CN104310409B - Functionalized polymer is in mesoporous nano silicon dioxide surface-assembled and de-assembly method - Google Patents
Functionalized polymer is in mesoporous nano silicon dioxide surface-assembled and de-assembly method Download PDFInfo
- Publication number
- CN104310409B CN104310409B CN201410538526.5A CN201410538526A CN104310409B CN 104310409 B CN104310409 B CN 104310409B CN 201410538526 A CN201410538526 A CN 201410538526A CN 104310409 B CN104310409 B CN 104310409B
- Authority
- CN
- China
- Prior art keywords
- functionalized polymer
- silicon dioxide
- nano silicon
- pyrocatechol
- mesoporous nano
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 174
- 229920000642 polymer Polymers 0.000 title claims abstract description 91
- 235000012239 silicon dioxide Nutrition 0.000 title claims abstract description 79
- 239000005543 nano-size silicon particle Substances 0.000 title claims abstract description 74
- 238000000034 method Methods 0.000 title claims abstract description 18
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 claims abstract description 131
- 239000007864 aqueous solution Substances 0.000 claims abstract description 48
- 150000001455 metallic ions Chemical class 0.000 claims abstract description 17
- 229910052814 silicon oxide Inorganic materials 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000002360 preparation method Methods 0.000 claims abstract description 8
- 238000005119 centrifugation Methods 0.000 claims abstract description 6
- 230000009514 concussion Effects 0.000 claims abstract description 6
- 239000002904 solvent Substances 0.000 claims abstract description 6
- 239000003929 acidic solution Substances 0.000 claims abstract description 5
- VDGJOQCBCPGFFD-UHFFFAOYSA-N oxygen(2-) silicon(4+) titanium(4+) Chemical compound [Si+4].[O-2].[O-2].[Ti+4] VDGJOQCBCPGFFD-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims description 23
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 150000001875 compounds Chemical class 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 8
- CVEPFOUZABPRMK-UHFFFAOYSA-N 2-methylprop-2-enoic acid;styrene Chemical compound CC(=C)C(O)=O.C=CC1=CC=CC=C1 CVEPFOUZABPRMK-UHFFFAOYSA-N 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- 239000002202 Polyethylene glycol Substances 0.000 claims description 6
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- LOZMAUHOAQHYDM-UHFFFAOYSA-N n-(4-aminophenyl)-2-methylprop-2-enamide Chemical compound CC(=C)C(=O)NC1=CC=C(N)C=C1 LOZMAUHOAQHYDM-UHFFFAOYSA-N 0.000 claims description 6
- 229920001223 polyethylene glycol Polymers 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- IBGBGRVKPALMCQ-UHFFFAOYSA-N 3,4-dihydroxybenzaldehyde Chemical compound OC1=CC=C(C=O)C=C1O IBGBGRVKPALMCQ-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- 229910021645 metal ion Inorganic materials 0.000 claims description 4
- 241000282326 Felis catus Species 0.000 claims description 3
- 238000001354 calcination Methods 0.000 claims description 3
- 238000012545 processing Methods 0.000 claims description 3
- PCYGLFXKCBFGPC-UHFFFAOYSA-N 3,4-Dihydroxy hydroxymethyl benzene Natural products OCC1=CC=C(O)C(O)=C1 PCYGLFXKCBFGPC-UHFFFAOYSA-N 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 238000007334 copolymerization reaction Methods 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 5
- 238000005516 engineering process Methods 0.000 abstract description 3
- 229960001866 silicon dioxide Drugs 0.000 description 54
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 10
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 230000005540 biological transmission Effects 0.000 description 6
- 239000003999 initiator Substances 0.000 description 5
- 239000000178 monomer Substances 0.000 description 5
- 239000000377 silicon dioxide Substances 0.000 description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 230000008014 freezing Effects 0.000 description 4
- 238000007710 freezing Methods 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 239000003814 drug Substances 0.000 description 3
- 229940079593 drug Drugs 0.000 description 3
- 238000012377 drug delivery Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 230000005587 bubbling Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000004043 responsiveness Effects 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- 239000013076 target substance Substances 0.000 description 2
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 1
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 description 1
- 229920000858 Cyclodextrin Polymers 0.000 description 1
- 101100373011 Drosophila melanogaster wapl gene Proteins 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 238000012637 gene transfection Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000002077 nanosphere Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 210000004483 pasc Anatomy 0.000 description 1
- 229910021426 porous silicon Inorganic materials 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- VVWRJUBEIPHGQF-UHFFFAOYSA-N propan-2-yl n-propan-2-yloxycarbonyliminocarbamate Chemical compound CC(C)OC(=O)N=NC(=O)OC(C)C VVWRJUBEIPHGQF-UHFFFAOYSA-N 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- HFHDHCJBZVLPGP-UHFFFAOYSA-N schardinger α-dextrin Chemical compound O1C(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(O)C2O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC2C(O)C(O)C1OC2CO HFHDHCJBZVLPGP-UHFFFAOYSA-N 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 230000005476 size effect Effects 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 230000035924 thermogenesis Effects 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
Landscapes
- Silicon Compounds (AREA)
- Medicinal Preparation (AREA)
- Catalysts (AREA)
Abstract
Functionalized polymer, in mesoporous nano silicon dioxide surface-assembled and de-assembly method, belongs to field of nanometer material technology.Water is solvent, the preparation of nano mesoporous silicon oxide aqueous solution, the pyrocatechol functionalized polymer aqueous solution, aqueous metallic ions, by the pyrocatechol functionalized polymer aqueous solution, aqueous metallic ions adds in the mesoporous nano silicon dioxide aqueous solution successively, pyrocatechol functionalized polymer and metallic ion coordination after concussion, assembling is realized on mesoporous nano silicon dioxide surface, obtain the mesoporous nano silicon dioxide aqueous solution of coated pyrocatechol functionalized polymer, centrifugation, the mesoporous nano silicon dioxide of coated pyrocatechol functionalized polymer is dispersed in water again, in the mesoporous nano silicon dioxide aqueous solution of coated pyrocatechol functionalized polymer, add acidic solution regulates pH to 5 ~ 6, pyrocatechol functionalized polymer can be made in meso-porous titanium dioxide silicon face generation de-assembly.
Description
Technical field
The invention belongs to field of nanometer material technology, particularly the assembling of a kind of pyrocatechol functionalized polymer on silicon dioxide nanosphere surface and de-assembly behavior.
Background technology
From the people such as Kresge in 1992 the reported first ordered mesoporous silicon-dioxide material of a kind of MCM-41 by name on Nature magazine, the research of mesoporous silicon oxide becomes rapidly international focus.The appearance of ordered meso-porous silicon oxide is the once leap in molecular sieve and porous mass development history.
Meso-porous nano silicon-dioxide can form hybrid inorganic-organic materials with organic or macromolecular material, so both can play the small-size effect of himself, surface and interface effect, quantum size effect.Meanwhile, different modifying method can give again material other performances diversified.Thus have a wide range of applications in catalysis, drug delivery and Co ntrolled release, gene transfection, heavy metal ion and biomolecule detection etc.
In drug delivery and Co ntrolled release field, mesoporous silicon oxide has development space widely as drug molecule carrier, but how effectively encapsulates the duct of mesoporous silicon oxide and deblocking is the focus of research at present.And be mainly chemical modification for the method for mesoporous silicon oxide finishing at present, namely by chemical bond, some responsive polymer is modified mesoporous silicon surface.(the ChiyoungPark such as ChiyoungPark, KyounghoOhetal.Angew.Chem.Int.Ed.2007,46,1455 – 1457) utilize APTES first to carry out surface modification to mesoporous silicon dioxide nano particle, make its surface with amino, and then recycling contains the polymkeric substance of end carboxyl and amido modified meso-porous titanium dioxide pasc reaction, at mesoporous silicon oxide finishing one deck responsive polymer, the drug molecule in controllable release mesoporous silicon oxide duct.(the HuanMeng such as Zink, MinXue, TianXiaetal.J.Am.Chem.Soc.2010,132 (36), 12690 – 12697) first with the MBI finishing mesoporous silicon oxide containing arylamine, being nested in by cyclodextrin molecular on MBI adds a cover on mesoporous hole again, and encapsulated drug molecule forms the drug delivery system with pH responsiveness.
To sum up, the method at present for mesoporous silicon oxide finishing is all too loaded down with trivial details, and a kind of polymkeric substance that can realize quickly and easily has no report in the method for the assembling of mesoporous silicon dioxide nano microsphere surface and de-assembly.
Summary of the invention
The object of the present invention is to provide a kind of functionalized polymer in mesoporous nano silicon dioxide surface-assembled and de-assembly method.
Described functionalized polymer is pyrocatechol functionalized polymer, described pyrocatechol functionalized polymer is the polymkeric substance containing two hydroxyl phenol structure, be designated as PEGMA-co-PMAAPHBA, obtain by modifying through 3,4-Dihydroxy benzaldehyde after N-(4 aminophenyl)-Methacrylamide and polyethylene glycol methacrylate-styrene polymer random copolymerization.
The preparation method of described functionalized polymer is with reference to Chinese patent 201410032517.9, and concrete steps are as follows:
(1) suitable solvent is selected, preparation monomer solution, by metering than adding initiator, the solution of N-(4 aminophenyl)-Methacrylamide and polyethylene glycol methacrylate-styrene polymer and initiator is placed in freezing degassed and lower 65 ~ 80 DEG C of reaction 24h of sealing after being filled with argon gas of reaction vessel, liquid nitrogen freezing 2min stopped reaction after polymerization;
(2) dissolving precipitated method is adopted to remove unreacted monomer, by precipitation agent precipitation after solubilizing agent dilution, dry.
(3) polymkeric substance obtained in step (2) is got 0.2 ~ 1g to be dissolved in 2 ~ 6ml methylene dichloride and to be made into solution A, 0.1 ~ 1g3,4-Dihydroxy benzaldehyde is dissolved in 0.5 ~ 2mL methanol solution and is made into B solution;
(4) by A, B two solution N
2after bubbling 15min, B solution is injected solution A and reacts 12h, reaction terminates rear washed with dichloromethane, suction filtration, drying, obtains target substance.
In step (1), described solvent can be tetrahydrofuran (THF), Isosorbide-5-Nitrae-dioxane etc., preferred tetrahydrofuran (THF) (THF); Described monomer concentration scope is 0.3 ~ 1.0mol/L; The scope of the mol ratio of described monomer polyethylene glycol methacrylate-styrene polymer and N-(4 aminophenyl)-Methacrylamide is 1 ~ 4; Described initiator is the compound that can add thermogenesis free radical and cause polyethylene glycol methacrylate-styrene polymer and the polymerization of N-(4 aminophenyl)-Methacrylamide, preferred Diisopropyl azodicarboxylate (AIBN); The scope of the mol ratio of described monomer and initiator is 50 ~ 100.
In step (2), described precipitation agent can be selected from the one in normal hexane, sherwood oil, methyl alcohol etc., preferred normal hexane.
Described functionalized polymer, in mesoporous nano silicon dioxide surface-assembled and de-assembly method, comprises the following steps:
(1) select water as solvent, the preparation of nano mesoporous silicon oxide aqueous solution, the pyrocatechol functionalized polymer aqueous solution, aqueous metallic ions;
(2) the pyrocatechol functionalized polymer aqueous solution, aqueous metallic ions are added in the mesoporous nano silicon dioxide aqueous solution successively, pyrocatechol functionalized polymer and metallic ion coordination after concussion, realize assembling on mesoporous nano silicon dioxide surface, obtain the mesoporous nano silicon dioxide aqueous solution of coated pyrocatechol functionalized polymer;
(3) the mesoporous nano silicon dioxide aqueous solution centrifugation of coated pyrocatechol functionalized polymer step (2) obtained, the mesoporous nano silicon dioxide of coated pyrocatechol functionalized polymer is dispersed in water again, in the mesoporous nano silicon dioxide aqueous solution of coated pyrocatechol functionalized polymer, add acidic solution regulates pH to 5 ~ 6, and pyrocatechol functionalized polymer can be made in meso-porous titanium dioxide silicon face generation de-assembly.
In step (1), described mesoporous nano silicon dioxide can be prepared as follows:
A. the cats product of 0.3 ~ 0.9g is joined in 40 ~ 60mLPBS buffered soln, at 95 DEG C, stir 30min;
B. 0.5 ~ 1.0g tetraethyl orthosilicate (TEOS) is added drop-wise to the solution in step a, stirring reaction 6 ~ 10h at 95 DEG C;
C. end is reacted, centrifugal, by throw out drying treatment 1.5h under the condition of 50 DEG C, be then calcination processing 6h under the condition of 550 DEG C in temperature, obtain mesoporous nano silicon dioxide;
In step (1), the mass concentration of described mesoporous nano silicon dioxide solution can be 2 ~ 10mg/mL, and the mass concentration of polymers soln can be 2 ~ 10mg/mL, and the mass concentration of metal ion solution can be 10 ~ 20mg/mL; Described metal ion can be containing Fe
3+, Zn
2+compound, described containing Fe
3+compound can be selected from FeCl
3or Fe
2(SO
4)
3deng; Described containing Zn
2+compound can be selected from ZnCl
2or Zn (SO
4)
2deng; Preferred FeCl
3.
In step (2), the volume ratio of the described pyrocatechol functionalized polymer aqueous solution, aqueous metallic ions, the mesoporous nano silicon dioxide aqueous solution can be (0.5 ~ 2): (0.1 ~ 1): (1 ~ 2).
In step (3), described acidic solution can be selected from the one in hydrochloric acid soln, acetum, phosphoric acid solution etc.
The present invention utilizes a kind of polymkeric substance (PEGMA-co-PMAAPHBA) containing pyrocatechol structure to be coated on meso-porous titanium dioxide silicon face with metal ion-chelant self-assembly, forms effective encapsulation to mesoporous silicon oxide; And the two hydroxyl on pyrocatechol and the interaction of meso-porous titanium dioxide silicon face have pH responsiveness, de-assembly can be there is in lower pH (about 5.6) environment, be convenient to mesoporous silicon oxide release guest molecule.
Accompanying drawing explanation
Fig. 1 is the Flied emission transmission electron microscope (TEM) of the mesoporous nano silicon dioxide of not coated pyrocatechol functionalized polymer in embodiment 1;
Fig. 2 is the Flied emission transmission electron microscope (TEM) of pyrocatechol functionalized polymer after mesoporous nano silicon dioxide surface-assembled in embodiment 1;
Fig. 3 is the Flied emission transmission electron microscope (TEM) of pyrocatechol functionalized polymer after the de-assembly of mesoporous nano silicon dioxide surface in embodiment 1;
Fig. 4 is the change of size figure of pyrocatechol functionalized polymer after mesoporous nano silicon dioxide surface-assembled and de-assembly in embodiment 1.
Embodiment
Embodiment will the invention will be further described by reference to the accompanying drawings below.
Embodiment 1
The preparation of PEGMA-co-PMAAPHBA:
(1) take that N-(4 aminophenyl)-Methacrylamide 0.176g and polyethylene glycol methacrylate-styrene polymer 0.475g and initiator 10mg is dissolved in 1.5mLTHF, solution is placed in freezing degassed and lower 65 ~ 80 DEG C of reaction 24h of sealing after being filled with argon gas of reaction vessel, liquid nitrogen freezing 2min stopped reaction after polymerization;
(2) by reacted solution 100mL normal hexane precipitation twice, drying.
(3) polymkeric substance obtained in step (2) is got 0.4g and be dissolved in wiring solution-forming A in 5mL methylene dichloride, 0.15g3,4-Dihydroxy benzaldehyde is dissolved in wiring solution-forming B in 1mL methanol solution;
(4) by A, B two solution N
2after bubbling 15min, B solution is injected solution A and reacts 12h, reaction terminates rear washed with dichloromethane, suction filtration, drying, obtains target substance.
The assembling of pyrocatechol functionalized polymer on mesoporous nano silicon dioxide surface and de-assembly:
1. prepare mesoporous nano silicon dioxide
(1) cats product of 0.5g is joined in 50mLPBS buffered soln, at 95 DEG C, stir 30min;
(2) 0.8g tetraethyl orthosilicate (TEOS) is slowly added drop-wise to the solution in step (1), stirring reaction 8h at 95 DEG C;
(3) reaction terminates, centrifugal, by throw out drying treatment 1.5h under the condition of 50 DEG C, is then calcination processing 6h under the condition of 550 DEG C in temperature, obtains mesoporous nano silicon dioxide.
2. prepare the mesoporous nano silicon dioxide aqueous solution, the pyrocatechol functionalized polymer aqueous solution of 5g/L, the FeCl of 20g/L of 5g/L
3the aqueous solution; By pyrocatechol functionalized polymer aqueous solution 2mL, aqueous metallic ions 1mL adds in the mesoporous nano silicon dioxide aqueous solution of 2mL successively, pyrocatechol functionalized polymer and metallic ion coordination after concussion, realize assembling on mesoporous nano silicon dioxide surface, obtain the mesoporous nano silicon dioxide aqueous solution of coated pyrocatechol functionalized polymer.
3. by the mesoporous nano silicon dioxide aqueous solution centrifugation of the coated pyrocatechol functionalized polymer in 2, the mesoporous nano silicon dioxide of the coated pyrocatechol functionalized polymer obtained is dispersed in water again, in the mesoporous nano silicon dioxide aqueous solution of the coated pyrocatechol functionalized polymer of 1mL, adds hydrochloric acid soln regulate pH can realize the de-assembly of pyrocatechol functionalized polymer on mesoporous nano silicon dioxide surface to 5.0.
In embodiment 1, the Flied emission transmission electron microscope (TEM) of the mesoporous nano silicon dioxide of not coated pyrocatechol functionalized polymer is see Fig. 1, the Flied emission transmission electron microscope (TEM) of pyrocatechol functionalized polymer after mesoporous nano silicon dioxide surface-assembled is see Fig. 2, the Flied emission transmission electron microscope (TEM) of pyrocatechol functionalized polymer after the de-assembly of mesoporous nano silicon dioxide surface is see Fig. 3, and the change of size figure of pyrocatechol functionalized polymer after mesoporous nano silicon dioxide surface-assembled and de-assembly is see Fig. 4.
Embodiment 2
1. with reference to polymer P EGMA-co-PMAAPHBA and the mesoporous nano silicon dioxide of embodiment 1 preparation.
2. prepare the mesoporous nano silicon dioxide aqueous solution, the pyrocatechol functionalized polymer aqueous solution of 5g/L, the FeCl of 20g/L of 5g/L
3the aqueous solution; By pyrocatechol functionalized polymer aqueous solution 1.5mL, aqueous metallic ions 0.5mL adds in the mesoporous nano silicon dioxide aqueous solution of 2mL successively, pyrocatechol functionalized polymer and metallic ion coordination after concussion, realize assembling on mesoporous nano silicon dioxide surface, obtain the mesoporous nano silicon dioxide aqueous solution of coated pyrocatechol functionalized polymer.
3. by the mesoporous nano silicon dioxide aqueous solution centrifugation of the coated pyrocatechol functionalized polymer in 2, the mesoporous nano silicon dioxide of the coated pyrocatechol functionalized polymer obtained is dispersed in water again, in the mesoporous nano silicon dioxide aqueous solution of the coated pyrocatechol functionalized polymer of 1mL, adds acetum regulate pH can realize the de-assembly of pyrocatechol functionalized polymer on mesoporous nano silicon dioxide surface to 5.5.
Embodiment 3
1. with reference to polymer P EGMA-co-PMAAPHBA and the mesoporous silicon oxide of embodiment 1 preparation.
2. prepare the mesoporous nano silicon dioxide aqueous solution, the pyrocatechol functionalized polymer aqueous solution of 5g/L, the FeCl of 20g/L of 5g/L
3the aqueous solution; By pyrocatechol functionalized polymer aqueous solution 1.5mL, aqueous metallic ions 0.4mL adds in the mesoporous nano silicon dioxide aqueous solution of 1.5mL successively, pyrocatechol functionalized polymer and metallic ion coordination after concussion, realize assembling on mesoporous nano silicon dioxide surface, obtain the mesoporous nano silicon dioxide aqueous solution of coated pyrocatechol functionalized polymer.
3. by the mesoporous nano silicon dioxide aqueous solution centrifugation of the coated pyrocatechol functionalized polymer in 2, the mesoporous nano silicon dioxide of the coated pyrocatechol functionalized polymer obtained is dispersed in water again, in the mesoporous nano silicon dioxide aqueous solution of the coated pyrocatechol functionalized polymer of 1mL, adds acetum regulate pH can realize the de-assembly of pyrocatechol functionalized polymer on mesoporous nano silicon dioxide surface to 6.0.
Claims (7)
1. functionalized polymer is in mesoporous nano silicon dioxide surface-assembled and de-assembly method, it is characterized in that described functionalized polymer is pyrocatechol functionalized polymer, described pyrocatechol functionalized polymer is the polymkeric substance containing two hydroxyl phenol structure, be designated as PEGMA-co-PMAAPHBA, obtain by modifying through 3,4-Dihydroxy benzaldehyde after N-(4 aminophenyl)-Methacrylamide and polyethylene glycol methacrylate-styrene polymer random copolymerization;
Described functionalized polymer, in mesoporous nano silicon dioxide surface-assembled and de-assembly method, comprises the following steps:
(1) select water as solvent, the preparation of nano mesoporous silicon oxide aqueous solution, the pyrocatechol functionalized polymer aqueous solution, aqueous metallic ions; The mass concentration of described mesoporous nano silicon dioxide solution is 2 ~ 10mg/mL, and the mass concentration of polymers soln is 2 ~ 10mg/mL, and the mass concentration of metal ion solution is 10 ~ 20mg/mL;
(2) the pyrocatechol functionalized polymer aqueous solution, aqueous metallic ions are added in the mesoporous nano silicon dioxide aqueous solution successively, pyrocatechol functionalized polymer and metallic ion coordination after concussion, realize assembling on mesoporous nano silicon dioxide surface, obtain the mesoporous nano silicon dioxide aqueous solution of coated pyrocatechol functionalized polymer; The volume ratio of the described pyrocatechol functionalized polymer aqueous solution, aqueous metallic ions, the mesoporous nano silicon dioxide aqueous solution is (0.5 ~ 2): (0.1 ~ 1): (1 ~ 2);
(3) the mesoporous nano silicon dioxide aqueous solution centrifugation of coated pyrocatechol functionalized polymer step (2) obtained, the mesoporous nano silicon dioxide of coated pyrocatechol functionalized polymer is dispersed in water again, in the mesoporous nano silicon dioxide aqueous solution of coated pyrocatechol functionalized polymer, add acidic solution regulates pH to 5 ~ 6, makes pyrocatechol functionalized polymer in meso-porous titanium dioxide silicon face generation de-assembly.
2. functionalized polymer, in mesoporous nano silicon dioxide surface-assembled and de-assembly method, is characterized in that described mesoporous nano silicon dioxide is prepared as follows in step (1) as claimed in claim 1:
A. the cats product of 0.3 ~ 0.9g is joined in 40 ~ 60mLPBS buffered soln, at 95 DEG C, stir 30min;
B. 0.5 ~ 1.0g tetraethyl orthosilicate (TEOS) is added drop-wise to the solution in step a, stirring reaction 6 ~ 10h at 95 DEG C;
C. end is reacted, centrifugal, by throw out drying treatment 1.5h under the condition of 50 DEG C, be then calcination processing 6h under the condition of 550 DEG C in temperature, obtain mesoporous nano silicon dioxide.
3. functionalized polymer, in mesoporous nano silicon dioxide surface-assembled and de-assembly method, is characterized in that in step (1) as claimed in claim 1, and described metal ion is for containing Fe
3+, Zn
2+compound.
4. functionalized polymer, in mesoporous nano silicon dioxide surface-assembled and de-assembly method, is characterized in that described containing Fe as claimed in claim 3
3+compound be selected from FeCl
3or Fe
2(SO
4)
3.
5. functionalized polymer, in mesoporous nano silicon dioxide surface-assembled and de-assembly method, is characterized in that described containing Fe as claimed in claim 4
3+compound be FeCl
3.
6. functionalized polymer, in mesoporous nano silicon dioxide surface-assembled and de-assembly method, is characterized in that described containing Zn as claimed in claim 3
2+compound be selected from ZnCl
2or Zn (SO
4)
2.
7. functionalized polymer, in mesoporous nano silicon dioxide surface-assembled and de-assembly method, is characterized in that described acidic solution is selected from the one in hydrochloric acid soln, acetum, phosphoric acid solution in step (3) as claimed in claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410538526.5A CN104310409B (en) | 2014-10-14 | 2014-10-14 | Functionalized polymer is in mesoporous nano silicon dioxide surface-assembled and de-assembly method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410538526.5A CN104310409B (en) | 2014-10-14 | 2014-10-14 | Functionalized polymer is in mesoporous nano silicon dioxide surface-assembled and de-assembly method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104310409A CN104310409A (en) | 2015-01-28 |
| CN104310409B true CN104310409B (en) | 2016-02-17 |
Family
ID=52365763
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410538526.5A Expired - Fee Related CN104310409B (en) | 2014-10-14 | 2014-10-14 | Functionalized polymer is in mesoporous nano silicon dioxide surface-assembled and de-assembly method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104310409B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104826119B (en) * | 2015-04-16 | 2018-04-24 | 厦门大学 | The preparation of the mesoporous silicon oxide@polymer drug carriers of pH and glucose doubling sensitivity |
| CN111557306B (en) * | 2020-05-21 | 2021-05-18 | 中国热带农业科学院南亚热带作物研究所 | Nano-drug preparation and application thereof in prevention and control of banana vascular wilt |
| CN113387365B (en) * | 2021-07-19 | 2022-08-19 | 安徽瑞联节能科技股份有限公司 | Method for organically modifying nano silicon dioxide aerogel |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4732887A (en) * | 1984-10-12 | 1988-03-22 | Asahi Kasei Kogyo Kabushiki Kaisha | Composite porous material, process for production and separation of metallic element |
| DE19847630A1 (en) * | 1998-10-15 | 2000-04-20 | Basf Ag | Silica having mesopores and micropores, useful for making catalysts, catalyst supports or carriers for pharmacologically active substances, enzymes or pigments |
| CN102642843B (en) * | 2012-05-10 | 2014-07-16 | 北京理工大学 | Method for simultaneously preparing multilevel-structure mesoporous silicon dioxide and carbon nano material |
| CN103239728A (en) * | 2013-04-28 | 2013-08-14 | 天津大学 | Polycation surface-modified large-pore and mesoporous silicon nanoparticle, complex of nanoparticle and nucleic acid and application of nanoparticle |
| CN103755980B (en) * | 2014-01-24 | 2015-12-09 | 厦门大学 | A kind of preparation method of autofluorescence nano-micelle |
| CN103803565B (en) * | 2014-02-11 | 2015-09-09 | 厦门大学 | A kind of preparation method of monodispersity hollow mesoporous silicon dioxide nano particle |
-
2014
- 2014-10-14 CN CN201410538526.5A patent/CN104310409B/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN104310409A (en) | 2015-01-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Zheng et al. | Polydopamine coatings in confined nanopore space: toward improved retention and release of hydrophilic cargo | |
| Shen et al. | Molecular imprinting in Pickering emulsions: a new insight into molecular recognition in water | |
| Liu et al. | pH-mediated fluorescent polymer particles and gel from hyperbranched polyethylenimine and the mechanism of intrinsic fluorescence | |
| CN104310409B (en) | Functionalized polymer is in mesoporous nano silicon dioxide surface-assembled and de-assembly method | |
| Zhang et al. | Polymeric core–shell assemblies mediated by host–guest interactions: versatile nanocarriers for drug delivery | |
| Wan et al. | pH‐disintegrable polyelectrolyte multilayer‐coated mesoporous silica nanoparticles exhibiting triggered co‐release of cisplatin and model drug molecules | |
| Tudisco et al. | Cyclodextrin anchoring on magnetic Fe3O4 nanoparticles modified with phosphonic linkers | |
| SG173455A1 (en) | Hollow silica particle with a polymer thereon | |
| CN105713046B (en) | A kind of platinum antineoplastic pro-drug, nano-hydrogel drug and preparation method thereof | |
| WO2011099932A1 (en) | Smart polymers functionalized hollow silica vesicles | |
| CN104826119A (en) | Preparation method of pH and glucose dual-sensitive mesoporous silica@polymer drug carrier | |
| CN102294040B (en) | Magnetic nanometer polymer vesicle for magnetic resonance imaging and medicine carrier and preparation method of magnetic nanometer polymer vesicle | |
| Chen et al. | Acidity and Glutathione Dual‐Responsive Polydopamine‐Coated Organic‐Inorganic Hybrid Hollow Mesoporous Silica Nanoparticles for Controlled Drug Delivery | |
| CN104436199A (en) | Preparation method of porous ferroferric oxide composite nanometre microspheres efficiently loaded with pharmorubicin | |
| Du et al. | Preparation of highly cross-linked raspberry-like nano/microspheres and surface tailoring for controlled immunostimulating peptide adsorption | |
| Morgese et al. | Ultrastable suspensions of polyoxazoline-functionalized ZnO single nanocrystals | |
| Li et al. | Novel biocompatible pH-stimuli responsive superparamagnetic hybrid hollow microspheres as tumor-specific drug delivery system | |
| Tang et al. | Electrolyte and pH-sensitive amphiphilic alginate: synthesis, self-assembly and controlled release of acetamiprid | |
| Zhang et al. | Histamine-functionalized copolymer micelles as a drug delivery system in 2D and 3D models of breast cancer | |
| Yang et al. | Multifunctional mesoporous silica nanoparticles with different morphological characteristics for in vitro cancer treatment | |
| Jin et al. | Pollen-like silica nanoparticles as a nanocarrier for tumor targeted and pH-responsive drug delivery | |
| WO2015096607A1 (en) | Poss-containing in situ composite nano-gel with magnetic responsiveness and preparation method therefor | |
| Sun et al. | Boronate ester bond-based core–shell nanocarriers with pH response for anticancer drug delivery | |
| TWI459966B (en) | Nanoparticle drug carrier, pharmaceutical composition and manufacturing method thereof | |
| CN104387591B (en) | A kind of hydrophilic polyglycol hydrophobicity poly phosphate block copolymer and its production and use |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20160217 |