CN104211979A - Preparation method for amine-group-rich polymerization film - Google Patents
Preparation method for amine-group-rich polymerization film Download PDFInfo
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- CN104211979A CN104211979A CN201410406190.7A CN201410406190A CN104211979A CN 104211979 A CN104211979 A CN 104211979A CN 201410406190 A CN201410406190 A CN 201410406190A CN 104211979 A CN104211979 A CN 104211979A
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Abstract
A disclosed preparation method for an amine-group polymerization film is characterized by comprising performing copolymerization on an organic amine compound with amine groups at two ends and a polyphenol compound containing catechol, and regulating the reaction conditions, so as to obtain the film rich in amine functional groups on the surface of a basic material. The prepared polymerization film has relatively high surface amine content, and is applicable to fixation of a plurality of biological molecules. The prepared film is good in stability, the catechol compound has extremely strong binding force with the base material, and also introduction of the organic amine compound helps to improve the crosslinking degree of the film and further enhancing the stability of the film. The preparation method is simple and practicable, can used to perform deposition on surfaces of a plurality of materials, does not need complex equipment, is low in technological cost, and establishes a base for applying the film to surface modification of biological materials.
Description
Technical field
The present invention relates to and a kind ofly prepare the method having and enrich amidine functional group polymer thin film, be applied to the surface modification of biomaterial.
Background technology
Biomaterial surface modification is under the prerequisite not affecting material body character, improve the technology of material surface performance or raising special surface character, play in chemistry, biology, Materials science and applied science, engineering, technical field the vital role do not replaced.Existing self-assembled film, silanization, physical/chemical vapour deposition and surface grafting etc. are comprised to the mode that material surface carries out functional modification, although these methods are in daily use under study for action, but there is a lot of limitation in a lot of method in widespread use, such as to the requirement of the chemical specificity between modifying interface and surface, the equipment complexity of use, requirement, complicated operation etc. to base material shape and size.Therefore, it is extremely important and necessary for seeking a kind of mode that is simple, that can carry out surface modification to multiple material.
The modification mode that the organic film having a reactive functionality in material surface deposition is used for fixing biomolecules is study hotspot, and the Dopamine HCL film particularly based on Polyphenols causes concern especially.Dopamine HCL film can obtain significant progress with almost all kinds material mortise and for biomolecules grafting provides the advantage of reaction site to modify field at biomaterial because having.This provides platform for being modified dissimilar material by the mode of simple chemistry and prepared functional composite material.But, the secondary reaction of Dopamine HCL film is confined to the biomolecules only can fixedly with sulfydryl or amine groups, because of the secondary reaction of Dopamine HCL film be amido on the phenolic hydroxyl group or quinonyl and biomolecules that retain on Dopamine HCL film or sulfydryl generation Michael addition or schiff bases reaction based on.For the grafting of biomolecules as heparin etc. with groups such as carboxyls, Dopamine HCL film just lacks reactive functionality as primary amine groups etc.In addition, appropriate amidine functional group has the character promoting cell adhesion, and for skin regeneration material, bone and cartilage repair material, obtain amidine functional group is very necessary.
Based on this, we have prepared a kind of functional film of rich amido.This kind of film is the inspiration of the adhesion protein being subject to mussel secretion, wherein mussel foot protein-3 and mussel foot albumen-5 are generally considered the crucial binder that mediation mussel is combined with material surface, and these two kinds of albumen all include a high proportion of DOPA and abundant Methionin.Existing result of study shows, the mortise of mussel and material surface is based on the phenolic hydroxyl group of DOPA or the strong covalency between quinonyl and base material and noncovalent interaction.In addition, Methionin plays important role in crosslinking reaction, thus the solidification of the liquid protein binder causing mussel to secrete.
Based on this, the organic amine compound (for hexanediamine) that we adopt the catechol of class DOPA (for Dopamine HCL) and have a both-end amidine functional group prepares a kind of highly cross-linked rich amido copolymerization film.Hexanediamine, chemical formula NH
2(CH
2)
6nH
2, be the small organic molecule containing amidine functional group, can be used for organic synthesis, the polymerization of macromolecular compound, the solidifying agent of epoxy resin etc., organic crosslinking agent.Under the effect of alkaline environment and oxygen, the quinones that the oxidable one-tenth of the catechol group in dopamine structure is active or half quinones.This single step reaction relates to phenol and quinonyl equilibrium process in aqueous, and under alkaline environment, molecular balance, to the skew of quinonyl direction, is of value to the spontaneous oxidation reaction of Dopamine HCL.The amido of hexanediamine can with active quinonyl generation Michael reaction or schiff base reaction, cause intermolecular being cross-linked with each other.Meanwhile, Dopamine HCL-benzoquinones generation cyclisation, forms five-ring, and oxidation, molecular transposition, cause intermolecular cross-linking further.The larger film of surface amine groups density can be obtained by regulation and control reaction conditions.And there is no the report introduced hexanediamine and Dopamine HCL copolymerization and prepare film at present.
The present invention is based on the inspiration of the albumen of mussel secretion, propose a kind of simple, novel method and can prepare the polymer thin film having and enrich amidine functional group, for the further grafting biomolecules of base material provides platform.The surface modification of bio-medical metal_based material (Fe and alloy, mg-based material, 316L SS, Ti, Ti alloy Ni-Ti alloy and CoCr alloy etc.), inorganic materials (Ti-O, TiN etc.), macromolecular material (as: PET, PTFE, PDMS etc.) and degradable tissue engineering bracket material (as PLA, PLGA and PCL etc.) can be widely used in.
Summary of the invention
The invention provides a kind of preparation method of rich amido polymer thin film, the film adopting this kind of method to prepare not only can be provided for the abundant amidine functional group of grafting target molecule, and has satisfactory stability.
The technical solution adopted for the present invention to solve the technical problems is: a kind of preparation method of rich amido polymer thin film, introduce organic amine compound and the catechol copolymerization with amidine functional group, by regulation and control reaction conditions, obtain the film being rich in amidine functional group at different base material surface.
Based on this, its exemplary steps is:
A, material prepare.
The base material carrying out modification will be needed, include but not limited to: Fe and alloy, magnesium and alloy thereof, 316L SS, Ti, Ti alloy, Ni-Ti alloy and CoCr alloy, Si, Ti-O, TiN, PET, PTFE, PDMS, PLA, PLGA, PCL, Au, Ag, Pt, Pd, Cu, hydroxyapatite, calcium phosphate, bio-vitric, aluminum oxide, silicon oxide, PS, PE, PC, PEEK, PU, through cleaning, drying, stand-by;
The preparation of B, film.
0.01-20mg/ml catechol and 0.01-40mg/ml organic amine compound are dissolved in alkaline Tris-base damping fluid, 1-48h is reacted in solution after the base material prepared in A is soaked in reactant Homogeneous phase mixing, then with the abundant rinsing of distilled water, drying, obtains surface amine groups density 1-200nmol/cm
2target compound film.
Compared with prior art, beneficial effect is the inventive method:
One, the polymer film surface amido amount of preparation is comparatively large, can be used for the fixing of various biomolecules.
Two, the thin film stability of preparation is good, and catechol and base material have very strong bonding force, and the introducing of organic amine compound simultaneously can improve the degree of crosslinking of film, and then enhanced film stability.
Three, preparation method is simple, precious metal (Au, Ag, Pt, Pd) can be comprised at multiple material, the surface depositions such as oxide compound (Cu, titanium oxide, aluminum oxide, silicon oxide, stainless steel, CoCrMo alloy, NiTi alloy), pottery, semiconductor material, polymer (PS, PE, PC, PET, PTFE, PDMS, PLA, PLGA, PCL, PEEK, PU), do not need complicated equipment, process costs is low, for the surface modification that this kind of film is applied to biomaterial is afterwards laid a good foundation.
Embodiment
Embodiment 1
A preparation method for rich amido polymer thin film, the steps include:
A, material prepare.
By needing the base material 316L SS of surface modification to carry out polishing, cleaning, drying, stand-by;
The preparation of B, film.
1mg/ml Dopamine HCL and 20mg/ml hexanediamine are dissolved in alkaline Tris-base damping fluid, 48h is reacted in solution after the base material prepared in A is soaked in reactant Homogeneous phase mixing, then with the abundant rinsing of distilled water, dry, obtain the film of rich surface amino-contained.
Embodiment 2
A preparation method for rich amido polymer thin film, the steps include:
A, material prepare.
Needs are carried out modified substrate material PTFE carry out cleaning, dry, stand-by;
The preparation of B, film.
2mg/ml Dopamine HCL and 15mg/ml quadrol are dissolved in alkaline Tris-base damping fluid, 24h is reacted in solution after the base material prepared in A is soaked in reactant Homogeneous phase mixing, then with the abundant rinsing of distilled water, dry, obtain the film of rich surface amino-contained.
Embodiment 3
A preparation method for rich amido polymer thin film, the steps include:
A, material prepare.
Needs are carried out modified substrate material 316LSS and carry out polishing, cleaning, drying, stand-by;
The preparation of B, film.
1mg/ml Dopamine HCL and 20mg/ml poly-lysine (PLL) are dissolved in alkaline Tris-base damping fluid, 12h is reacted in solution after the base material prepared in A is soaked in reactant Homogeneous phase mixing, then with the abundant rinsing of distilled water, drying, obtains the film of rich surface amino-contained.
Embodiment 4
A preparation method for rich amido polymer thin film, the steps include:
A, material prepare.
Needs are carried out modified substrate material PTFE carry out cleaning, dry, stand-by;
The preparation of B, film.
1mg/ml Dopamine HCL and 20mg/ml polyetherimide (PEI) are dissolved in alkaline Tris-base damping fluid, 12h is reacted in solution after the base material prepared in A is soaked in reactant Homogeneous phase mixing, then with the abundant rinsing of distilled water, drying, obtains the film of rich surface amino-contained.
Embodiment 5
A preparation method for rich amido polymer thin film, the steps include:
A, material prepare.
Needs are carried out modified substrate material 316LSS and carry out polishing, cleaning, drying, stand-by;
The preparation of B, film.
1mg/ml pyrocatechol and 2mg/ml hexanediamine are dissolved in alkaline Tris-base damping fluid, 24h is reacted in solution after the base material prepared in A is soaked in reactant Homogeneous phase mixing, then with the abundant rinsing of distilled water, dry, obtain the film of rich surface amino-contained.
Embodiment 6
A preparation method for rich amido polymer thin film, the steps include:
A, material prepare.
Needs are carried out modified substrate material PTFE carry out cleaning, dry, stand-by;
The preparation of B, film.
1mg/ml pyrocatechol and 2mg/ml quadrol are dissolved in alkaline Tris-base damping fluid, 12h is reacted in solution after the base material prepared in A is soaked in reactant Homogeneous phase mixing, then with the abundant rinsing of distilled water, dry, obtain the film of rich surface amino-contained.
Embodiment 7
A preparation method for rich amido polymer thin film, the steps include:
A, material prepare.
Needs are carried out modified substrate material 316LSS and carry out polishing, cleaning, drying, stand-by;
The preparation of B, film.
1mg/ml pyrocatechol and 10mg/ml poly-lysine (PLL) are dissolved in alkaline Tris-base damping fluid, 12h is reacted in solution after the base material prepared in A is soaked in reactant Homogeneous phase mixing, then with the abundant rinsing of distilled water, drying, obtains the film of rich surface amino-contained.
Embodiment 8
A preparation method for rich amido polymer thin film, the steps include:
A, material prepare.
Needs are carried out modified substrate material PTFE carry out cleaning, dry, stand-by;
The preparation of B, film.
1mg/ml pyrocatechol and 20mg/ml polyetherimide (PEI) are dissolved in alkaline Tris-base damping fluid, 48h is reacted in solution after the base material prepared in A is soaked in reactant Homogeneous phase mixing, then with the abundant rinsing of distilled water, drying, obtains the film of rich surface amino-contained.
Claims (4)
1. the preparation method of a rich amido polymer thin film, it is characterized in that: will there is both-end amidine functional group organic amine compound and the polyphenolic substance copolymerization containing pyrocatechol, by regulation and control reaction conditions, obtain on base material surface the film being rich in amidine functional group.
2. the preparation method of a kind of rich amido polymer thin film according to claim 1, the steps include:
A, material prepare
The base material carrying out modification will be needed, include but not limited to: Fe and alloy, magnesium and alloy thereof, 316L SS, Ti, Ti alloy, Ni-Ti alloy and CoCr alloy, Si, Ti-O, TiN, PET, PTFE, PDMS, PLA, PLGA, PCL, Au, Ag, Pt, Pd, Cu, hydroxyapatite, calcium phosphate, bio-vitric, aluminum oxide, silicon oxide, PS, PE, PC, PEEK, PU, through cleaning, drying, stand-by;
The preparation of B, film
0.01-20mg/ml catechol and 0.01-40mg/ml organic amine compound are dissolved in alkaline Tris-base damping fluid, 1-48h is reacted in solution after the base material prepared in A is soaked in reactant Homogeneous phase mixing, then with the abundant rinsing of distilled water, drying, obtains surface amine groups density 1-200nmol/cm
2target compound film.
3. the preparation method of a kind of rich amido polymer thin film according to claim 1, is characterized in that, the described polyphenolic substance containing pyrocatechol comprises Dopamine HCL, pyrocatechol.
4. the preparation method of a kind of rich amido polymer thin film according to claim 1, is characterized in that, described in there is double-end amino functional group organic amine compound comprise hexanediamine, quadrol, poly-lysine, polyetherimide (PEI).
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105238116A (en) * | 2015-09-21 | 2016-01-13 | 国家电网公司 | Corrosion protection layer of hollow copper conductor used in internal cooling water of generator and preparation method thereof |
| CN107837421A (en) * | 2017-09-15 | 2018-03-27 | 北京化工大学 | A kind of high-strength bone reparation with bioactivity modified Nano particle composite thermoplastic polymer 3D printing material and preparation |
| CN108939149A (en) * | 2018-07-18 | 2018-12-07 | 西南交通大学 | Prepare the method and PEEK biomaterial of PEEK biological coating |
| CN110016089A (en) * | 2019-04-17 | 2019-07-16 | 西南交通大学 | Rich amine base catecholamine compound and preparation method thereof, rich amine primary surface modified product, material and its dip-coating method |
| CN113150680A (en) * | 2019-12-25 | 2021-07-23 | 南京金斯瑞生物科技有限公司 | Chip coating, preparation method and application thereof |
| US11407921B2 (en) | 2016-12-22 | 2022-08-09 | Henkel Ag & Co. Kgaa | Reaction products of catechol compounds and functionalized co-reactant compounds for metal pretreatment applications |
| US11891534B2 (en) | 2016-12-22 | 2024-02-06 | Henkel Ag & Co. Kgaa | Treatment of conversion-coated metal substrates with preformed reaction products of catechol compounds and functionalized co-reactant compounds |
-
2014
- 2014-08-18 CN CN201410406190.7A patent/CN104211979A/en active Pending
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105238116A (en) * | 2015-09-21 | 2016-01-13 | 国家电网公司 | Corrosion protection layer of hollow copper conductor used in internal cooling water of generator and preparation method thereof |
| US11407921B2 (en) | 2016-12-22 | 2022-08-09 | Henkel Ag & Co. Kgaa | Reaction products of catechol compounds and functionalized co-reactant compounds for metal pretreatment applications |
| US11891534B2 (en) | 2016-12-22 | 2024-02-06 | Henkel Ag & Co. Kgaa | Treatment of conversion-coated metal substrates with preformed reaction products of catechol compounds and functionalized co-reactant compounds |
| CN107837421A (en) * | 2017-09-15 | 2018-03-27 | 北京化工大学 | A kind of high-strength bone reparation with bioactivity modified Nano particle composite thermoplastic polymer 3D printing material and preparation |
| CN108939149A (en) * | 2018-07-18 | 2018-12-07 | 西南交通大学 | Prepare the method and PEEK biomaterial of PEEK biological coating |
| CN110016089A (en) * | 2019-04-17 | 2019-07-16 | 西南交通大学 | Rich amine base catecholamine compound and preparation method thereof, rich amine primary surface modified product, material and its dip-coating method |
| CN110016089B (en) * | 2019-04-17 | 2020-06-16 | 西南交通大学 | Amino-rich catechol amine compound and preparation method thereof, amino-rich surface modified product, material and dip-coating method thereof |
| CN113150680A (en) * | 2019-12-25 | 2021-07-23 | 南京金斯瑞生物科技有限公司 | Chip coating, preparation method and application thereof |
| CN113150680B (en) * | 2019-12-25 | 2023-11-24 | 南京金斯瑞生物科技有限公司 | Chip coating, preparation method and application thereof |
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