CN105218847B - A kind of material surface and interface functional modification method based on polyphenol compound - Google Patents
A kind of material surface and interface functional modification method based on polyphenol compound Download PDFInfo
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Abstract
The invention discloses a kind of material surface and interface functional modification methods based on polyphenol compound.This method is that the base material that will be modified is soaked in the mixed solution of polyphenol compound, silane coupling agent and functional molecular, polyphenol compound reacted with substrate surface and autohemagglutination during react with functional molecular, eventually form one layer of polyphenol compound/functional molecular composite coating；Or the base material to be modified is soaked in the solution of polyphenol compound and silane coupling agent, using the autohemagglutination of polyphenol compound a strata polyphenol compound layer is formed in substrate surface, then it is reacted with functional molecular solution, obtains that there is functional coating.The present invention provides a kind of universality, simple and practicable new method for the surface-functionalized modification of different materials, and the surface for being suitable for almost any base material is modified.The secured coating of functionality finally obtained, can be obviously improved substrate surface performance.
Description
Technical field
The invention belongs to field of material surface modification, and in particular to polyphenol compound reacted with several functions molecule into
And to broad spectrum activity method that different materials surface is modified.
Background technology
The method that surface is modified is varied, cuts both ways.Two major class of physical method and chemical method can be generally divided into.
Physical method includes blending and simple spraying；Chemical method includes carrying out covalent bonding, surface grafting etc. to material surface.With
The discovery application and the raising to material performance requirement under various complex environments for various new materials, material surface modifying
Ask also in urgent need to be improved, simple and practicable, environmentally protective, energy-efficient is basic demand.
Containing multiple phenolic group groups in polyphenol compound, using dopamine and tannic acid as representative in field of surface modification.
Contain a large amount of catechol functional group in dopamine and tannin acid molecule so that the meeting under aerobic environment of their solution exists
Material surface forms one layer from poly layer.We can be by polyphenol compound from collecting process or autohemagglutination rear surface is big
The active group of amount carries out functional modification.In 104194023 A of Chinese invention patent CN, improved using dopamine medical poly-
Urethane material surface hydrophily and biocompatibility.In 104524986 A of Chinese invention patent CN, DOPA is coated using surface
The method of amine and polyethyleneimine amine cation is prepared for hydrophilic antimicrobial film.Although above-mentioned patent uses polyphenol compound dopamine
Hydrophily of material etc. is improved, but method is complicated, and coating is not very secured.
Invention content
The present invention for existing for existing surface modifying method the shortcomings of complex steps, inefficiency, insecure coating,
Provide a kind of pervasive method of modifying of material surface and interface functionalization based on polyphenol compound.The present invention is in Process of Surface Modification
In add silane coupling agent.Silane coupling agent includes hydrolyzable groups OMe, OEt and functional end-group NH2, SH, epoxy
Deng.In the process of polyphenol compound autohemagglutination, silane coupling agent on the one hand can be with the quinone of formation during Polyphenols autohemagglutination
Formula react, on the one hand can with material surface reaction bonded, so as to form a kind of silane coupling agent-polyphenol compound crosslinking net
Structure, and firmly it is fixed on substrate surface.It is simple and practicable in field of surface modification that this structure has polyphenol compound
The advantages of, but also with the performance that the simple polyphenol compound of analogy is more solid and reliable.Different work(is added in modifying process
Energy molecule, such as polyethyleneimine, amino polyvinyl alcohol, chitosan so that the further functionalization of material surface is applicable to parent
Water is modified, antibacterial modified, anti-/ demands such as protein stimulatory is adhesion modified.Compared with existing method of modifying, step of the present invention is simple, fits
Strong with property, the functional coating of preparation is more secured so that material can be applied to maintain performance in more rugged environment
It is constant.There is wide potential application foreground in fields such as medical instrument, material antiseptics.
The method of modifying of the present invention is divided into one-step method and two-step method.One-step method is that the base material to be modified is soaked in Polyphenols
In the mixed solution of compound, silane coupling agent and functional molecular, polyphenol compound is reacting and autohemagglutination with substrate surface
During reacted with functional molecular, eventually form one layer of polyphenol compound/functional molecular composite coating.Two-step method is that handle will
Modified base material is soaked in the solution of polyphenol compound and silane coupling agent, using the autohemagglutination of polyphenol compound in base material
Surface forms a strata polyphenol compound layer, is then reacted with functional molecular solution, obtains having functional coating.
The method one of material surface and interface functional modification method of the present invention based on polyphenol compound is：
(1) functional molecular is dissolved in trishydroxymethylaminomethane-hydrochloride buffer that pH value is 8-10, standby function
Addition polyphenol compound and silane coupling agent after molecular melting, a concentration of 1-5g/L of functional molecular, polyphenol compound
A concentration of 0.5-5g/L, a concentration of 0.1-0.5g/L of silane coupling agent；
(2) base material to be modified is soaked in the mixed solution of step (1) preparation, is reacted 6-48 hours at 30-60 DEG C；
(3) after reaction, base material is taken out, is rinsed well with deionized water, it is dry, obtain substrate surface coating polymerization
The composite coating of polyphenol compound and functional molecular.
Required temperature range is 37-50 DEG C during dissolving in the step of the method one (1).
The method two of material surface and interface functional modification method of the present invention based on polyphenol compound is：
1) polyphenol compound and silane coupling agent are dissolved in trishydroxymethylaminomethane-hydrochloric acid that pH value is 8-10
In buffer solution, a concentration of 0.5-5g/L of polyphenol compound, a concentration of 0.1-0.5g/L of silane coupling agent；Base material is impregnated
It 6-24 hours in above-mentioned solution, then takes out, and rinsed well with deionized water, obtains surface coated with polyphenol compound
Base material；
2) functional molecular is dissolved in the phosphate buffer solution that pH value is 8-10, a concentration of 1-5g/ of functional molecular
L；The base material that surface is coated with to polyphenol compound is immersed in the phosphate buffer solution of above-mentioned functional molecular, 30-60 DEG C
Lower reaction 6-48 hours；
3) base material after reaction, is taken out, is rinsed well with deionized water, it is dry, obtain substrate surface coating polymerization
The composite coating of polyphenol compound and functional molecular.
The base material is selected from glass, ceramics, polypropylene, polyethylene, polyamide, polyurethane, stainless steel, aluminium alloy.
Surface decontamination processing is first carried out before the substrate modifications.
The polyphenol compound is dopamine, tannic acid.
The functional molecular is Quaternary Polyethyleneimine, chitosan, amino-polyethyleneglycols, gelatin, heparin, heparin
Sodium, gentamicin.
The silane coupling agent is selected from KH540, KH550, KH560, KH580, KH590.
The base material immersion way be totally immersed into solution and to be modified it is face-up.
The one-step method of the present invention is to utilize polyphenol compound in the process of autohemagglutination, abundant active group, example
Such as amino, hydroxyl are reacted with the active function groups of different function molecule, such as amino, carboxyl, sulfydryl etc., and are added a small amount of
Silane coupling agent, formed one layer of polyphenol compound/functional molecular composite coating.The one-step method can be applied to material surface
Hydrophilic modifying promotes protein adherence, cell adherence, surface anti-pollution, anticorrosive modification etc..Two-step method is first to consolidate in substrate surface
Fixed one layer of polyphenol compound, followed by the activity of the abundant active group in polyphenol compound surface and different function molecule
Functional group reactions, so as to which functional molecular is securely seated between substrate surface.The two-step method modified substrate surface, in addition to having one
Outside the function that footwork modification can have, anti-protein, the functions such as cell adherence, antibacterial can also be carried out to different substrate materials surface
It is modified.The present invention provides a kind of universality, simple and practicable new method, Ji Hushi for the surface-functionalized modification of different materials
It is modified for the surface of any base material.The secured coating of functionality finally obtained, can be obviously improved substrate surface performance.
Figure of description
Fig. 1 is that the surface water contact angle of polypropylene base and process dopamine/gelatin coating are modified before modified in embodiment 1
Surface water contact angle later；Left figure is 104.3 ° before modified, and right figure is modified 51.6 °；
Fig. 2 is the adherency growing state and process on the HEK293 cells surface of polypropylene base before modification in embodiment 1
The adherency growing state on the surface after dopamine/gelatin coating is modified；Left figure is before modified, right figure is modified；
Fig. 3 is that the surface water contact angle of stainless steel substrate and process dopamine/gelatin coating are modified before modified in embodiment 2
Surface water contact angle later；Left figure is 86.5 ° before modified, and right figure is modified 46.5 °；
Fig. 4 be embodiment 5 in before modified the surface water contact angle of glass baseplate and pass through poly-dopamine-activated polyethylene glycol
Surface water contact angle after coating is modified；Left figure is 44.9 ° before modified, and right figure is modified 32.3 °；
Fig. 5 is that the adherency growing state on the surface of glass baseplate and process are poly- before modification for HEK293 cells in embodiment 5
The adherency growing state on the surface after dopamine-amino-polyethyleneglycols coating is modified.Left figure is before modified, right figure is is modified
Afterwards；
Fig. 6 is that the surface water contact angle of glass baseplate and process poly-dopamine-polyethyleneimine apply before modified in embodiment 6
Cover the surface water contact angle after being modified；Left figure is 42.7 ° before modified, and right figure is modified 36.2 °；
Fig. 7 is that the adherency growing state on the surface of glass baseplate and process are poly- before modification for HEK293 cells in embodiment 6
The adherency growing state on the surface after dopamine-Quaternary Polyethyleneimine coating is modified；Left figure is before modified, right figure is changes
After property.
Specific embodiment
It is further illustrated the present invention below by embodiment, but is not limited to following embodiment.Reading this
After inventing the content lectured, those skilled in the art can make various modifications or changes to the present invention, as long as the present invention's
Within spirit and principle, change, modification of such equivalent forms etc. should all be included in the protection scope of the present invention.
Embodiment 1
One-step method is in polypropylene base surface construction poly-dopamine/gelatin-compounded coating：5g gelatin is added to tri- hydroxyls of 1L
In vlmethyl methane-hydrochloride buffer (pH=8.5), solution, which is heated to 37 DEG C, makes Gelatin；By 2g dopamines with
And 0.5g silane coupling agents KH540 is added in above-mentioned solution, is stirred evenly；Sheet-like polypropylene base material (2cm × 2cm) is advanced
The processing of row surface decontamination, what is be then totally immersed into the mixed solution of above-mentioned preparation and to be modified is face-up, is taken out after 12h
Polypropylene base is rinsed 5 times with deionized water, and poly-dopamine/gelatin-compounded coating is obtained after dry.It is not taken off using sharp instrument scraped finish
It falls.Water contact angle is measured, unmodified polypropylene base water contact angle is 104.3 °, modified polypropylene base water contact angle
For 51.6 ° (Fig. 1).HEK293 cells are on unmodified polypropylene base surface and by poly-dopamine/gelatin coating modification
The growing state on polypropylene base surface afterwards is as shown in Figure 2.This it appears that unmodified polypropylene base surface is not glued
Attached cell, and through substrate surface cell adherence and well-grown after modification.This shows by poly-dopamine/gelatin surface
Polypropylene base after modification has good biocompatibility, can promote the adherency and growth of cell.
Embodiment 2
One-step method forms poly-dopamine/gelatin-compounded coating on stainless steel substrate surface：Stainless steel substrate is respectively placed in
It is cleaned by ultrasonic 5min in deionized water, acetone, ethanol solution.Polypropylene base in embodiment 1 is substituted for stainless steel substrate,
Other experiment conditions are same as Example 1, and the stainless base steel for the biocompatibility that cell adherence can be promoted to grow is prepared
Material.As shown in figure 3, stainless steel substrate water contact angle before modified is 86.5 °, water contact angle becomes 46.5 ° after modification.
Embodiment 3
One-step method forms poly- tannic acid/gelatin-compounded coating on polypropylene base surface：Dopamine in embodiment 1 is replaced
Change tannic acid into, other experiment conditions are same as Example 1, and the biocompatibility that cell adherence can be promoted to grow is prepared
The coating of poly- tannic acid/gelatin stainless steel substrate.
Embodiment 4
One-step method forms poly- tannic acid/gelatin-compounded coating on stainless steel substrate surface：By the polypropylene-base in embodiment 1
Material is substituted for stainless steel substrate, and dopamine is substituted for tannic acid, other experiment conditions are same as Example 1, and being prepared can be with
Promote the stainless steel substrate of poly- tannic acid/gelatin coating of the biocompatibility of cell adherence growth.
Embodiment 5
Two-step method builds polyethylene glycol functionalized surface in glass substrate surface：By 2g dopamines and 0.5g silane coupling agents
KH590 is dissolved in 1L trishydroxymethylaminomethanes-hydrochloride buffer (pH=8.5), by glass baseplate (2cm × 2cm) first
Surface decontamination processing is carried out, what is be then totally immersed into above-mentioned dopamine solution and to be modified is face-up, is taken out after 12h,
It is rinsed well with deionized water；The glass baseplate for being coated with dopamine rinsed well is immersed to the poly- second of amino of a concentration of 5g/L
In the phosphate buffered saline solution (pH=8.5) of glycol (molecular weight 4000), face that base material is totally immersed into solution and to be modified
Upward；Reaction is placed in 37 DEG C of insulating box for 24 hours；It treats after reaction, to take out base material, be rinsed 5 times with deionized water, after cleaning
Obtain the glass baseplate that poly-dopamine-activated polyethylene glycol coating is coated with to surface.Measure water contact angle, unmodified glass base
Material water contact angle is 44.9 °, and modified glass baseplate water contact angle is 32.3 ° (Fig. 4).HEK293 cells are in unmodified glass
Glass substrate surface and the growing state such as figure that the glass substrate surface after being modified is coated by poly-dopamine-activated polyethylene glycol
Shown in 5.This it appears that in unmodified glass substrate surface, cell can attach growth, and pass through poly-dopamine-work
Glass substrate surface cell after polyethylene glycol coating is modified will not attach growth substantially.This shows by passing through two-step method
After glass substrate surface is grafted the activated polyethylene glycol for inhibiting cell, glass baseplate has the function of inhibiting cell adherence
Property.
Embodiment 6
Two-step method builds polyethyleneimine functionalized surface in glass substrate surface：By the poly- second two of activation in embodiment 5
Alcohol is substituted for Quaternary Polyethyleneimine (molecular weight 25000), other experiment conditions are same as Example 5, are prepared both
It can inhibit cell adherence, and can be with the glass baseplate of antibacterial.Water contact angle is measured, unmodified glass baseplate water contact angle is
42.7 °, modified glass baseplate water contact angle is 36.2 ° (Fig. 6).HEK293 cells in unmodified glass substrate surface and
Growing state by glass substrate surface of the poly-dopamine-Quaternary Polyethyleneimine coating after modified is as shown in Figure 7.It can
Will become apparent from unmodified glass substrate surface, cell can attach growth, and pass through poly-dopamine-quaternized poly- second
Glass substrate surface cell after the coating of alkene imines is modified will not attach growth substantially.Antibacterial experiment discovery is carried out to base material,
By glass baseplate of the poly-dopamine-Quaternary Polyethyleneimine coating after modified with good antibacterial effect.
Embodiment 7
Two-step method builds chitosan functionalized surface in glass substrate surface：Activated polyethylene glycol in embodiment 5 is replaced
Change chitosan into, other experiment conditions are same as Example 5, and the glass baseplate with anti-microbial property is prepared.To base material into
Row antibacterial experiment is found, by glass baseplate of the poly-dopamine-chitosan coating after modified with good antibacterial effect.
Embodiment 8
Two-step method builds gentamicin functionalized surface in glass substrate surface：By the activated polyethylene glycol in embodiment 5
Gentamicin is substituted for, other experiment conditions are same as Example 5, and the glass baseplate with anti-microbial property is prepared.To base
Material carries out antibacterial experiment discovery, by glass baseplate of the poly-dopamine-chitosan coating after modified with good antibacterial effect
Fruit.
Embodiment 9
Two-step method builds heparin sodium functionalized surface in glass substrate surface：Activated polyethylene glycol in embodiment 5 is replaced
Change heparin sodium into, other experiment conditions are same as Example 5, and the glass baseplate with blood compatibility performance is prepared.Pass through
Activating part thromboplastin time (APTT), which measures, to be found, the clotting time on unmodified glass baseplate passed through less than 30 seconds
The clotting time on glass baseplate crossed after poly-dopamine-heparin sodium coating is modified is obviously prolonged, can be more than 1 minute.Pass through
Scanning electron microscope microscope photo it has also been discovered that the blood platelet of unmodified glass sheet surface by a degree of activation, it will be apparent that
Pseudopodium is stretched out, and the platelet PLA2 on the glass baseplate passed through after poly-dopamine-heparin sodium coating is modified compares rounding, quilt
Activation degree is relatively low.
Claims (7)
- A kind of 1. material surface and interface functional modification method based on polyphenol compound, which is characterized in that this method it is specific Step is：（1）Functional molecular is dissolved in trishydroxymethylaminomethane-hydrochloride buffer that pH value is 8-10, standby function molecule Polyphenol compound and silane coupling agent, a concentration of 1-5 g/L of functional molecular, the concentration of polyphenol compound are added in after dissolving For 0.5-5g/L, a concentration of 0.1-0.5 g/L of silane coupling agent；（2）Base material to be modified is soaked in step（1）In the mixed solution of preparation, reacted 6-48 hours at 30-60 DEG C；（3）After reaction, base material is taken out, is rinsed well with deionized water, it is dry, obtain the polyphenol of substrate surface coating polymerization The composite coating of class compound and functional molecular；The polyphenol compound is dopamine, tannic acid；The functional molecular is Quaternary Polyethyleneimine, chitosan, amino-polyethyleneglycols, gelatin, heparin, heparin sodium, celebrating Big mycin.
- A kind of 2. material surface and interface functional modification method based on polyphenol compound, which is characterized in that this method it is specific Step is：1）Polyphenol compound and silane coupling agent are dissolved in trishydroxymethylaminomethane-hydrochloride buffer that pH value is 8-10 In liquid, a concentration of 0.5-5g/L of polyphenol compound, a concentration of 0.1-0.5 g/L of silane coupling agent；Base material is soaked in It 6-24 hours in above-mentioned solution, then takes out, and rinsed well with deionized water, obtains surface and be coated with polyphenol compound Base material；2）Functional molecular is dissolved in the phosphate buffer solution that pH value is 8-10, a concentration of 1-5 g/L of functional molecular；It will The base material that surface is coated with polyphenol compound is immersed in the phosphate buffer solution of above-mentioned functional molecular, anti-at 30-60 DEG C It answers 6-48 hours；3）After reaction, base material is taken out, is rinsed well with deionized water, it is dry, obtain the polyphenol of substrate surface coating polymerization The composite coating of class compound and functional molecular；The polyphenol compound is dopamine, tannic acid；The functional molecular is Quaternary Polyethyleneimine, chitosan, amino-polyethyleneglycols, gelatin, heparin, heparin sodium, celebrating Big mycin.
- 3. according to the method described in claim 1, it is characterized in that, step（1）Required temperature range is 37- during middle dissolving 50℃。
- 4. method according to claim 1 or 2, which is characterized in that the base material is selected from glass, ceramics, polypropylene, gathers Ethylene, polyamide, polyurethane, stainless steel, aluminium alloy.
- 5. method according to claim 1 or 2, which is characterized in that first carried out at surface decontamination before the substrate modifications Reason.
- 6. method according to claim 1 or 2, which is characterized in that the silane coupling agent is selected from KH540, KH550, KH560, KH580, KH590.
- 7. method according to claim 1 or 2, which is characterized in that the base material immersion way is is totally immersed into solution And it to be modified face-up.
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