wherein, Dipole molecule is the organic molecule with bigger intrinsic dipole moment, but is made up of strong electron-withdrawing group group, strong conjugation group and silanization group, and its structure is provided by following chemical general formula:
Figure G2009102477298D00022
Wherein, R1 representes strong electron-withdrawing group group, and R1 is selected from cyanic acid, nitro, thiocyanogen, isothiocyano and sulfur sulfydryl; But R2 representes the silanization group, and R2 is an alkene; R3 is phenyl ring or acetenyl; But said silanization group is an olefinic double bonds; Silane end group grafting agent is selected from triethoxysilane, trimethoxy silane, chlorodimethyl silane and methyl dimethoxysilane.
Said silicon dioxide with pore passage structure is selected from MCM-41 and SBA-15; It is said that to have the grafted dipole molecule of silane end group be [4-(3-benzonitrile) butyl] triethoxysilicane.
The method for preparing of dipolar molecule-modified mesoporous silicon material comprises the steps:
(1) preparation has grafted dipole molecule raw material of silane end group and the mesoporous silicon raw material with pore passage structure respectively;
(2), and react with the raw materials mix for preparing in the step (1);
(3) cleaning of product and dry.
Said to have the grafted dipole molecule raw material of silane end group be that dipole molecule and silane end group are synthetic under inert gas shielding, and synthesis temperature is-90～0 ℃; Synthetic method with mesoporous silicon raw material of pore passage structure mainly contains hydro-thermal method, sol-gal process etc.About 1～the 100nm of institute's former blanking aperture of synthetic mesoporous silicon, specific surface area is at 100～2000m 2/ g, XRD figure has the ordered mesoporous pore canals characteristic diffraction peak in (100), (110) and (220) direction.And hydroxyl and unsaturated residual bond are contained in the surface, and hydrophilic is stronger.
In the step (2), mixed material is that mol ratio is the mixture of 1: 0.005～0.1 MCM-41 and [4-(3-benzonitrile) butyl] triethoxysilicane, or the mixture of the SBA-15 of mol ratio 1: 0.005～0.1 and [4-(3-benzonitrile) butyl] triethoxysilicane; Be reflected under the anhydrous condition and carry out, reaction temperature is 0～100 ℃.
In the step (3), baking temperature is 30～240 ℃.
A kind of controlled drug delivery system is to make behind the carrier loaded hydrophobic or hydrophilic small molecules medicine with said dipolar molecule-modified mesoporous silicon material, one preferred embodiment in, carrying medicament is ibuprofen (IBU) or aspirin (Asp).
Provided by the present invention is that the controlled drug delivery system of carrier can be realized the height control to guest molecule rate of release in the hole with dipolar molecule-modified mesoporous silicon material.Said dipole molecule is a kind of strong dipolar dipole molecule that has that has; When modifying when mesoporous silicon is inner; Can swing with the variation of the direction of extra electric field, be equivalent to the effect of " stirrer ", make under the outer field action arbitrarily that drug release rate becomes possibility in the regulation and control duct.
The present invention utilizes the insulating self-control mesh electrode of a kind of novel surface to realize the height control to guest molecule rate of release in the hole; The insulating self-control mesh electrode of said novel surface is self-control, and the dull and stereotyped conductive metal sheet that adopts the porose or atresia of surface-coated dielectric film is done paired electrode and the sample that is opposite to therebetween carries out electric field controls; Free or atresia conducting metal sheet material is selected from: Pt, Ag, Au, Fe, Cu, Zn and Al (but market is buied); Insulating film material insullac, nial polish or ambroin (but market is buied).
Controlled drug delivery system can be realized the regulation and control to drug release rate through the frequency of regulating extra electric field.The dispose procedure that makes medicine is non-Fick flooding mechanism by the Fick diffusion transformation under the added electric field not; The rate of releasing drug of said controlled drug delivery system increases with the increase of extra electric field frequency, and the rate of releasing drug under 1Hz extra electric field frequency is more than 1 times of rate of releasing drug during added electric field not.
Concrete scheme of the present invention is following:
1. dipole molecule raw material 4-(3-benzonitrile)-butylene is synthetic
4-bromo-1-butylene, anhydrous and oxygen-free ether and t-butyl lithium are joined in the Schlenk reaction bulb under noble gas (like argon) protection, react 1～4h down at-90～0 ℃.The diethyl ether solution that under inert gas shielding, dropwise adds 3-bromo-benzene nitrile then behind reaction 2～10h under-90～0 ℃, rises to room temperature automatically with reaction system and finishes reaction.The feed ratio is: 4-bromo-1-butylene: 3-bromo-benzene nitrile: t-butyl lithium: anhydrous and oxygen-free ether=1: 0.5～1.5: 1～10: 20～100 (mol ratio).Water and NaCl handle crude product, and the reuse extracted with diethyl ether is an eluant with chloroform, oily ether behind the filtration drying, purifies through silica gel column layer, finally obtains lurid product 4-(3-benzonitrile)-butylene.
2. synthesizing of dipolar molecule-modified mesoporous silicon material
Under inert gas shielding, 4-(3-benzonitrile)-butylene, triethoxysilane, anhydrous and oxygen-free toluene 1: 0.5 in molar ratio～1.5: 20～150 are added in the reaction bulb.After stirring, add platinum catalyst (1～10 -6Mmol), continue reaction 2～48h and get product [4-(3-benzonitrile) butyl] triethoxysilicane.
Mesoporous silicon material MCM-41 or SBA-15 are added in the reaction bulb, add after dry toluene fully soaks into it again, add [4-(3-benzonitrile) butyl] triethoxysilicane, 0～100 ℃ is stirred down, and mixing time is preferably 0.5～24h.Wherein the feed ratio of MCM-41 or SBA-15 and [4-(3-benzonitrile) butyl] triethoxysilicane is 1: 0.005～0.01 (mol ratio).Product heats more than the 24h down in 30～240 ℃ under vacuum after selecting the evaporation separation.Wash back drying under 30～240 ℃ successively with toluene, ethanol then, the mesoporous silicon material that gets final product dipolar molecule-modifiedly is designated as FMSS.
3. the preparation of controlled drug delivery system
Join in the saturated solution of medicine after exsiccant FMSS weighed, stirring reaction is realized the load to medicine more than 1 day.FMSS behind the drug loading is placed on below 240 ℃ dry in the baking oven through separation, washing.The small pieces that then dried sample are pressed into more than the diameter 1cm are subsequent use.
4. the performance test of controlled drug delivery system
(1) dielectric properties test
MCM-41, SBA-15 and FMSS sample are depressed to small pieces about 0.1g at the pressure more than the 3MPa respectively, and (d >=1cm), be placed on the electrochemistry workbench measures its impedance spectrum, calculates dielectric constant then.For measuring the impedance spectrum of dipole molecule, we are added in the dipole molecule drips of solution on MCM-41, the SBA-15 mesoporous material sample, obtain sample MCMH or SBAH, and sample is placed on the laboratory table, survey its impedance spectrum, calculate dielectric constant.
(2) controlled drug delivery system medicine-releasing performance test
FMSS sample behind the medicine carrying is placed in the middle of the silver electrode of good seal, immerses in about 37 ℃ the simulated body fluid.Apply the square-wave voltage of 0～10Hz, every setting-up time is taken a sample for detection of drugs concentration, and replenishes with the fresh solution of equal volume.Drug level is detected by the UV:Vis spectrophotometer, and characteristic absorption is at 200-400nm.
5. structural characterization
Utilize x-ray diffractometer (XRD), the hydrogen nuclear magnetic resonance appearance ( 1HNMR), Fourier's infrared spectrum (FTIR), transmission electron microscope (TEM), specific surface appearance heat, analyser and UV:Vis spectrophotometer characterize sample.
Solvent used in the present invention mainly is the solvent to the mesoporous silicon with pore passage structure; Purpose is in order to make mesoporous silicon oxide dispersibility therein better; And the functional organic molecule with the end group modification does not react, and mainly is selected from benzene,toluene,xylene and N, dinethylformamide.
Cleaning solvent used in the present invention is the solvent to excess reactant, mainly is selected from ethanol, ether, methanol, toluene and acetone.
The invention has the beneficial effects as follows: (1) controlled drug delivery system of the present invention can be realized the seriality sustained release of guest molecule in the system through regulating extra electric field; (2) dielectric properties test shows, controlled drug delivery system of the present invention has good electric field response; (3) after the controlled drug delivery system release of the present invention, just can reuse through simple clean.
Description of drawings
The TEM figure of Fig. 1, mesoporous silicon material MCM-41.
Fig. 2, dipole molecule 4-(3-benzonitrile)-butylene 1HNMR figure.
The FTIR spectrogram of Fig. 3, FMSS.
The dielectric constant of Fig. 4, FMSS is with the variation relation of frequency.
The dielectric absorption of Fig. 5, FMSS is with the variation relation of frequency.
Weightless (TG-DTA) analytical curve of the thermogravimetric of Fig. 6, mesoporous silicon material MCM-41-differential thermal.
Fig. 7, FMSS weightless (TG-DTA) analytical curve of thermogravimetric-differential thermal.
Weightless (TG-DTA) analytical curve of the thermogravimetric of the FMSS of Fig. 8, IBU load-differential thermal.
The little angle XRD figure spectrum of Fig. 9, sample: (a) mesoporous silicon material MCM-41, (b) FMSS, (c) FMSS of IBU load, (d) the IBU load FMSS behind the drug release.
The N of the FMSS of the FMSS of Figure 10, mesoporous silicon material MCM-41, FMSS, IBU load, the IBU load behind the drug release 2Adsorption isotherm.
The pore size distribution curve of the FMSS of the FMSS of Figure 11, mesoporous silicon material MCM-41, FMSS, IBU load, the IBU load behind the drug release.
Figure 12, the FMSS drug release behavior under the different frequency extra electric field.
FMSS behind Figure 13, medicine carrying Peppas equation model analytical curve of (SBF) in simulated body fluid.
The specific embodiment
Embodiment 1
In the NaOH concentrated solution, add a certain amount of cetyl trimethyl ammonium bromide (CTAB), 80 ℃ add silicon dioxide after being stirred to clear liquid, are transferred to then in the water heating kettle; In 115 ℃ baking oven, heat 24h; Take out after-filtration, washing, dry mesoporous silicon crude product PMCM.The raw material ratio that add this moment is: 1SiO 2: 0.05NaOH: 0.1CTAB: 20H 2O (mol ratio).PMCM places ethanol with crude product, adds an amount of HCl (1M) again, and reflux 8h filters, washing, oven dry get final product the MCM-41 mesoporous material.This moment, ethanol was about 10: 1 (volume ratio) with HCl feed ratio.Can know that from the TEM photo of Fig. 1 sample MCM-41 material gained MCM-41 mesoporous material has good pore passage structure, aperture homogeneous, the about 3.0nm of average pore size.
4-bromo-1-butylene, anhydrous and oxygen-free ether and t-butyl lithium are joined in the Schlenk reaction bulb under the argon gas protection, react 2h down at-78 ℃.The diethyl ether solution that under inert gas shielding, dropwise adds 3-bromo-benzene nitrile then behind reaction 4h under-78 ℃, rises to room temperature automatically with reaction system and finishes reaction.The feed ratio is: 4-bromo-1-butylene: 3-bromo-benzene nitrile: t-butyl lithium: anhydrous and oxygen-free ether=1: 1: 2.3: 40 (mol ratios).Water and NaCl handle crude product, and the reuse extracted with diethyl ether is an eluant with chloroform, petroleum ether behind the filtration drying, purifies through silica gel column layer, finally obtains lurid product 4-(3-benzonitrile)-butylene.
Fig. 2 is dipole molecule 4-(3-benzonitrile)-butylene 1The HNMR spectrogram.Wherein 5.87 with the signal at 5.05ppm place corresponding to the proton hydrogen on the molecule pair keys.And 8.08,7.87,7.65 and the proton hydrogen signal peak at 7.33ppm place can belong to four proton hydrogen on the aryl.In addition, 3.08 with the proton hydrogen at 2.51ppm place and two CH in the butylene 2On proton hydrogen corresponding.This proves absolutely that we have successfully synthesized the target dipole molecule.
Under inert gas shielding, 4-(3-benzonitrile)-butylene, triethoxysilane, anhydrous and oxygen-free toluene 1: 1.1: 72.3 in molar ratio (mol ratio) are added in the reaction bulb.After stirring, add platinum catalyst (2.6 * 10 -7Mmol), continue reaction 12h and get product [4-(3-benzonitrile) butyl] triethoxysilicane.
MCM-41 is added in the reaction bulb, adds dry toluene (10mL) again, treat that it fully soaks into after, add [4-(3-benzonitrile) butyl] triethoxysilicane, stir 2h under the room temperature.Wherein MCM-41 is 1: 0.015 (mol ratio) with the feed ratio of [4-(3-benzonitrile) butyl] triethoxysilicane.Product heats 24h down in 120 ℃ under vacuum after selecting the evaporation separation.Wash back drying under 80 ℃, the mesoporous silicon material that gets final product dipolar molecule-modifiedly (FMSS) successively with toluene, ethanol then.Utilize FTIR that synthetic FMSS is characterized, as shown in Figure 3, at 2840～3000cm -1The stretching vibration peak of C-H appears in the place, at 1300～1500cm -1The infrared vibration peak of C-C key appears in the place.Simultaneously at 797cm -1The place vibration peak of Si-C key occurred and in the vibration peak of the Si-O-Si of 1078cm-1 place key, and these are all strong shows in the MCM-41 mesoporous material that successful group has been loaded onto dipole molecule.
MCM and FMSS sample are depressed to the small pieces (d=12cm) of 0.1g respectively at the pressure of 3MPa, get a slice and be placed on the electrochemistry workbench, measure its impedance spectrum, calculate dielectric constant then.For measuring the impedance spectrum of dipole molecule, we are added in the dipole molecule drips of solution on the mesoporous material MCM sample, obtain sample MCMH, and sample is placed on the laboratory table, survey its impedance spectrum, calculate dielectric constant.Like Fig. 4 and shown in Figure 5, the dielectric constant of FMSS and dielectric absorption all reduce with the increase of electric field frequency.Can find out that by Fig. 5 the FMSS sample has two relaxation processes, less than 10 3What Hz was stronger is the directed relaxation of dipole of dipole molecule chain, and 10 4Near the Hz more weak is the directed relaxation of end cyanic acid in rotary course.Being parallel to the strong intrinsic dipole of molecular long axis direction just because of dipole molecule end cyanic acid makes functional device have good electric field response.
Embodiment 2
In the NaOH concentrated solution, add a certain amount of CTAB, 80 ℃ add silicon dioxide after being stirred to clear liquid, are transferred to then in the water heating kettle, in 115 ℃ baking oven, heat 24h, take out after-filtration, washing, dry mesoporous silicon crude product PMCM.The raw material ratio that add this moment is: 1SiO 2: 0.05NaOH: 0.1CTAB: 20H 2O (mol ratio).PMCM places ethanol with crude product, adds an amount of HCl (1M) again, and reflux 8h filters, washing, oven dry get final product the MCM-41 mesoporous material.This moment, ethanol was about 10: 1 (volume ratio) with HCl feed ratio.
4-bromo-1-butylene, anhydrous and oxygen-free ether and t-butyl lithium are joined in the Schlenk reaction bulb under the argon gas protection, react 2h down at-78 ℃.The diethyl ether solution that under inert gas shielding, dropwise adds 3-bromo-benzene nitrile then behind reaction 4h under-78 ℃, rises to room temperature automatically with reaction system and finishes reaction.The feed ratio is: 4-bromo-1-butylene: 3-bromo-benzene nitrile: t-butyl lithium: anhydrous and oxygen-free ether=1: 1: 2.3: 40 (mol ratios).Water and NaCl handle crude product, and the reuse extracted with diethyl ether is an eluant with chloroform, petroleum ether behind the filtration drying, purifies through silica gel column layer, finally obtains lurid product 4-(3-benzonitrile)-butylene.
Under inert gas shielding, 4-(3-benzonitrile)-butylene, triethoxysilane, anhydrous and oxygen-free toluene 1: 1.1: 72.3 in molar ratio (mol ratio) are added in the reaction bulb.After stirring, add platinum catalyst (2.6 * 10 -7Mmol), continue reaction 12h and get product [4-(3-benzonitrile) butyl] triethoxysilicane.
MCM-41 is added in the reaction bulb, adds dry toluene (10mL) again, treat that it fully soaks into after, add [4-(3-benzonitrile) butyl] triethoxysilicane, stir 2h under the room temperature.Wherein MCM-41 is 1: 0.015 (mol ratio) with the feed ratio of [4-(3-benzonitrile) butyl] triethoxysilicane.Product heats 24h down in 120 ℃ under vacuum after selecting the evaporation separation.Wash back drying under 80 ℃ successively with toluene, ethanol then, the mesoporous silicon material that gets final product dipolar molecule-modifiedly is designated as FMSS.
Join in the saturated hexane solution of ibuprofen after exsiccant FMSS weighed, stirring reaction 24h realizes the load to medicine.FMSS behind the drug loading is placed in 60 ℃ of baking ovens dry through separation, washing.It is subsequent use then dried sample to be pressed into the small pieces of diameter 6cm.
Weightless (TG-DTA) analytical curve of the thermogravimetric of the FMSS (IBU-FMSS) of sample MCM-41, FMSS, IBU load-differential thermal such as Fig. 6, Fig. 7 and shown in Figure 8.Sample is owing to removing of physical absorption water and impurity produces in the weightlessness below 180 ℃.To sample MCM-41, be to cause 180～300 ℃ weightlessness, and mainly be because the desorption of bound water causes in the weightlessness more than 300 ℃ owing to the impurity of mesopore orbit internal adsorption breaks away from.For sample F MSS, 180～300 ℃ weightlessness mainly is because the thermal decomposition desorption of dipole molecule causes, and mainly is because the desorption of bound water and the burning of dipole molecule cause jointly in 7.8% weightlessness more than 300 ℃.The content of dipole molecule reaches more than 5% in this functions nano-device.For sample IBU-FMSS, mainly be because the decomposition of ibuprofen pharmaceutical causes between 180～300 ℃, can get the drug loading amount and be about 35.6%.
Sample behind the medicine carrying is placed in the middle of the silver electrode of good seal, immerses in 37 ℃ the simulated body fluid.Apply the square-wave voltage of 0Hz, every setting-up time is taken a sample for detection of drugs concentration, and replenishes with the fresh solution of equal volume.Drug level is detected by the UV:Vis spectrophotometer, and characteristic absorption is about 265nm.
The little angle XRD figure sheet of the FMSS (Released-IBU-FMSS) of the IBU load behind sample mesoporous silicon material MCM-41, FMSS, IBU-FMSS, the drug release is as shown in Figure 9.It is thus clear that synthesising mesoporous silicon materials MCM-41 has the characteristic diffraction peak of mesoporous material in (100), (110) and (200) direction.And FMSS decreases than the FMSS diffraction peak intensity than MCM-4, IBU-FMSS, and this is because the dipole molecule of modifying in the duct and the drug molecule of absorption cause slackening of sample X-ray diffraction.And still having characteristic diffraction peak interpret sample pore passage structure behind drug release of mesoporous material, the Released-IBU-FMSS sample still remains intact.
Figure 10 and Figure 11 have provided the N of sample mesoporous silicon material MCM-41, FMSS, IBU-FMSS and Released-IBU-FMSS respectively 2Adsorption-desorption isothermal line and corresponding pore size distribution curve.It is thus clear that, in load after the IBU molecule, the N2 adsorbance of IBU-FMSS sample sharply descends, and shows that storage has a lot of drug molecules to make the specific surface area S of sample in the mesoporous material duct BETDrop to 150m by 977 2/ g, pore volume also drops to 0.226cm by 0.936 3/ g.This point can be found out also that by pore-size distribution behind the IBU drug loading, the most probable aperture size of sample IBU-FMSS is 2.51nm, and behind drug release, the most probable aperture size of Released-IBU-FMSS sample is increased to 2.73nm again.
Figure 12 is the drug release behavior of FMSS under the 0Hz extra electric field behind the medicine carrying, and is visible by figure, and this moment, the rate of release of delivery system was comparatively slow, and 8h reaches and only reaches 62% drug release.This is that dipole molecule is owing to molecular thermalmotion owing to do not having in the presence of the extra electric field, and dipole is impartial to the effect of all directions, does not have the reason of performance " agitator " effect.Peppas equation model by the drug release behavior of IBU-FMSS among Figure 13 is visible, and this moment, drug diffusion coefficient n was 0.5, is typical Fick flooding mechanism.
Embodiment 3
In the NaOH concentrated solution, add a certain amount of CTAB, 80 ℃ add silicon dioxide after being stirred to clear liquid, are transferred to then in the water heating kettle, in 115 ℃ baking oven, heat 24h, take out after-filtration, washing, dry mesoporous silicon crude product PMCM.The raw material ratio that add this moment is: 1SiO 2: 0.05NaOH: 0.1CTAB: 20H 2O (mol ratio).PMCM places ethanol with crude product, adds an amount of HCl (1M) again, and reflux 8h filters, washing, oven dry get final product the MCM-41 mesoporous material.This moment, ethanol was about 10: 1 (volume ratio) with HCl feed ratio.
4-bromo-1-butylene, anhydrous and oxygen-free ether and t-butyl lithium are joined in the Schlenk reaction bulb under the argon gas protection, react 2h down at-78 ℃.The diethyl ether solution that under inert gas shielding, dropwise adds 3-bromo-benzene nitrile then behind reaction 4h under-78 ℃, rises to room temperature automatically with reaction system and finishes reaction.The feed ratio is: 4-bromo-1-butylene: 3-bromo-benzene nitrile: t-butyl lithium: anhydrous and oxygen-free ether=1: 1: 2.3: 40 (mol ratios).Water and NaCl handle crude product, and the reuse extracted with diethyl ether is an eluant with chloroform, petroleum ether behind the filtration drying, purifies through silica gel column layer, finally obtains lurid product 4-(3-benzonitrile)-butylene.
Under inert gas shielding, 4-(3-benzonitrile)-butylene, triethoxysilane, anhydrous and oxygen-free toluene 1: 1.1: 72.3 in molar ratio (mol ratio) are added in the reaction bulb.After stirring, add platinum catalyst (2.6 * 10 -7Mmol), continue reaction 12h and get product [4-(3-benzonitrile) butyl] triethoxysilicane.
MCM-41 is added in the reaction bulb, adds dry toluene (10mL) again, treat that it fully soaks into after, add [4-(3-benzonitrile) butyl] triethoxysilicane, stir 2h under the room temperature.Wherein MCM-41 is 1: 0.015 (mol ratio) with the feed ratio of [4-(3-benzonitrile) butyl] triethoxysilicane.Product heats 24h down in 120 ℃ under vacuum after selecting the evaporation separation.Wash back drying under 80 ℃ successively with toluene, ethanol then, the mesoporous silicon material that gets final product dipolar molecule-modifiedly is designated as FMSS.
Join in the saturated hexane solution of ibuprofen after exsiccant FMSS weighed, stirring reaction 24h realizes the load to medicine.FMSS behind the drug loading is placed in 60 ℃ of baking ovens dry through separation, washing.It is subsequent use then dried sample to be pressed into the small pieces of diameter 6cm.Sample behind the medicine carrying is placed in the middle of the silver electrode of good seal, immerses in 37 ℃ the simulated body fluid.Apply the square-wave voltage of 0.1Hz, every setting-up time is taken a sample for detection of drugs concentration, and replenishes with the fresh solution of equal volume.Drug level is detected by the UV:Vis spectrophotometer, and characteristic absorption is about 265nm.
Figure 12 is the drug release behavior of FMSS under the 0.1Hz extra electric field behind the medicine carrying, and is visible by figure, and this moment, drug molecule IBU rate of release was very fast relatively, reached 85% drug release at 6 hours.This is that the effect that is equivalent to " agitator " causes the rapid release of carrying medicament because under the effect of alternating electric field, the dipole molecule of modification is because solid dipolar effect is done directed movement along electric field.Peppas equation model visible this moment of drug diffusion coefficient n by the drug release behavior of IBU-FMSS among Figure 13 is 0.6, is non-Fick flooding mechanism.
Embodiment 4
In the NaOH concentrated solution, add a certain amount of CTAB, 80 ℃ add silicon dioxide after being stirred to clear liquid, are transferred to then in the water heating kettle, in 115 ℃ baking oven, heat 24h, take out after-filtration, washing, dry mesoporous silicon crude product PMCM.The raw material ratio that add this moment is: 1SiO 2: 0.05NaOH: 0.1CTAB: 20H 2O (mol ratio).PMCM places ethanol with crude product, adds an amount of HCl (1M) again, and reflux 8h filters, washing, oven dry get final product the MCM-41 mesoporous material.This moment, ethanol was about 10: 1 (volume ratio) with HCl feed ratio.
4-bromo-1-butylene, anhydrous and oxygen-free ether and t-butyl lithium are joined in the Schlenk reaction bulb under the argon gas protection, react 2h down at-78 ℃.The diethyl ether solution that under inert gas shielding, dropwise adds 3-bromo-benzene nitrile then behind reaction 4h under-78 ℃, rises to room temperature automatically with reaction system and finishes reaction.The feed ratio is: 4-bromo-1-butylene: 3-bromo-benzene nitrile: t-butyl lithium: anhydrous and oxygen-free ether=1: 1: 2.3: 40 (mol ratios).Water and NaCl handle crude product, and the reuse extracted with diethyl ether is an eluant with chloroform, petroleum ether behind the filtration drying, purifies through silica gel column layer, finally obtains lurid product 4-(3-benzonitrile)-butylene.
Under inert gas shielding, 4-(3-benzonitrile)-butylene, triethoxysilane, anhydrous and oxygen-free toluene 1: 1.1: 72.3 in molar ratio (mol ratio) are added in the reaction bulb.After stirring, add platinum catalyst (2.6 * 10 -7Mmol), continue reaction 12h and get product [4-(3-benzonitrile) butyl] triethoxysilicane.
MCM-41 is added in the reaction bulb, adds dry toluene (10mL) again, treat that it fully soaks into after, add [4-(3-benzonitrile) butyl] triethoxysilicane, stir 2h under the room temperature.Wherein MCM-41 is 1: 0.015 (mol ratio) with the feed ratio of [4-(3-benzonitrile) butyl] triethoxysilicane.Product heats 24h down in 120 ℃ under vacuum after selecting the evaporation separation.Wash back drying under 80 ℃ successively with toluene, ethanol then, the mesoporous silicon material that gets final product dipolar molecule-modifiedly is designated as FMSS.
Join in the saturated SBF solution of aspirin after exsiccant FMSS weighed, stirring reaction 24h realizes the load to medicine.FMSS behind the drug loading is placed in 60 ℃ of baking ovens dry through separation, washing.It is subsequent use then dried sample to be pressed into the small pieces of diameter 6cm.Sample behind the medicine carrying is placed in the middle of the silver electrode of good seal, immerses in 37 ℃ the simulated body fluid.Apply the square-wave voltage of 1Hz, every setting-up time is taken a sample for detection of drugs concentration, and replenishes with the fresh solution of equal volume.Drug level is detected by the UV:Vis spectrophotometer, and characteristic absorption is about 296nm.
FMSS behind the medicine carrying increases than the rate of release under the 0.1Hz in the drug release behavior under the 1Hz extra electric field to some extent, and 3h can reach 90% drug release, and medicine discharges basically and finishes behind the 8h.In conjunction with embodiment 3 and 4 visible, release rate of drugs can realize regulation and control by the frequency that changes extra electric field.Peppas equation model by the drug release behavior of Asp-FMSS can know that this moment, drug release was non-Fick flooding mechanism.
Embodiment 5
With block copolymer EO 20PO 70EO 20(P123) be dissolved in an amount of HCl solution, after 35 ℃ of stirring and dissolving, after adding ethyl orthosilicate (TEOS) continues to stir 20h, its ageing 24h in 80 ℃ baking oven taken out filtration, washs.Calcine 6h down in 500 ℃ at last and get end-product SBA-15.The mass ratio that adds raw material is generally: 1TEOS: 0.47P123: 1.03HCl: 17.65H 2O.
4-bromo-1-butylene, anhydrous and oxygen-free ether and t-butyl lithium are joined in the Schlenk reaction bulb under the argon gas protection, react 2h down at-78 ℃.The diethyl ether solution that under inert gas shielding, dropwise adds 3-bromo-benzene nitrile then behind reaction 4h under-78 ℃, rises to room temperature automatically with reaction system and finishes reaction.The feed ratio is: 4-bromo-1-butylene: 3-bromo-benzene nitrile: t-butyl lithium: anhydrous and oxygen-free ether=1: 1: 2.3: 40 (mol ratios).Water and NaCl handle crude product, and the reuse extracted with diethyl ether is an eluant with chloroform, petroleum ether behind the filtration drying, purifies through silica gel column layer, finally obtains lurid product 4-(3-benzonitrile)-butylene.
Under inert gas shielding, 4-(3-benzonitrile)-butylene, triethoxysilane, anhydrous and oxygen-free toluene 1: 1.1: 72.3 in molar ratio (mol ratio) are added in the reaction bulb.After stirring, add platinum catalyst (2.6 * 10 -7Mmol), continue reaction 12h and get product [4-(3-benzonitrile) butyl] triethoxysilicane.
SBA-15 is added in the reaction bulb, adds dry toluene (10mL) again, treat that it fully soaks into after, add [4-(3-benzonitrile) butyl] triethoxysilicane, stir 24h under the room temperature.Wherein SBA-15 is 1: 0.015 (mol ratio) with the feed ratio of [4-(3-benzonitrile) butyl] triethoxysilicane.Product heats 24h down in 120 ℃ under vacuum after selecting the evaporation separation.Wash back drying under 80 ℃ successively with toluene, ethanol then, the mesoporous silicon material that gets final product dipolar molecule-modifiedly is designated as FMSS.
Join in the saturated SBF solution of aspirin after exsiccant FMSS weighed, stirring reaction 24h realizes the load to medicine.FMSS behind the drug loading is placed in 60 ℃ of baking ovens dry through separation, washing.It is subsequent use then dried sample to be pressed into the small pieces of diameter 6cm.Sample behind the medicine carrying is placed in the middle of the silver electrode of good seal, immerses in 37 ℃ the simulated body fluid.Apply the square-wave voltage of 10Hz, every setting-up time is taken a sample for detection of drugs concentration, and replenishes with the fresh solution of equal volume.Drug level is detected by the UV:Vis spectrophotometer, and characteristic absorption is about 296nm.
FMSS is similar with the rate of release under 1Hz in the drug release behavior under the 10Hz extra electric field; It is thus clear that this moment, the orientation of function dipole molecule was rotated the variation that has not caught up with electric field; Make the polar molecule can't be, thereby the rate of release of medicine is not had too big influence along the direction of an electric field normal orientation.
Embodiment 6
In the NaOH concentrated solution, add a certain amount of CTAB, 80 ℃ add silicon dioxide after being stirred to clear liquid, are transferred to then in the water heating kettle, in 115 ℃ baking oven, heat 24h, take out after-filtration, washing, dry mesoporous silicon crude product PMCM.The raw material ratio that add this moment is: 1SiO 2: 0.05NaOH: 0.1CTAB: 20H 2O (mol ratio).PMCM places ethanol with crude product, adds an amount of HCl (1M) again, and reflux 8h filters, washing, oven dry get final product the MCM-41 mesoporous material.This moment, ethanol was about 10: 1 (volume ratio) with HCl feed ratio.
4-bromo-1-butylene, anhydrous and oxygen-free ether and t-butyl lithium are joined in the Schlenk reaction bulb under the argon gas protection, react 2h down at-90 ℃.The diethyl ether solution that under inert gas shielding, dropwise adds 3-bromo-benzene nitrile then behind reaction 4h under-90 ℃, rises to room temperature automatically with reaction system and finishes reaction.The feed ratio is: 4-bromo-1-butylene: 3-bromo-benzene nitrile: t-butyl lithium: anhydrous and oxygen-free ether=1: 1: 2.3: 40 (mol ratios).Water and NaCl handle crude product, and the reuse extracted with diethyl ether is an eluant with chloroform, petroleum ether behind the filtration drying, purifies through silica gel column layer, finally obtains lurid product 4-(3-benzonitrile)-butylene.
Under inert gas shielding, 4-(3-benzonitrile)-butylene, triethoxysilane, anhydrous and oxygen-free toluene 1: 1.1: 72.3 in molar ratio (mol ratio) are added in the reaction bulb.After stirring, add platinum catalyst (2.6 * 10 -7Mmol), continue reaction 12h and get product [4-(3-benzonitrile) butyl] triethoxysilicane.
MCM-41 is added in the reaction bulb, adds dry toluene (10mL) again, treat that it fully soaks into after, add [4-(3-benzonitrile) butyl] triethoxysilicane, 0 ℃ is stirred 24h down.Wherein MCM-41 is 1: 0.1 (mol ratio) with the feed ratio of [4-(3-benzonitrile) butyl] triethoxysilicane.Product heats 24h down in 120 ℃ under vacuum after selecting the evaporation separation.Wash back drying under 240 ℃ successively with toluene, ethanol then, the mesoporous silicon material that gets final product dipolar molecule-modifiedly is designated as FMSS.
Having the percentage ratio that the grafted dipole molecule of silane end group accounts for mesoporous silicon gross mass in the products therefrom is 20wt%.
Join in the saturated SBF solution of aspirin after exsiccant FMSS weighed, stirring reaction 24h realizes the load to medicine.FMSS behind the drug loading is placed in 60 ℃ of baking ovens dry through separation, washing.It is subsequent use then dried sample to be pressed into the small pieces of diameter 6cm.Sample behind the medicine carrying is placed in the middle of the silver electrode of good seal, immerses in 37 ℃ the simulated body fluid.Apply the square-wave voltage of 1Hz, every setting-up time is taken a sample for detection of drugs concentration, and replenishes with the fresh solution of equal volume.Drug level is detected by the UV:Vis spectrophotometer, and characteristic absorption is about 296nm.
Embodiment 7
In the NaOH concentrated solution, add a certain amount of CTAB, 80 ℃ add silicon dioxide after being stirred to clear liquid, are transferred to then in the water heating kettle, in 115 ℃ baking oven, heat 24h, take out after-filtration, washing, dry mesoporous silicon crude product PMCM.The raw material ratio that add this moment is: 1SiO 2: 0.05NaOH: 0.1CTAB: 20H 2O (mol ratio).PMCM places ethanol with crude product, adds an amount of HCl (1M) again, and reflux 8h filters, washing, oven dry get final product the MCM-41 mesoporous material.This moment, ethanol was about 10: 1 (volume ratio) with HCl feed ratio.
4-bromo-1-butylene, anhydrous and oxygen-free ether and t-butyl lithium are joined in the Schlenk reaction bulb under the argon gas protection, react 2h down at 0 ℃.The diethyl ether solution that under inert gas shielding, dropwise adds 3-bromo-benzene nitrile then behind reaction 4h under 0 ℃, rises to room temperature automatically with reaction system and finishes reaction.The feed ratio is: 4-bromo-1-butylene: 3-bromo-benzene nitrile: t-butyl lithium: anhydrous and oxygen-free ether=1: 1: 2.3: 40 (mol ratios).Water and NaCl handle crude product, and the reuse extracted with diethyl ether is an eluant with chloroform, petroleum ether behind the filtration drying, purifies through silica gel column layer, finally obtains lurid product 4-(3-benzonitrile)-butylene.
Under inert gas shielding, 4-(3-benzonitrile)-butylene, triethoxysilane, anhydrous and oxygen-free toluene 1: 1.1: 72.3 in molar ratio (mol ratio) are added in the reaction bulb.After stirring, add platinum catalyst (2.6 * 10 -7Mmol), continue reaction 2h and get product [4-(3-benzonitrile) butyl] triethoxysilicane.
MCM-41 is added in the reaction bulb, adds dry toluene (10mL) again, treat that it fully soaks into after, add [4-(3-benzonitrile) butyl] triethoxysilicane, 100 ℃ are stirred 0.5h down.Wherein MCM-41 is 1: 0.005 (mol ratio) with the feed ratio of [4-(3-benzonitrile) butyl] triethoxysilicane.Product heats 24h down in 120 ℃ under vacuum after selecting the evaporation separation.Wash back drying under 30 ℃ successively with toluene, ethanol then, the mesoporous silicon material that gets final product dipolar molecule-modifiedly is designated as FMSS.
Having the percentage ratio that the grafted dipole molecule of silane end group accounts for mesoporous silicon gross mass in the products therefrom is 0.05wt%.
Join in the saturated SBF solution of aspirin after exsiccant FMSS weighed, stirring reaction 24h realizes the load to medicine.FMSS behind the drug loading is placed in 60 ℃ of baking ovens dry through separation, washing.It is subsequent use then dried sample to be pressed into the small pieces of diameter 6cm.Sample behind the medicine carrying is placed in the middle of the silver electrode of good seal, immerses in 37 ℃ the simulated body fluid.Apply the square-wave voltage of 1Hz, every setting-up time is taken a sample for detection of drugs concentration, and replenishes with the fresh solution of equal volume.Drug level is detected by the UV:Vis spectrophotometer, and characteristic absorption is about 296nm.
Embodiment 8
In the NaOH concentrated solution, add a certain amount of CTAB, 80 ℃ add silicon dioxide after being stirred to clear liquid, are transferred to then in the water heating kettle, in 115 ℃ baking oven, heat 24h, take out after-filtration, washing, dry mesoporous silicon crude product PMCM.The raw material ratio that add this moment is: 1SiO 2: 0.05NaOH: 0.1CTAB: 20H 2O (mol ratio).PMCM places ethanol with crude product, adds an amount of HCl (1M) again, and reflux 48h filters, washing, oven dry get final product the MCM-41 mesoporous material.This moment, ethanol was about 10: 1 (volume ratio) with HCl feed ratio.
4-bromo-1-butylene, anhydrous and oxygen-free ether and t-butyl lithium are joined in the Schlenk reaction bulb under the argon gas protection, react 2h down at-45 ℃.The diethyl ether solution that under inert gas shielding, dropwise adds 3-bromo-benzene nitrile then behind reaction 4h under-45 ℃, rises to room temperature automatically with reaction system and finishes reaction.The feed ratio is: 4-bromo-1-butylene: 3-bromo-benzene nitrile: t-butyl lithium: anhydrous and oxygen-free ether=1: 1: 2.3: 40 (mol ratios).Water and NaCl handle crude product, and the reuse extracted with diethyl ether is an eluant with chloroform, petroleum ether behind the filtration drying, purifies through silica gel column layer, finally obtains lurid product 4-(3-benzonitrile)-butylene.
Under inert gas shielding, 4-(3-benzonitrile)-butylene, triethoxysilane, anhydrous and oxygen-free toluene 1: 1.1: 72.3 in molar ratio (mol ratio) are added in the reaction bulb.After stirring, add platinum catalyst (2.6 * 10 -7Mmol), continue reaction 48h and get product [4-(3-benzonitrile) butyl] triethoxysilicane.
MCM-41 is added in the reaction bulb, adds dry toluene (10mL) again, treat that it fully soaks into after, add [4-(3-benzonitrile) butyl] triethoxysilicane, 60 ℃ are stirred 24h down.Wherein MCM-41 is 1: 0.075 (mol ratio) with the feed ratio of [4-(3-benzonitrile) butyl] triethoxysilicane.Product heats 24h down in 120 ℃ under vacuum after selecting the evaporation separation.Wash back drying under 180 ℃ successively with toluene, ethanol then, the mesoporous silicon material that gets final product dipolar molecule-modifiedly is designated as FMSS.
Having the percentage that the grafted dipole molecule of silane end group accounts for mesoporous silicon gross mass in the products therefrom is 10wt%.
Join in the saturated SBF solution of aspirin after exsiccant FMSS weighed, stirring reaction 24h realizes the load to medicine.FMSS behind the drug loading is placed in 60 ℃ of baking ovens dry through separation, washing.It is subsequent use then dried sample to be pressed into the small pieces of diameter 6cm.Sample behind the medicine carrying is placed in the middle of the silver electrode of good seal, immerses in 37 ℃ the simulated body fluid.Apply the square-wave voltage of 1Hz, every setting-up time is taken a sample for detection of drugs concentration, and replenishes with the fresh solution of equal volume.Drug level is detected by the UV:Vis spectrophotometer, and characteristic absorption is about 296nm.
The strong electron-withdrawing group of dipole molecule group is nitro, thiocyanogen, isothiocyano or sulfur sulfydryl among the present invention; Strong conjugation group is biphenyl or phenylacetylene base; When silane end group grafting agent was trimethoxy silane, chlorodimethyl silane or methyl dimethoxysilane, method for preparing was accomplished with reference to above embodiment.

Claims (4)

1. dipolar molecule-modified mesoporous silicon material; It is characterized in that; Process through the siliconoxygen bond coupling with mesoporous silicon by having the grafted dipole molecule of silane end group with pore passage structure; Said have the grafted dipole molecule of silane end group and account for said 0.05wt%～50wt% with mesoporous silicon gross mass of pore passage structure, and said mesoporous silicon with pore passage structure is selected from MCM-41 and SBA-15; It is said that to have the grafted dipole molecule of silane end group be [4-(3-benzonitrile) butyl] triethoxysilicane; The method for preparing of said dipolar molecule-modified mesoporous silicon material comprises the steps:
(1) preparation has grafted dipole molecule raw material of silane end group and the mesoporous silicon raw material with pore passage structure respectively;
(2) with the raw materials mix for preparing in the step (1); And react; Mixed material is that mol ratio is the mixture of 1: 0.005～0.1 MCM-41 and [4-(3-benzonitrile) butyl] triethoxysilicane, or the mixture of the SBA-15 of mol ratio 1: 0.005～0.1 and [4-(3-benzonitrile) butyl] triethoxysilicane; Be reflected under the anhydrous condition and carry out, reaction temperature is 0～100 ℃;
(3) product is cleaned and is dry.
2. the method for preparing of the described dipolar molecule-modified mesoporous silicon material of claim 1 is characterized in that, comprises the steps:
(1) preparation has grafted dipole molecule raw material of silane end group and the mesoporous silicon raw material with pore passage structure respectively;
(2) with the raw materials mix for preparing in the step (1); And react; Mixed material is that mol ratio is the mixture of 1: 0.005～0.1 MCM-41 and [4-(3-benzonitrile) butyl] triethoxysilicane, or the mixture of the SBA-15 of mol ratio 1: 0.005～0.1 and [4-(3-benzonitrile) butyl] triethoxysilicane; Be reflected under the anhydrous condition and carry out, reaction temperature is 0～100 ℃;
(3) product is cleaned and is dry.
3. method for preparing as claimed in claim 2 is characterized in that, in the step (1), said to have the grafted dipole molecule raw material of silane end group be that dipole molecule and silane end group are synthetic under inert gas shielding, and synthesis temperature is-90～0 ℃.
4. method for preparing as claimed in claim 2 is characterized in that, in the step (3), baking temperature is 30～240 ℃.
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