CN103205006B - Surface patterning high-strength and high-toughness hybrid hydrogel membrane and preparation method thereof - Google Patents
Surface patterning high-strength and high-toughness hybrid hydrogel membrane and preparation method thereof Download PDFInfo
- Publication number
- CN103205006B CN103205006B CN201310112802.7A CN201310112802A CN103205006B CN 103205006 B CN103205006 B CN 103205006B CN 201310112802 A CN201310112802 A CN 201310112802A CN 103205006 B CN103205006 B CN 103205006B
- Authority
- CN
- China
- Prior art keywords
- tenacity
- preparation
- patterning
- patterned surface
- gel film
- 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.)
- Active
Links
- 238000000059 patterning Methods 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 239000000017 hydrogel Substances 0.000 title abstract description 28
- 239000012528 membrane Substances 0.000 title abstract description 7
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 37
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 24
- 239000010703 silicon Substances 0.000 claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000000178 monomer Substances 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 15
- 150000003839 salts Chemical class 0.000 claims abstract description 12
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims abstract description 10
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims abstract description 8
- 235000010413 sodium alginate Nutrition 0.000 claims abstract description 8
- 239000000661 sodium alginate Substances 0.000 claims abstract description 8
- 229940005550 sodium alginate Drugs 0.000 claims abstract description 8
- 229910052751 metal Inorganic materials 0.000 claims abstract description 6
- 239000002184 metal Substances 0.000 claims abstract description 6
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000004113 cell culture Methods 0.000 claims abstract description 5
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 5
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 claims abstract description 5
- 210000000130 stem cell Anatomy 0.000 claims abstract description 5
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 claims abstract description 3
- 108010025899 gelatin film Proteins 0.000 claims description 32
- 239000008367 deionised water Substances 0.000 claims description 18
- 239000000243 solution Substances 0.000 claims description 15
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 10
- QNILTEGFHQSKFF-UHFFFAOYSA-N n-propan-2-ylprop-2-enamide Chemical compound CC(C)NC(=O)C=C QNILTEGFHQSKFF-UHFFFAOYSA-N 0.000 claims description 9
- 239000012745 toughening agent Substances 0.000 claims description 9
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 claims description 8
- 239000004160 Ammonium persulphate Substances 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 claims description 6
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims description 6
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 6
- 235000019395 ammonium persulphate Nutrition 0.000 claims description 6
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 6
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims description 6
- 238000001291 vacuum drying Methods 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 4
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 claims description 4
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims description 4
- -1 vulcabond Chemical compound 0.000 claims description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 4
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 3
- 235000005121 Sorbus torminalis Nutrition 0.000 claims description 3
- 244000152100 Sorbus torminalis Species 0.000 claims description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 3
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 claims description 3
- 229910001626 barium chloride Inorganic materials 0.000 claims description 3
- 229940045511 barium chloride Drugs 0.000 claims description 3
- XZKRXPZXQLARHH-UHFFFAOYSA-N buta-1,3-dienylbenzene Chemical compound C=CC=CC1=CC=CC=C1 XZKRXPZXQLARHH-UHFFFAOYSA-N 0.000 claims description 3
- 239000001110 calcium chloride Substances 0.000 claims description 3
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 3
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 3
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 3
- 239000003814 drug Substances 0.000 claims description 3
- 230000000694 effects Effects 0.000 claims description 3
- 229910021389 graphene Inorganic materials 0.000 claims description 3
- 229910052588 hydroxylapatite Inorganic materials 0.000 claims description 3
- 239000005543 nano-size silicon particle Substances 0.000 claims description 3
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 claims description 3
- 230000001172 regenerating effect Effects 0.000 claims description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 3
- GNWBLLYJQXKPIP-ZOGIJGBBSA-N (1s,3as,3bs,5ar,9ar,9bs,11as)-n,n-diethyl-6,9a,11a-trimethyl-7-oxo-2,3,3a,3b,4,5,5a,8,9,9b,10,11-dodecahydro-1h-indeno[5,4-f]quinoline-1-carboxamide Chemical compound CN([C@@H]1CC2)C(=O)CC[C@]1(C)[C@@H]1[C@@H]2[C@@H]2CC[C@H](C(=O)N(CC)CC)[C@@]2(C)CC1 GNWBLLYJQXKPIP-ZOGIJGBBSA-N 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- 229920000877 Melamine resin Polymers 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- YYRMJZQKEFZXMX-UHFFFAOYSA-L calcium bis(dihydrogenphosphate) Chemical compound [Ca+2].OP(O)([O-])=O.OP(O)([O-])=O YYRMJZQKEFZXMX-UHFFFAOYSA-L 0.000 claims description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L calcium carbonate Substances [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 2
- NEEHYRZPVYRGPP-IYEMJOQQSA-L calcium gluconate Chemical compound [Ca+2].OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O.OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O NEEHYRZPVYRGPP-IYEMJOQQSA-L 0.000 claims description 2
- FUFJGUQYACFECW-UHFFFAOYSA-L calcium hydrogenphosphate Chemical compound [Ca+2].OP([O-])([O-])=O FUFJGUQYACFECW-UHFFFAOYSA-L 0.000 claims description 2
- MKJXYGKVIBWPFZ-UHFFFAOYSA-L calcium lactate Chemical compound [Ca+2].CC(O)C([O-])=O.CC(O)C([O-])=O MKJXYGKVIBWPFZ-UHFFFAOYSA-L 0.000 claims description 2
- 239000001527 calcium lactate Substances 0.000 claims description 2
- 229960002401 calcium lactate Drugs 0.000 claims description 2
- 235000011086 calcium lactate Nutrition 0.000 claims description 2
- 239000001506 calcium phosphate Substances 0.000 claims description 2
- 239000002041 carbon nanotube Substances 0.000 claims description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 2
- 238000010894 electron beam technology Methods 0.000 claims description 2
- 230000005251 gamma ray Effects 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Natural products OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 2
- 229910000150 monocalcium phosphate Inorganic materials 0.000 claims description 2
- 235000019691 monocalcium phosphate Nutrition 0.000 claims description 2
- 239000012802 nanoclay Substances 0.000 claims description 2
- 239000011592 zinc chloride Substances 0.000 claims description 2
- 235000005074 zinc chloride Nutrition 0.000 claims description 2
- 230000005855 radiation Effects 0.000 claims 1
- 150000003254 radicals Chemical class 0.000 claims 1
- 210000004027 cell Anatomy 0.000 abstract description 16
- 238000005516 engineering process Methods 0.000 abstract description 5
- 239000000463 material Substances 0.000 abstract description 5
- 239000003431 cross linking reagent Substances 0.000 abstract description 4
- 238000011161 development Methods 0.000 abstract description 4
- 230000018109 developmental process Effects 0.000 abstract description 4
- 238000010382 chemical cross-linking Methods 0.000 abstract description 2
- 239000002105 nanoparticle Substances 0.000 abstract description 2
- 230000008569 process Effects 0.000 abstract description 2
- 230000017423 tissue regeneration Effects 0.000 abstract description 2
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 abstract 2
- 238000003501 co-culture Methods 0.000 abstract 1
- 238000005728 strengthening Methods 0.000 abstract 1
- 239000012620 biological material Substances 0.000 description 7
- 239000000499 gel Substances 0.000 description 7
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 230000021164 cell adhesion Effects 0.000 description 3
- 230000007246 mechanism Effects 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 238000001259 photo etching Methods 0.000 description 3
- 210000001519 tissue Anatomy 0.000 description 3
- 108010037362 Extracellular Matrix Proteins Proteins 0.000 description 2
- 102000010834 Extracellular Matrix Proteins Human genes 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 210000002744 extracellular matrix Anatomy 0.000 description 2
- 238000000338 in vitro Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000002174 soft lithography Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 108010010803 Gelatin Proteins 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- 229910003978 SiClx Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 235000010443 alginic acid Nutrition 0.000 description 1
- 229920000615 alginic acid Polymers 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 210000000845 cartilage Anatomy 0.000 description 1
- 230000012292 cell migration Effects 0.000 description 1
- 230000001413 cellular effect Effects 0.000 description 1
- 230000030570 cellular localization Effects 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000004069 differentiation Effects 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 229920001600 hydrophobic polymer Polymers 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000033001 locomotion Effects 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 230000000638 stimulation Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Landscapes
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Graft Or Block Polymers (AREA)
Abstract
With the continuous development of tissue engineering, a surface patterning technology is concerned by people more and more and widely applied; and a micro-patterning technology is already used for accurately controlling the position and form of a cell and the co-culture of multiple cells, but a micro-pattern is more difficult to be directly constructed on the surface of hydrogel with good biocompatibility. The high-elasticity and high-toughness patterning hydrogel membrane is prepared on a patterning silicon slice base body by taking sodium alginate as a high-molecular framework, acrylamide and a derivative thereof as polymerization monomers, divinylbenzene, N,N'-methylene bisacrylamide or ethylene glycol dimethacrylate as chemical cross-linking agents and a metal salt water solution as an ionic cross-linking agent and adding inorganic nanoparticles as strengthening agents. The preparation method disclosed by the invention has the advantages of good controllability, simple process, low cost, good material biocompatibility, and the like; and the patterning hydrogel membrane disclosed by the invention is hopeful to be applied to the fields of stem cell culture, tissue regeneration, and the like.
Description
Technical field
The present invention relates to a kind of patterned surface high-intensity high-tenacity hybrid gel film and preparation method thereof, belong to functional materials and technical field of biological material.
Background technology
In recent years along with the development of organizational project and regenerative medicine, the problem of the aspects such as related materials surface modification and cell adhesion causes people more and more to pay close attention to.Tissue can be considered to be the complex body of cell and extracellular matrix, if the novel biomaterial of imitative extracellular matrix can be utilized to construct certain class biotic environment, and at its surface or inner cultivation cell, we just can utilize bionical means to study the important vital movement of internal body in vitro like this.Will construct the complex body of cell and biomaterial in vitro, just must understand many Fundamental Aspects of cell and biomaterial interaction aspect, wherein one of the problem of most critical is exactly the adherence mechanism of cell at biomaterial surface.In research cell adhesion mechanism, the patterned process of biomaterial surface makes originally complicated question simplification, and for more in depth studying the active mechanism such as cell adhesion, migration provides opportunity [Sun Jianguo, the golden micro-patterning modification of PEG-hydrogel and superficial cell thereof stick the research [D] of behavior. Fudan University, 2009].In addition, traditional cell research mode, such as on culture plate, study cell, be difficult to overcome the problems such as cell migration, micro-patterning technique that new development is got up then can realize cellular localization, contribute to studying cell contact etc. affect cell activities associated problem [Tang Jian, the preparation of micropatterned surface and cell contact affect the research [D] of differentiation of stem cells. Fudan University, 2010.].Therefore, along with the development of organizational project, surface patterning technique more and more receives the concern of people, is widely used.Oneself warp of micro-patterning technology is used for accurately controlling the position of cell and the co-cultivation of form (especially unicellular) and various kinds of cell, and oneself studies the interactional platform of cell-material on a cellular level through having built one for it.
High-molecular gel causes with good biocompatibility and pays close attention to widely.High-molecular gel is the multicomponent system by polymer three-dimensional network and solvent composition, to environmental stimulus as temperature, pH, electric field, solvent property, light intensity and optical wavelength, pressure, ionic strength, ion density and special chemical stimulation (as sugar) etc., produce the polymer network of great variety in shape in macroscopic view (volume).Macromole base component in the structure of hydrogel and body is close, is desirable cell culture vector.But the physical strength of most of artificial Common hydrogels is very poor, is easily out of shape, and along with water content difference occur swelling and deswelling.Such as gelatin is when water regain is 5 times of xerogel weight, and its fracture tensile strength is approximately 70KPa, and elongation at break is 10%.When absorbing water to 40 times, its fracture tensile strength only has its elongation at break of 6KPa to be 11%.The method improving hydrogel intensity traditionally mainly concentrates on to be improved on the cross-linking density of hydrogel, but the intensity of hydrogel fundamentally can not be improved only by raising cross-linking density, and greatly can reduce the snappiness of hydrogel, make hydrogel become very crisp.
The biomaterial preparing patterning modification has a lot of method, and the most frequently used has photoetching technique and the soft lithography based on this.Simple photoetching technique cost is high and purposes is limited, although and soft lithography has expanded the Application Areas of photoetching technique widely, if simply cover use; be faced with the stability problem of pattern in water.Existing patterning techniques is mostly for minority hydrophobic polymers such as hard matrix or silicon rubber, construct suitable micro-pattern in character close to the soft wet hydrogel surface of human body most tissues and then there is technical difficulty, because hydrogel poor toughness, easy distortion [Liu Peng, the Study on Preparation Technology [D] of material surface micron-nanometer heterozygosis pattern. Fudan University, 2009].Sun Jianguo etc. employ a kind of transfer techniques, and the Au patterning achieving its surface dexterously in PEG-hydrogel polymerization process is modified.[Sun Jianguo, Tang Jian, Ding Jiandong, based on surperficial micro-patterning technical study cell orientation [J]. Science Bulletin, 2009,5410:1344-1349.].N-isopropylacrylamide is modified the silicon substrate surface with different nanoscale grooves by this grade of primary track [18], have studied temperature-responsive [the Reversible Switchingbetween Superhydrophilicity and Superhydrophobicity.Surface Chemistry of modified surface, 2004,43:357-360].But aforesaid method step more complicated, cost is also high.Therefore, setting up of simple and practical hydrogel surface micro-patterning preparation method is significant.
The researchist of Harvard University have developed the hydrogel of snappiness and high tenacity, its composition is alginates and polyacrylamide [Highly stretchable and tough hydrogels, Nature, 2012,489 (7414): 133-136].The hydrogel elastic that these two kinds of materials are formed separately and toughness are all little, if but they are mixed by a certain percentage be polymerized in water, a kind of novel hydrogels can be obtained.Although about 90% is water in novel hydrogels, its elasticity is superpower, can be stretched to more than 20 times of original length and constantly, can also restore to the original state voluntarily afterwards.Its toughness is also fine, and one block of such hydrogel is broken disconnected, needs the energy that expends and to break disconnected one block of natural rubber similar.The hydrogel of such elasticity and toughness reaches the requirement of the tissues such as alternative cartilage, can be used for manufacturing associated medical devices, such as can manufacture artificial intervertebral disc with it.The report of micro-pattern is not also built at present in this kind of hydrogel surface.
The present invention take sodium alginate as macromolecular scaffold, with acrylamide and derivative thereof for polymerization single polymerization monomer, add chemical cross-linking agent, take aqueous metal salt as ion crosslinking agent, add inorganic nano-particle as toughener, the silicon chip matrix with patterning is prepared the patterning aquagel membrane of snappiness and high tenacity.This preparation method has the advantages such as controllability is good, technique is simple, cost is low, Biocompatibility is good, and this patterning aquagel membrane is expected to obtain application in fields such as stem cell cultivation, tissue regenerations.
Summary of the invention
For the deficiencies in the prior art, quasi-solution of the present invention is determined, and hydrogel is difficult to that patterned surface, hydrogel intensity and toughness are low, aquagel membrane thickness is difficult to control the problems such as even.
The technical scheme that the present invention solves that above-mentioned hydrogel is difficult to that patterned surface, hydrogel intensity and toughness are low, aquagel membrane thickness is difficult to control the problem such as even is a kind of patterned surface high-intensity high-tenacity hybrid gel film of design.
The invention provides a kind of patterned surface high-intensity high-tenacity hybrid gel film and preparation method thereof, it is characterized in that comprising the following steps:
A) successively have the silicon chip of patterning respectively by dilute hydrochloric acid, dehydrated alcohol and washed with de-ionized water, then 60-80 DEG C of vacuum-drying 8-24h, obtains dried patterning silicon chip;
B) 5-15g polymerization single polymerization monomer is taken, 0.5-2g sodium alginate, the linking agent of polymerization single polymerization monomer mass percent 0.03%-0.15%, be dissolved in 50-100ml deionized water together, stirring and dissolving is even, then the toughener of polymerization single polymerization monomer mass percent 1%-200% is added, the ammonium persulphate of polymerization single polymerization monomer mass percent 0.1%-5% is added again after ultrasonic disperse is even, the sodium bisulfite of polymerization single polymerization monomer mass percent 0.1%-5% and the Tetramethyl Ethylene Diamine of polymerization single polymerization monomer mass percent 0.01%-2%, after dispersed with stirring is even, immediately this solution is poured on patterning silicon chip that step a) processed, strike off with the knifing rod that thickness is 20-3000 μm, form the film of uniform thickness, vacuum defoamation, at N
2be polymerized 8-24h under protection, obtain the patterned surface gel-film of chemically crosslinked,
C) by step b) aqueous metal salt of the gel 0.01%-10% of chemically crosslinked that obtains soaks 0.5-24h, and wash away the salts solution on surface with deionized water, obtain patterned surface high-intensity high-tenacity hybrid gel film.
Polymerization single polymerization monomer of the present invention is any one or two or more mixture in diacetone-acryloamide(DAA), N-isopropylacrylamide, acrylamide, Methacrylamide, DMAA, 2-acrylamide-2-methyl propane sulfonic, and described aqueous metal salt is any one or two or more mixture in copper sulfate, zinc chloride, bariumchloride, iron(ic) chloride, aluminum chloride, calcium chloride, monocalcium phosphate, calcium sulfate, nitrocalcite, calglucon, secondary calcium phosphate, the calcium lactate aqueous solution.
Linking agent of the present invention is any one or two or more mixture in Vinylstyrene, vulcabond, N, N '-methylene-bisacrylamide, Ethylene glycol dimethacrylate, melamine methylol etherate.
Patterning silicon chip of the present invention is any one or two or more combinations of patterns in wavy line, narrow vertical bar line, wide vertical bar line, cylindrical shape and chequer.
Toughener of the present invention is any one or two or more mixture in nano silicon, nano titanium oxide, nanometer hydroxyapatite, nanoclay, carbon nanotube, Graphene, nano-calcium carbonate, nano zine oxide.
The preparation method of a kind of patterned surface high-intensity high-tenacity hybrid gel film of the present invention, it is characterized in that the printing effect relying on patterning silicon chip, pattern is printed off on the hybrid gel film surface of high-intensity high-tenacity, its preparation method and technique simple, cost is low, and this patterned surface high-intensity high-tenacity hybrid gel film has good application prospect in fields such as organizational project, stem cell cultivation and regenerative medicines.
Embodiment
Introduce specific embodiments of the invention below, but the present invention is not by the restriction of embodiment.
Embodiment 1. 1 kinds of surface narrow vertical bar line patterning high-intensity high-tenacity gel-films and preparation method thereof
A) successively have the silicon chip of narrow vertical bar line patterning respectively by dilute hydrochloric acid, dehydrated alcohol and washed with de-ionized water, then 60 DEG C of vacuum-drying 24h, obtain dried patterning silicon chip;
B) 15g N-isopropylacrylamide is taken, 0.5g sodium alginate, the Ethylene glycol dimethacrylate of N-isopropylacrylamide mass percent 0.03%, be dissolved in 100ml deionized water together, stirring and dissolving is even, then the toughener nanometer hydroxyapatite of N-isopropylacrylamide mass percent 1% is added, the ammonium persulphate of N-isopropylacrylamide mass percent 5% is added again after ultrasonic disperse is even, the sodium bisulfite of N-isopropylacrylamide mass percent 5% and the Tetramethyl Ethylene Diamine of N-isopropylacrylamide mass percent 0.01%, after dispersed with stirring is even, immediately this solution is poured on patterning silicon chip that step a) processed, strike off with the knifing rod that thickness is 20 μm, form the film of uniform thickness, vacuum defoamation, at N
2the lower free radical polymerization of protection, reaction 8h, obtains the surface narrow vertical bar line patterning gel-film of chemically crosslinked,
C) by step b) gel of chemically crosslinked that the obtains barium chloride solution of 0.01% soaks 24h, and wash away the salts solution on surface with deionized water, obtain surperficial narrow vertical bar line patterning high-intensity high-tenacity hybrid gel film.
Embodiment 2. 1 kinds of surface wide vertical bar line patterning high-intensity high-tenacity gel-films and preparation method thereof
A) successively have the silicon chip of wide vertical bar line patterning respectively by dilute hydrochloric acid, dehydrated alcohol and washed with de-ionized water, then 80 DEG C of vacuum-drying 8h, obtain dried wide vertical bar line patterning silicon chip;
B) 5g diacetone-acryloamide(DAA) is taken, 2g sodium alginate, the Vinylstyrene of diacetone-acryloamide(DAA) mass percent 0.15%, be dissolved in 50ml deionized water together, stirring and dissolving is even, then the toughener nano silicon of diacetone-acryloamide(DAA) mass percent 200% is added, the ammonium persulphate of diacetone-acryloamide(DAA) mass percent 5% is added again after ultrasonic disperse is even, the sodium bisulfite of diacetone-acryloamide(DAA) mass percent 5% and the Tetramethyl Ethylene Diamine of diacetone-acryloamide(DAA) mass percent 0.1%, after dispersed with stirring is even, immediately this solution is poured on patterning silicon chip that step a) processed, strike off with the knifing rod that thickness is 200 μm, form the film of uniform thickness, vacuum defoamation, at N
2the lower uv-light polymerization of protection, reaction 8h, obtains the surface wide vertical bar line patterning gel-film of chemically crosslinked,
C) by step b) gel of chemically crosslinked that the obtains solder(ing)acid of 10% soaks 0.5-24h, and wash away the salts solution on surface with deionized water, obtain surperficial wide vertical bar line patterning high-intensity high-tenacity hybrid gel film.
Embodiment 3. 1 kinds of surface cylindrical shape patterning high-intensity high-tenacity gel-films and preparation method thereof
A) successively have the silicon chip of cylindrical shape patterning respectively by dilute hydrochloric acid, dehydrated alcohol and washed with de-ionized water, then 80 DEG C of vacuum-drying 8h, obtain dried patterning silicon chip;
B) 15g acrylamide is taken, 0.5g sodium alginate, the Ethylene glycol dimethacrylate of acrylamide mass percent 0.03%, be dissolved in 100ml deionized water together, stirring and dissolving is even, then the toughener nano titanium oxide of acrylamide mass percent 1% is added, the ammonium persulphate of acrylamide mass percent 0.1% is added again after ultrasonic disperse is even, the sodium bisulfite of acrylamide mass percent 0.1% and the Tetramethyl Ethylene Diamine of acrylamide mass percent 0.01%, after dispersed with stirring is even, immediately this solution is poured on patterning silicon chip that step a) processed, strike off with the knifing rod that thickness is 20 μm, form the film of uniform thickness, vacuum defoamation, at N
2the lower high-power electron beam initiated polymerization of protection, reaction 24h, obtains the surface cylindrical shape patterning gel-film of chemically crosslinked,
C) by step b) gel of chemically crosslinked that the obtains calcium chloride water of 2% soaks 0.5h, and wash away the salts solution on surface with deionized water, obtain surface cylindrical shape patterning high-intensity high-tenacity hybrid gel film.
Embodiment 4. 1 kinds surperficial graticule patterning high-intensity high-tenacity gel-film and preparation method thereof
A) successively have the silicon chip of graticule patterning respectively by dilute hydrochloric acid, dehydrated alcohol and washed with de-ionized water, then 70 DEG C of vacuum-drying 12h, obtain dried chequer SiClx sheet;
B) 10g Methacrylamide is taken, 1.5g sodium alginate, the N of Methacrylamide mass percent 0.1%, N '-methylene-bisacrylamide, be dissolved in 50ml deionized water together, stirring and dissolving is even, then the toughener Graphene of Methacrylamide mass percent 50% is added, the ammonium persulphate of Methacrylamide mass percent 1% is added again after ultrasonic disperse is even, the sodium bisulfite of Methacrylamide mass percent 1% and the Tetramethyl Ethylene Diamine of Methacrylamide mass percent 0.02%, after dispersed with stirring is even, immediately this solution is poured on patterning silicon chip that step a) processed, strike off with the knifing rod that thickness is 400 μm, form the film of uniform thickness, vacuum defoamation, at N
2the lower gamma ray initiated polymerization of protection, reaction 24h, obtains the surperficial graticule patterning gel-film of chemically crosslinked,
C) by step b) gel of chemically crosslinked that the obtains copper sulfate solution of 5% soaks 8h, and wash away the salts solution on surface with deionized water, obtain surperficial graticule patterning high-intensity high-tenacity hybrid gel film.
Claims (9)
1. a preparation method for patterned surface high-intensity high-tenacity hybrid gel film, is characterized in that comprising the following steps:
A) successively have the silicon chip of patterning respectively by dilute hydrochloric acid, dehydrated alcohol and washed with de-ionized water, then 60-80 DEG C of vacuum-drying 8-24h, obtains dried patterning silicon chip;
B) 5-15g polymerization single polymerization monomer is taken, 0.5-2g sodium alginate, the linking agent of polymerization single polymerization monomer mass percent 0.03%-0.15%, be dissolved in 50-100ml deionized water together, stirring and dissolving is even, then the toughener of polymerization single polymerization monomer mass percent 1%-200% is added, the ammonium persulphate of polymerization single polymerization monomer mass percent 0.1%-5% is added again after ultrasonic disperse is even, the sodium bisulfite of polymerization single polymerization monomer mass percent 0.1%-5% and the Tetramethyl Ethylene Diamine of polymerization single polymerization monomer mass percent 0.01%-2%, after dispersed with stirring is even, immediately this solution is poured on patterning silicon chip that step a) processed, strike off with the knifing rod that thickness is 20-3000 μm, form the film of uniform thickness, vacuum defoamation, at N
2the lower initiated polymerization of protection, reaction 8-24h, obtains the patterned surface gel-film of chemically crosslinked,
C) by step b) aqueous metal salt of the gel-film 0.01%-10% of chemically crosslinked that obtains soaks 0.5-24h, and wash away the salts solution on surface with deionized water, obtain patterned surface high-intensity high-tenacity hybrid gel film.
2. the preparation method of a kind of patterned surface high-intensity high-tenacity hybrid gel film as claimed in claim 1, what it is characterized in that described polymerization single polymerization monomer is any one in diacetone-acryloamide(DAA), N-isopropylacrylamide, acrylamide, Methacrylamide, DMAA, 2-acrylamide-2-methyl propane sulfonic or two or more mixture.
3. the preparation method of a kind of patterned surface high-intensity high-tenacity hybrid gel film as claimed in claim 1, is characterized in that described aqueous metal salt is any one or two or more mixture in copper sulfate, zinc chloride, bariumchloride, iron(ic) chloride, aluminum chloride, calcium chloride, monocalcium phosphate, calcium sulfate, nitrocalcite, calglucon, secondary calcium phosphate, the calcium lactate aqueous solution.
4. the preparation method of a kind of patterned surface high-intensity high-tenacity hybrid gel film as claimed in claim 1, it is characterized in that described linking agent is any one or two or more mixture in Vinylstyrene, vulcabond, N, N '-methylene-bisacrylamide, Ethylene glycol dimethacrylate, melamine methylol etherate.
5. the preparation method of a kind of patterned surface high-intensity high-tenacity hybrid gel film as claimed in claim 1, is characterized in that described patterning silicon chip is any one or two or more combinations of patterns in wavy line, narrow vertical bar line, wide vertical bar line, cylindrical shape and chequer.
6. the preparation method of a kind of patterned surface high-intensity high-tenacity hybrid gel film as claimed in claim 1, is characterized in that described toughener is any one or two or more mixture in nano silicon, nano titanium oxide, nanometer hydroxyapatite, nanoclay, carbon nanotube, Graphene, nano-calcium carbonate, nano zine oxide.
7. the preparation method of a kind of patterned surface high-intensity high-tenacity hybrid gel film as claimed in claim 1, it is characterized in that its initiated polymerization mode be free radical cause, microwave radiation cause, UV-light cause, high-power electron beam cause, gamma ray cause, plasma cause in any one.
8. the preparation method of a kind of patterned surface high-intensity high-tenacity hybrid gel film as claimed in claim 1, is characterized in that the printing effect relying on patterning silicon chip, prints off pattern on the hybrid gel film surface of high-intensity high-tenacity.
9. the preparation method of a kind of patterned surface high-intensity high-tenacity hybrid gel film as claimed in claim 1, it is characterized in that preparation method's technique is simple, cost is low, and this patterned surface high-intensity high-tenacity hybrid gel film has good application prospect in organizational project, stem cell cultivation and regenerative medicine field.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310112802.7A CN103205006B (en) | 2013-04-02 | 2013-04-02 | Surface patterning high-strength and high-toughness hybrid hydrogel membrane and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310112802.7A CN103205006B (en) | 2013-04-02 | 2013-04-02 | Surface patterning high-strength and high-toughness hybrid hydrogel membrane and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103205006A CN103205006A (en) | 2013-07-17 |
| CN103205006B true CN103205006B (en) | 2015-04-22 |
Family
ID=48752424
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310112802.7A Active CN103205006B (en) | 2013-04-02 | 2013-04-02 | Surface patterning high-strength and high-toughness hybrid hydrogel membrane and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103205006B (en) |
Families Citing this family (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103449420B (en) * | 2013-08-22 | 2015-03-25 | 中国科学院金属研究所 | High-quality graphene dispersion method and film preparation method |
| CN103845757B (en) * | 2013-12-13 | 2015-12-09 | 天津大学 | A kind of artificial articular cartilage material and preparation method thereof |
| CN104311860A (en) * | 2014-10-10 | 2015-01-28 | 齐鲁工业大学 | Preparation method of high-strength dual-mesh nano-meter titanium dioxide composite hydrogel |
| CN104311859A (en) * | 2014-10-10 | 2015-01-28 | 齐鲁工业大学 | Preparation method of high-strength dual-mesh nano-meter aluminum oxide composite hydrogel |
| CN104341556A (en) * | 2014-10-10 | 2015-02-11 | 齐鲁工业大学 | Preparation method of high-strength double-network nano hectorite composite aquagel |
| CN106555253B (en) * | 2015-09-28 | 2018-11-20 | 天津工业大学 | A kind of high-intensity and high-tenacity hydrogel nanofiber and preparation method thereof |
| CN105294955B (en) * | 2015-10-23 | 2018-04-24 | 华中科技大学 | A kind of photocuring hydrogel broken up for many cells sorting and stem cell constituency and preparation method thereof |
| CN108659440B (en) * | 2018-06-08 | 2020-06-16 | 天津工业大学 | Preparation method for obtaining high-strength hydrogel through secondary swelling and crosslinking |
| CN108714246B (en) * | 2018-06-15 | 2021-03-02 | 天津工业大学 | Preparation method of high-strength hydrogel cartilage substitute capable of being combined with subchondral bone |
| CN109163653B (en) * | 2018-09-10 | 2020-06-09 | 中国工程物理研究院电子工程研究所 | Preparation method of patterned graphene flexible strain sensor |
| CN109294002B (en) * | 2018-09-15 | 2021-05-04 | 深圳先进技术研究院 | Controllable bidirectional three-dimensional deformation hydrogel film, preparation method thereof and flexible microelectrode array |
| CN112111073B (en) * | 2020-09-18 | 2023-09-12 | 苏州凝智新材料发展有限公司 | Anti-fatigue full-hydrogel composite material and preparation method and application thereof |
| CN113754828B (en) * | 2021-08-23 | 2022-08-30 | 南京工业大学 | Method for preparing patterned gel material by polymerization of front end of micro-channel |
| CN113984235B (en) * | 2021-11-10 | 2024-04-19 | 武汉大学 | Flexible stretchable thermocouple based on ionic thermoelectric hydrogel and preparation method thereof |
| CN115418344A (en) * | 2022-08-12 | 2022-12-02 | 广东省科学院生物与医学工程研究所 | Method for simply and rapidly preparing patterned cell film |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7045062B1 (en) * | 2003-01-21 | 2006-05-16 | Seventy-Seventh Meridian Corporation, Llc | Pervaporation membranes and methods of use |
| CN102030482A (en) * | 2010-10-13 | 2011-04-27 | 中国科学院化学研究所 | Method for preparing nanometer patterning bipolymer brush |
-
2013
- 2013-04-02 CN CN201310112802.7A patent/CN103205006B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7045062B1 (en) * | 2003-01-21 | 2006-05-16 | Seventy-Seventh Meridian Corporation, Llc | Pervaporation membranes and methods of use |
| CN102030482A (en) * | 2010-10-13 | 2011-04-27 | 中国科学院化学研究所 | Method for preparing nanometer patterning bipolymer brush |
Non-Patent Citations (1)
| Title |
|---|
| "Highly stretchable and tough hydrogels";Jeong-Yun Sun et.al;《Nature》;20120906;第489卷;第133页右栏第2段 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103205006A (en) | 2013-07-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103205006B (en) | Surface patterning high-strength and high-toughness hybrid hydrogel membrane and preparation method thereof | |
| CN103254539B (en) | A kind of high-intensity high-tenacity protein molecule engram hybrid gel film and preparation method thereof | |
| Ding et al. | Environment tolerant, adaptable and stretchable organohydrogels: Preparation, optimization, and applications | |
| Zhu et al. | Recent advances in conductive hydrogels: classifications, properties, and applications | |
| CN103224633B (en) | Self-reinforced hybrid hydrogel used for artificial muscles and preparation method thereof | |
| Zhou et al. | Advances and challenges in conductive hydrogels: From properties to applications | |
| Tong et al. | Highly stretchable and compressible cellulose ionic hydrogels for flexible strain sensors | |
| Wang et al. | Three-dimensional printing of shape memory hydrogels with internal structure for drug delivery | |
| Jing et al. | Mussel-inspired electroactive chitosan/graphene oxide composite hydrogel with rapid self-healing and recovery behavior for tissue engineering | |
| Li et al. | Hofmeister effect mediated strong PHEMA-gelatin hydrogel actuator | |
| CN103435951B (en) | A kind of Nanometer composite high-molecular dual-network hydrogel and preparation method thereof | |
| CN109627461B (en) | Polypyrrole nano composite conductive hydrogel and preparation method thereof | |
| CN107141407B (en) | It is a kind of can spontaneous driving polyampholyte hydrogel driver and preparation method thereof and driving method | |
| CN105086001A (en) | Hyaluronic acid-gelatin/acrylamide double-network aquagel and preparation method thereof | |
| Wu et al. | Natural-wood-inspired ultrastrong anisotropic hybrid hydrogels targeting artificial tendons or ligaments | |
| CN109125813A (en) | A kind of conductive adherency hydrogel preparation method and application for tissue repair | |
| CN110372885A (en) | A kind of chitosan/amphoteric ion and acrylic copolymer dual network self-healing hydrogel and preparation method thereof | |
| CN110265232A (en) | A kind of self-healing hydrogel electrolytic thin-membrane and its preparation method and application | |
| Wang et al. | Facile preparation of agar/polyvinyl alcohol-based triple-network composite hydrogels with excellent mechanical performances | |
| CN110157012A (en) | A kind of preparation method of high-intensity and high-tenacity gelatin based aquagel | |
| CN108714246A (en) | A kind of preparation method for the high intensity hydrogel cartilage substitute that can be combined with subchondral bone | |
| Fan et al. | Polyelectrolyte-based conductive hydrogels: from theory to applications | |
| Zhao et al. | Synthesis of macroporous thermosensitive hydrogels: A novel method of controlling pore size | |
| CN112480312B (en) | Preparation method of high-elasticity high-strength double-crosslinking porous hydrogel | |
| CN106267366B (en) | A method of high-strength and high ductility polyion hydrogel scaffold is prepared using 3D printing |
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 | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20211207 Address after: 314500 Tongxiang, Jiaxing, Zhejiang, Wutong Street East Road (East) 55, Tongxiang chamber of Commerce Building 1 unit 1702, 1703 room -D-403 Patentee after: Jiaxing zhideruikong new energy Co.,Ltd. Address before: 300160 Tianjin City Hedong District Forest Road No. 63 Patentee before: TIANJIN POLYTECHNIC University |
|
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20240415 Address after: Room 502, 4th Floor, Building 3, No. 82 East Fourth Ring Middle Road, Chaoyang District, Beijing, 100000 Patentee after: Lexiang Guoyi (Beijing) Internet Hospital Co.,Ltd. Country or region after: China Address before: 314500 Tongxiang, Jiaxing, Zhejiang, Wutong Street East Road (East) 55, Tongxiang chamber of Commerce Building 1 unit 1702, 1703 room -D-403 Patentee before: Jiaxing zhideruikong new energy Co.,Ltd. Country or region before: China |
|
| TR01 | Transfer of patent right |