CN108250477B - Modified SEBS material and preparation method and application thereof - Google Patents
Modified SEBS material and preparation method and application thereof Download PDFInfo
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- A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
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- A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
- A61L31/14—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
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- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
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- C08J2353/00—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
- C08J2353/02—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers of vinyl aromatic monomers and conjugated dienes
Abstract
The invention belongs to the field of high polymer materials, and particularly relates to a modified SEBS material, a preparation method and an application thereof, wherein the material comprises the following components: the modified polyurethane SEBS comprises a dopamine modified SEBS and a hydrophilic polymer, wherein two end groups of the hydrophilic polymer are grafted on the surface of the SEBS; the two end groups of the hydrophilic polymer are selected from sulfydryl, amino, carboxyl or sulfonic acid groups. The invention takes dopamine as a bionic adhesive, fixes two ends of a hydrophilic polymer on the surface of SEBS to construct loop conformation of the hydrophilic polymer, and avoids pollution and toxicity of an organic solvent because no organic solvent is used in the whole surface grafting process. According to the invention, the hydrophilic polymer with loop conformation is constructed on the surface of the SEBS, so that the capability of resisting protein and platelet adhesion of the SEBS is further improved compared with the hydrophilic polymer with brush conformation constructed on the surface of the SEBS, excellent blood compatibility is shown, and good social and economic benefits can be generated when the SEBS is applied to the field of biomedical materials.
Description
Technical Field
The invention belongs to the field of high polymer materials, and particularly relates to a modified SEBS material, and a preparation method and application thereof.
Background
With the development of medicine, life science and material science, biological materials have good development prospects, such as application in artificial hearts, artificial blood vessels, blood bags and the like, which are closely related to human health. The polymer material has wide application in the field of biological materials due to the specific performance of the polymer material. At present, polyvinyl chloride (PVC) is the most widely used polymer material in the field of biological materials, but due to the defects that the PVC is easy to separate out a plasticizer di (2-ethyl) hexyl phthalate (DEHP) harmful to human bodies, the radiation resistance is poor, and sterilization is limited, a great deal of work is done at home and abroad in the aspect of developing medical PVC alternative materials.
The hydrogenated styrene-butadiene block copolymer (SEBS) is an ideal material for replacing medical PVC due to excellent aging resistance, thermal stability, thermoplasticity, high product transparency and easy sterilization. However, SEBS has low surface energy, and when the material is in contact with blood, plasma proteins are easily adsorbed on the surface of the material, so that the adhesion and activation of platelets are promoted, and coagulation and thrombosis are finally caused. Furthermore, the surface of SEBS has no reactive functional group, and there is a limit to the surface modification, and common surface modification means are as follows: ultraviolet radiation, ozone irradiation, surface-initiated-atom transfer radical polymerization and the like are difficult to implement or have high cost, which also limits the application range of the medical treatment field to a certain extent.
Polyethylene glycol (PEG) is commonly used for modifying the surface of materials due to its advantages of strong hydrophilicity, low immunocompetence, non-toxicity, etc., and most studies have focused on the influence of the length and density of graft chains on the antifouling property after PEG forms a brush shape (brush) on the surface of materials, and few studies have focused on the influence of the formation of a ring shape (loop) on the antifouling property.
Disclosure of Invention
In view of the above, the present invention aims to provide a modified SEBS material, and a preparation method and an application thereof, and the modified SEBS material provided by the present invention constructs a loop conformation of a hydrophilic polymer on a SEBS substrate, and has excellent blood compatibility.
The invention provides a modified SEBS material, which comprises: the modified polyurethane SEBS comprises a dopamine modified SEBS and a hydrophilic polymer, wherein two end groups of the hydrophilic polymer are grafted on the surface of the SEBS;
the two end groups of the hydrophilic polymer are selected from sulfydryl, amino, carboxyl or sulfonic acid groups.
Preferably, the hydrophilic polymer comprises one or more of bis-sulfhydryl PEG, bis-amino PEG, bis-carboxyl PEG, bis-sulfo PEG, bis-sulfhydryl polyamino acid, bis-amino polyamino acid, bis-carboxyl polyamino acid, bis-sulfhydryl polyamino acid derivative, bis-amino polyamino acid derivative, bis-carboxyl polyamino acid derivative, bis-sulfo polyamino acid derivative, bis-sulfhydryl zwitterionic polymer, bis-amino zwitterionic polymer, bis-carboxyl zwitterionic polymer and bis-sulfo zwitterionic polymer.
Preferably, the number average molecular weight of the hydrophilic polymer is 1000 to 20000.
The invention provides a preparation method of a modified SEBS material, which comprises the following steps:
providing a dopamine modified SEBS, wherein the SEBS reacts in a hydrophilic polymer solution to obtain a modified SEBS material;
the two end groups of the hydrophilic polymer are selected from sulfydryl, amino, carboxyl or sulfonic acid groups.
Preferably, the content of the hydrophilic polymer in the hydrophilic polymer solution is 0.05-10 mg/ml.
Preferably, the reaction temperature is 25-90 ℃, the reaction time is 1-12 h, and the reaction pH value is 7.2-10.
Preferably, the dopamine modified SEBS is prepared according to the following method:
and (3) reacting the SEBS substrate in a dopamine solution to obtain the dopamine modified SEBS.
Preferably, the content of the dopamine in the dopamine solution is 0.05-30 wt%.
Preferably, the temperature of the SEBS substrate in the dopamine solution is 25-50 ℃, the reaction time is 2-24 hours, and the pH value of the reaction is 7.2-10.
The invention provides a medical apparatus which comprises the modified SEBS material in the technical scheme or the modified SEBS material prepared by the method in the technical scheme.
Compared with the prior art, the invention provides a modified SEBS material and a preparation method and application thereof. The modified SEBS material provided by the invention comprises: the modified polyurethane SEBS comprises a dopamine modified SEBS and a hydrophilic polymer, wherein two end groups of the hydrophilic polymer are grafted on the surface of the SEBS; the two end groups of the hydrophilic polymer are selected from sulfydryl, amino, carboxyl or sulfonic acid groups. The invention takes dopamine as a bionic adhesive, fixes two ends of a hydrophilic polymer on the surface of SEBS to construct loop conformation of the hydrophilic polymer, and avoids pollution and toxicity of an organic solvent because no organic solvent is used in the whole surface grafting process. According to the invention, the hydrophilic polymer with loop conformation is constructed on the surface of SEBS, so that the capability of the SEBS to resist the adhesion of protein and platelets is greatly improved, the SEBS shows excellent blood compatibility, and good social and economic benefits can be generated when the SEBS is applied to the field of biomedical materials. Experimental results show that compared with the unmodified SEBS and the SEBS modified by PEG to form a surface with a brush conformation, the PEG loop conformation modified SEBS material provided by the invention has greatly improved blood compatibility.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the provided drawings without creative efforts.
FIG. 1 is an IR spectrum of a different modified surface provided in example 1 of the present invention;
FIG. 2 is a water contact angle measurement result of different modified surfaces provided in example 1 of the present invention;
FIG. 3 is a histogram of the adsorption amounts of four proteins Fib, BSA, IgG and lysozyme provided in example 1 of the present invention on different modified surfaces;
FIG. 4 is a CLSM map of platelets provided in example 1 of the present invention adhering to various modified surfaces;
FIG. 5 is SEM images of the adhesion of platelets to various modified surfaces provided in example 1 of the present invention;
FIG. 6 is a histogram of the amount of platelets adhering to various modified surfaces as provided in example 1 of the present invention;
FIG. 7 shows QCM-D results of grafting of 5000 molecular weight mono-bis-thiol PEG on the surface of modified material provided in example 2 of the present invention;
FIG. 8 is a bar graph of the adsorption capacity of Fib proteins provided in example 2 of the present invention on the grafted surface with different PEG conformations with the same grafting quality;
FIG. 9 is a bar graph of the amount of adsorption of BSA protein provided in example 2 of the present invention on the grafted surface with different PEG conformations with the same grafting quality;
FIG. 10 shows the results of QCM-D grafting of 5000 molecular weight monothio-PEG and 10000 molecular weight dimercapto PEG on the surface of modified material provided in example 3 of the present invention;
FIG. 11 is a histogram of the adsorption capacity of Fib proteins provided in example 3 of the present invention on the grafting surface of PEG conformation grafts of the same grafting quality and different grafting densities;
FIG. 12 is a bar graph of the amount of PEG-conformational grafted surface adsorbed by BSA protein provided in example 3 of the present invention at the same grafting mass and at the same grafting density.
Detailed Description
The technical solutions in the embodiments of the present invention are clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides a modified SEBS material, which comprises: the modified polyurethane SEBS comprises a dopamine modified SEBS and a hydrophilic polymer, wherein two end groups of the hydrophilic polymer are grafted on the surface of the SEBS;
the two end groups of the hydrophilic polymer are selected from sulfydryl, amino, carboxyl or sulfonic acid groups.
The modified SEBS material provided by the invention comprises a dopamine modified SEBS and a hydrophilic polymer. The bamine modified SEBS can be prepared by adopting the following method:
and (3) reacting the SEBS substrate in a dopamine solution to obtain the dopamine modified SEBS.
In the preparation method of the dopamine-modified SEBS provided by the invention, the SEBS base material is an SEBS material which is not modified or modified, and the SEBS material can be prepared from SEBS powder provided by Kraton company and having a brand number of G1652; the content of dopamine in the dopamine solution is preferably 0.05-30 wt%, and specifically can be 0.05 wt%, 0.5 wt%, 1 wt%, 2 wt%, 3 wt%, 4 wt%, 5 wt%, 6 wt%, 7 wt%, 8 wt%, 9 wt%, 10 wt%, 11 wt%, 12 wt%, 13 wt%, 14 wt%, 15 wt%, 20 wt%, 25 wt% or 30 wt%; the reaction temperature is preferably 25-50 deg.C, specifically 25 deg.C, 26 deg.C, 27 deg.C, 28 deg.C, 29 deg.C, 30 deg.C, 31 deg.C, 32 deg.C, 33 deg.C, 34 deg.C, 35 deg.C, 36 deg.C, 37 deg.C, 38 deg.C, 39 deg.C, 40 deg.C, 41 deg.C, 42 deg.C, 43 deg.C, 44 deg.C, 45 deg.; the reaction time is preferably 2-24 h, and specifically can be 2h, 3h, 4h, 5h, 6h, 7h, 8h, 9h, 10h, 11h, 12h, 13h, 14h, 15h, 16h, 17h, 18h, 19h, 20h, 21h, 22h, 23h or 24 h; the pH value of the reaction is preferably controlled to be 7.2-10, and more preferably 7.5-9.5. In the present invention, it is preferable to control the reaction pH by adding Tris-HCl buffer to the reaction system. In one embodiment of the present invention, Tris (Tris hydroxymethyl aminomethane), hydrochloric acid and water may be mixed to obtain an aqueous Tris-HCl solution with a suitable pH, and then the aqueous solution and dopamine may be mixed to obtain a dopamine solution with a suitable pH, and then the SEBS substrate may be reacted in the dopamine solution. And after the SEBS substrate reacts in the dopamine solution, washing and drying a reaction product to obtain the dopamine modified SEBS.
In the invention, two end groups of the hydrophilic polymer are grafted on the surface of the SEBS, and the two end groups of the hydrophilic polymer are selected from sulfydryl, amino, carboxyl or sulfonic acid. In the present invention, the hydrophilic polymer includes, but is not limited to, one or more of bis-thiol PEG, bis-amino PEG, bis-carboxyl PEG, bis-sulfo PEG, bis-thiol polyamino acid, bis-amino polyamino acid, bis-carboxyl polyamino acid, bis-thiol polyamino acid derivative, bis-amino polyamino acid derivative, bis-carboxyl polyamino acid derivative, bis-sulfo polyamino acid derivative, bis-thiol zwitterionic polymer, bis-amino zwitterionic polymer, bis-carboxyl zwitterionic polymer, and bis-sulfo zwitterionic polymer; the number average molecular weight of the hydrophilic polymer is preferably 1000 to 20000, and specifically may be 1000, 1500, 2000, 2500, 3000, 3500, 4000, 4500, 5000, 5500, 6000, 6500, 7000, 7500, 8000, 8500, 9000, 9500, 10000, 11000, 11500, 12000, 12500, 13000, 13500, 14000, 14500, 15000, 15500, 16000, 16500, 17000, 17500, 18000, 18500, 19000, 19500 or 20000.
The modified material provided by the invention takes dopamine as a bionic adhesive, and the two ends of a hydrophilic polymer are fixed on the surface of SEBS (styrene-ethylene-butylene-styrene copolymer) to construct a loop conformation of the hydrophilic polymer. According to the invention, the hydrophilic polymer surface with loop conformation is constructed on the surface of the SEBS, so that the blood compatibility of the SEBS is greatly improved, and the SEBS can generate good social and economic benefits when being applied to the field of biomedical materials. The experimental result shows that compared with the unmodified SEBS and the SEBS modified by PEG to form a surface with a brush conformation, the SEBS material modified by the loop conformation of the PEG provided by the invention has greatly improved blood compatibility.
The invention provides a preparation method of a modified SEBS material, which comprises the following steps:
providing a dopamine modified SEBS, wherein the SEBS reacts in a hydrophilic polymer solution to obtain a modified SEBS material;
the two terminal groups of the hydrophilic polymer are independently selected from thiol, amino, carboxyl or sulfonic acid groups.
In the preparation method provided by the invention, firstly, the dopamine modified SEBS is provided, and the preparation method of the dopamine modified SEBS is introduced above and is not described again here.
And after obtaining the SEBS modified by dopamine, reacting the SEBS in a hydrophilic polymer solution. Wherein, the hydrophilic polymer is already introduced in the above, and is not described in detail herein; the content of the hydrophilic polymer in the hydrophilic polymer solution is preferably 0.05-10 mg/ml, and specifically can be 0.05mg/ml, 0.1mg/ml, 0.5mg/ml, 1mg/ml, 1.5mg/ml, 2mg/ml, 2.5mg/ml, 3mg/ml, 3.5mg/ml, 4mg/ml, 4.5mg/ml, 5mg/ml, 5.5mg/ml, 6mg/ml, 6.5mg/ml, 7mg/ml, 7.5mg/ml, 8mg/ml, 8.5mg/ml, 9mg/ml, 9.5mg/ml or 10 mg/ml; the reaction temperature is preferably 25-90 ℃, and specifically can be 25 ℃, 30 ℃, 35 ℃, 40 ℃, 45 ℃, 50 ℃, 55 ℃, 60 ℃, 65 ℃, 70 ℃, 75 ℃, 80 ℃, 85 ℃ or 90 ℃; the reaction time is preferably 1-12 h, and specifically can be 1h, 1.5h, 2h, 2.5h, 3h, 3.5h, 4h, 4.5h, 5h, 5.5h, 6h, 6.5h, 7h, 7.5h, 8h, 8.5h, 9h, 9.5h, 10h, 10.5h, 11h, 11.5h or 12 h; the pH value of the reaction is preferably controlled to be 7.2-10, and more preferably 7.5-9.5. In the present invention, it is preferable to control the reaction pH by adding Tris-HCl buffer to the reaction system. In one embodiment provided by the present invention, Tris, hydrochloric acid and water may be mixed to obtain a Tris-HCl aqueous solution with an appropriate pH, and then the aqueous solution and a hydrophilic polymer are mixed to obtain a hydrophilic polymer solution with an appropriate pH, and then the dopamine-modified SEBS is reacted in the hydrophilic polymer solution. And after the reaction of the dopamine modified SEBS in the hydrophilic polymer solution is finished, washing and drying a reaction product to obtain the modified SEBS material provided by the invention.
According to the preparation method provided by the invention, dopamine is used as a bionic adhesive, and two ends of a hydrophilic polymer are grafted to the surface of SEBS, so that the loop conformation of the hydrophilic polymer is constructed, and the blood compatibility of the SEBS is greatly improved. The preparation method provided by the invention has the advantages of no participation of organic solvents, high grafting speed, simple preparation process, mild reaction conditions and suitability for large-scale production. The experimental result shows that compared with the unmodified SEBS and the SEBS modified by PEG to form a surface with a brush conformation, the SEBS material modified by the loop conformation of the PEG provided by the invention has greatly improved blood compatibility.
The invention also provides a medical apparatus which comprises the modified SEBS material or the modified SEBS material prepared by the method in the technical scheme.
The medical apparatus provided by the invention uses the modified SEBS material as part or all of the material, and the medical apparatus comprises but is not limited to an artificial heart, an artificial blood vessel or a blood bag. The medical device provided by the invention also has excellent blood compatibility due to the modified SEBS material.
For the sake of clarity, the following examples are given in detail.
Example 1
Mixing Tris and water and adjusting the pH value by using hydrochloric acid to obtain a Tris-HCl solution with the pH value of 7.5-9.5; mixing dopamine with the Tris-HCl solution to obtain a dopamine/Tris-HCl aqueous solution with the dopamine content of 2 wt%; mixing monothiol PEG (number average molecular weight 5k) with the Tris-HCl solution to obtain a monothiol PEG (5k)/Tris-HCl solution with the monothiol PEG content of 5 mg/ml; and mixing the dimercaptoPEG (the number average molecular weight is 5k) with the Tris-HCl solution to obtain the dimercaptoPEG (5k)/Tris-HCl solution with the dimercaptoPEG content of 5 mg/ml.
SEBS powder (manufactured by Kraton, brand G1652, polystyrene content 29 wt%) is prepared into a xylene solution of 15 wt% SEBS, and the solution is dripped on a glass plate and volatilized to obtain the SEBS film. And soaking the SEBS membrane into the dopamine/Tris-HCl aqueous solution, stirring at room temperature for reaction for 2 hours, washing with deionized water for three times, washing with ethanol for one time, and drying with nitrogen to obtain the dopamine-modified SEBS membrane.
And (2) placing the SEBS membrane modified by dopamine in a monothiol PEG (5k)/Tris-HCl solution, reacting for 7h at 40 ℃, washing with deionized water for three times, washing with ethanol for one time, drying with nitrogen, modifying the SEBS material with the monothiol PEG, wherein the monothiol PEG in the modified material forms a brush conformation on the surface of the SEBS.
And (2) placing the SEBS membrane modified by dopamine in a dimercapto PEG (5k)/Tris-HCl solution, reacting for 3h at 40 ℃, washing with deionized water for three times, washing with ethanol for one time, drying with nitrogen, modifying the SEBS material with the dimercapto PEG, wherein the dimercapto PEG in the modified material forms a loop conformation on the surface of the SEBS.
And (4) analyzing results:
1) the results of the infrared test on the surface of the material before and after modification are shown in FIG. 1, and FIG. 1 shows the infrared spectra of different modified surfaces provided in example 1 of the present invention, wherein (a) is 4000-750 cm-1And (b) is a spectrum in a wave number range of 2000-800, wherein SEBS in the graph 1 represents an unmodified SEBS film, SEBS-PDOPA represents a dopamine modified SEBS film, and SEBS-PDOPA-PEG represents a bis-sulfhydryl PEG modified SEBS material. As shown in FIG. 1(a), after grafting dopamine, at 3400cm-1The stretching vibration peak of N-H/OH appears on the left and the right, which indicates that the dopamine grafting is successful, and is 1110cm in the graph of (b)-1A C-O-C characteristic peak appears, which indicates that the PEG grafting is successful.
2) X-ray photoelectron spectroscopy (XPS) was performed on the obtained monothiol PEG-modified SEBS material and the dimercapto PEG-modified SEBS material, and the results are shown in table 1:
TABLE 1 PEG-modified SEBS surface element content in different conformations
As can be seen from table 1, the surface sulfur content of the dimercapto PEG modified is about twice that of the monothiomercapto PEG modified surface, when the PEG grafting qualities for loop conformation and brush conformation are close.
3) Testing and comparing the antifouling performance of the loop conformation modified surface formed by the dimercapto PEG and the antifouling performance of the brush conformation modified surface formed by the monothiomercapto PEG.
3-1) testing the water contact angle of the material before and after modification, the result is shown in fig. 2, fig. 2 is the detection result of the water contact angle of the surface with different modifications provided by the embodiment 1 of the present invention, in fig. 2, SEBS represents an unmodified SEBS film, PDA represents a dopamine-modified SEBS film, brush represents a mono-thiol PEG-modified SEBS material, and loop represents a bis-thiol PEG-modified SEBS material. As can be seen from FIG. 2, with the graft modification of dopamine and PEG, the surface water contact angle is obviously reduced, which indicates that the surface hydrophilicity of the modified material is enhanced, thereby being beneficial to anti-fouling.
3-2) the adsorption performance of the surfaces of the materials before and after modification on four proteins, namely Fib, BSA, IgG and lysozyme, is tested by using an enzyme-labeling instrument (the proteins are prepared into a protein PBS solution of 1mg/ml and are statically adsorbed for 2h at 37 ℃), and the results are shown in fig. 3, wherein fig. 3 is a histogram of adsorption amounts of the four proteins, namely Fib, BSA, IgG and lysozyme, on different modified surfaces provided in example 1 of the present invention, in fig. 3, SEBS represents an unmodified SEBS membrane, PDA represents a dopamine-modified SEBS membrane, brush represents a mono-thiol PEG-modified SEBS material, and loop represents a bis-thiol PEG-modified SEBS material. As can be seen from fig. 3, the adsorption amounts of the four proteins Fib, BSA, IgG and lysozyme are significantly reduced with the grafting of dopamine and PEG, and it is particularly worth mentioning that the loop conformation of PEG is reduced by 37.3%, 39.2%, 40.5% and 55.2% compared with the brush conformation.
3-3) testing the adhesion performance of platelets before and after modification of the material by using laser confocal CLSM (fresh rabbit blood is collected into an anticoagulant blood collection tube containing 3.8 wt% of sodium citrate, centrifuged at 1000rpm for 15min, upper-layer platelets are collected, 20 μ L of platelets are dropped on the surface of the material soaked in advance with PBS, statically adsorbed for 1h at 37 ℃, washed with PBS solution for three times, then fixed with 1ml of 2.5 v/v% glutaraldehyde/PBS solution at 4 ℃ overnight, washed with PBS solution for three times, then dehydrated with 10%, 30%, 50%, 70%, 90%, 100% ethanol aqueous solution in gradient, then placed in a vacuum oven for drying, and finally tested with CLSM and SEM), and the results are shown in fig. 4, wherein fig. 4 is a graph showing that platelets provided in example 1 of the present invention adhere to CLSM on different modified surfaces, fig. 4 is showing that SEBS membrane is not modified, and fig. 4 is showing that SEBS membrane is showing dopamine modified, brush represents a mono-sulfhydryl PEG modified SEBS material, and loop represents a bis-sulfhydryl PEG modified SEBS material. As can be seen from fig. 4, with the grafting of dopamine and PEG, the amount of platelet adhesion is significantly reduced, and the loop conformation of PEG has better effect on platelet adhesion than the brush conformation.
3-4) the adhesion performance of the platelets before and after modification of the material by SEM is further tested, and the result is shown in figure 5, and figure 5 is an SEM image of the adhesion of the platelets on different modified surfaces provided by example 1 of the invention. As can be seen from fig. 5, with the grafting of dopamine and PEG, the amount of platelet adhesion is significantly reduced, and the loop conformation of PEG is more effective than the brush conformation in resisting platelet adhesion, which is consistent with CLSM results.
The SEM test results are counted and quantitatively analyzed, and the results are shown in fig. 6, where fig. 6 is a histogram of the adhesion amount of platelets on different modified surfaces provided in example 1 of the present invention, in fig. 6, SEBS represents an unmodified SEBS membrane, PDA represents a dopamine-modified SEBS membrane, brush represents a mono-thiol PEG-modified SEBS material, and loop represents a bis-thiol PEG-modified SEBS material. As can be seen from fig. 6, with the grafting of dopamine and PEG, the amount of platelet adhesion is significantly reduced, and it is particularly worth mentioning that the loop conformation of PEG is reduced by 44.4% compared to the brush conformation.
Through protein adsorption and platelet adhesion tests, the surface of the material modified by PEG has reduced adsorption and platelet adhesion to four proteins, and particularly, the antifouling property of PEG on the surface of SEBS material is greatly improved compared with that of a brush structure after the PEG forms a loop conformation on the surface of SEBS.
Example 2
Mixing Tris and water and adjusting the pH value by using hydrochloric acid to obtain a Tris-HCl solution with the pH value of 7.5-9.5; mixing dopamine with the Tris-HCl solution to obtain a dopamine/Tris-HCl aqueous solution with the dopamine content of 2 wt%; mixing monothiol PEG (number average molecular weight 5k) with the Tris-HCl solution to obtain a monothiol PEG (5k)/Tris-HCl solution with the monothiol PEG content of 5 mg/ml; and mixing the dimercaptoPEG (the number average molecular weight is 5k) with the Tris-HCl solution to obtain the dimercaptoPEG (5k)/Tris-HCl solution with the dimercaptoPEG content of 5 mg/ml.
The SEBS is prepared into a 2 wt% SEBS toluene solution, 10 microliter of the SEBS toluene solution is dripped on a dissipative quartz crystal microbalance (QCM-D) gold chip, spin coating is carried out for 20s at 3000rpm by a spin coating instrument, vacuum drying is carried out overnight at 50 ℃, then the SEBS toluene solution is immersed in a dopamine/Tris-HCl aqueous solution, stirring reaction is carried out for 2h at room temperature, deionized water is used for washing for three times, ethanol is used for washing for one time, and nitrogen is used for drying. And placing the SEBS gold chip modified by dopamine into a QCM-D cavity, respectively introducing a monothio-PEG (5k)/Tris-HCl solution and a dimercapto-PEG (5k)/Tris-HCl solution into the QCM-D cavity, and reacting for a certain time at 40 ℃ to correspondingly obtain a monothio-PEG modified SEBS material and a dimercapto-PEG modified SEBS material. Wherein, the single-sulfydryl PEG forms a brush conformation on the surface of the SEBS, and the double-sulfydryl PEG forms a loop conformation on the surface of the SEBS.
And (4) analyzing results:
and (3) carrying out real-time online detection on the grafting amount of the 5k single-double-sulfydryl PEG with the molecular weight by using QCM-D, controlling the grafting amount of the PEG by controlling the reaction grafting time, and further testing the protein adsorption resistance of the PEG with two conformations when the grafting quality of the PEG with loop conformations is consistent with that of brush conformations.
FIG. 7 shows QCM-D results of 5000 molecular weight mono-bis-thiol PEG grafting on the surface of modified material provided in example 2 of the present invention. In FIG. 7, (a) corresponds to a monothiol PEG, and (b) corresponds to a dimercapto PEG. The adsorption of the surfaces of the modified PEG with the two conformations to the Fib and BSA proteins is tested when the grafting amount of PEG with the brush and loop conformations is about 22Hz (corresponding to reaction times of 1.2 and 2.0h respectively). The adsorption results of Fib and BSA are shown in FIGS. 8 and 9, FIG. 8 is a bar graph of the adsorption amounts of Fib proteins on the grafted surfaces of PEG conformations with the same Grafting mass and different PEG conformations provided by example 2 of the present invention, FIG. 9 is a bar graph of the adsorption amounts of the BSA proteins on the grafted surfaces of PEG conformations with the same Grafting mass and different PEG conformations provided by example 2 of the present invention, in the figure, mPEG-SH-5K represents a mono-sulfhydryl PEG modified SEBS material, SH-PEG-SH-5K represents a bis-sulfhydryl PEG modified SEBS material, PEG Grating represents a PEG Grafting amount, Fib adsorption represents a Fib adsorption amount, and BSA adsorption represents a BSA adsorption amount. As can be seen from fig. 8 and 9, under the condition that the grafting quality is close, the adsorption amounts of the PEG in the loop conformation and the PEG in the brush conformation are reduced by 43.3% and 72.0% for the Fib protein and the BSA protein, respectively. Therefore, under the condition of the same grafting quality, the loop conformation of the PEG has better anti-fouling effect on the surface modification of the SEBS material than that of the brush conformation.
Example 3
Mixing Tris and water and adjusting the pH value by using hydrochloric acid to obtain a Tris-HCl solution with the pH value of 7.5-9.5; mixing dopamine with the Tris-HCl solution to obtain a dopamine/Tris-HCl aqueous solution with the dopamine content of 2 wt%; mixing monothiol PEG (number average molecular weight 5k) with the Tris-HCl solution to obtain a monothiol PEG (5k)/Tris-HCl solution with the monothiol PEG content of 5 mg/ml; mixing the dimercaptoPEG (number average molecular weight 10k) with the Tris-HCl solution to obtain a dimercaptoPEG (10k)/Tris-HCl solution with the dimercaptoPEG content of 5 mg/ml.
The SEBS is prepared into a 2 wt% SEBS toluene solution, 10 microliter of the SEBS toluene solution is dripped on a dissipative quartz crystal microbalance (QCM-D) gold chip, spin coating is carried out for 20s at 3000rpm by a spin coating instrument, vacuum drying is carried out overnight at 50 ℃, then the SEBS toluene solution is immersed in a dopamine/Tris-HCl aqueous solution, stirring reaction is carried out for 2h at room temperature, deionized water is used for washing for three times, ethanol is used for washing for one time, and nitrogen is used for drying. And (3) putting the SEBS gold chip modified by dopamine into a QCM-D cavity, respectively introducing a monothio-PEG (5k)/Tris-HCl solution and a dimercapto-PEG (10k)/Tris-HCl solution into the QCM-D cavity, and reacting for a certain time at 40 ℃ to correspondingly obtain a monothio-PEG modified SEBS material and a dimercapto-PEG modified SEBS material. Wherein, the single-sulfydryl PEG forms a brush conformation on the surface of the SEBS, and the double-sulfydryl PEG forms a loop conformation on the surface of the SEBS.
And (4) analyzing results:
and (3) carrying out real-time online detection on the grafting amounts of 5k and 10k single-double-sulfydryl PEG respectively by using QCM-D, controlling the grafting amount of PEG by controlling the reaction grafting time, and further testing the protein adsorption resistance of PEG with two conformations when the grafting qualities of PEG with loop conformations and brush conformations are consistent.
FIG. 10 shows the results of QCM-D grafting of 5000 molecular weight monothio-PEG and 10000 molecular weight dimercapto PEG on the surface of modified material provided in example 3 of the present invention. In FIG. 10, (a) corresponds to QCM-D grafting results of 5000 molecular weight monothiol PEG on the surface of the modified material, and (b) corresponds to QCM-D grafting results of 10000 molecular weight dimercapto PEG on the surface of the modified material. When the grafting amount of PEG in the brush conformation and the loop conformation is about 20Hz (the corresponding reaction time is 60min and 16min respectively), the adsorption of the PEG modified surfaces of the two conformations on the Fib protein and the BSA protein is tested. The adsorption results of Fib and BSA are shown in FIGS. 11 and 12, where FIG. 11 is a histogram of the adsorption amounts of Fib proteins on the surface of PEG conformations with the same Grafting mass and the same Grafting density provided by example 3 of the present invention, FIG. 12 is a histogram of the adsorption amounts of the surface of the BSA proteins provided by example 3 of the present invention on the surface of PEG conformations with the same Grafting mass and the same Grafting density, and in the graphs, mPEG-SH-5K represents a mono-thiol PEG modified SEBS material, SH-PEG-SH-10K represents a bis-thiol PEG modified SEBS material, PEG Grafting represents a PEG Grafting amount, Fib adsorption represents a Fib adsorption amount, and BSA adsorption represents a BSA adsorption amount. As can be seen from FIGS. 11 and 12, the loop conformation of PEG was reduced by 30.2% and 76.0% as compared with the brush conformation for the adsorption of Fib and BSA proteins, respectively. Therefore, under the condition that the grafting quality and the grafting density are the same, the loop conformation of the PEG has better anti-fouling effect on the surface modification of the SEBS material than the brush conformation.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (4)
1. A preparation method of a modified SEBS material comprises the following steps:
reacting the SEBS substrate in a dopamine solution to obtain dopamine-modified SEBS;
the content of the dopamine in the dopamine solution is 1-5 wt%; the SEBS substrate is reacted in the dopamine solution at the temperature of 25-50 ℃ for 2-24 hours, and the pH value of the reaction is 7.2-10;
reacting the SEBS modified by dopamine in a hydrophilic polymer solution to obtain a modified SEBS material;
the hydrophilic polymer is dimercapto PEG; the reaction temperature of the SEBS modified by dopamine in the hydrophilic polymer solution is 25-90 ℃, the reaction time is 1-12 h, and the pH value of the reaction is 7.5-9.5.
2. The method according to claim 1, wherein the hydrophilic polymer has a number average molecular weight of 1000 to 20000.
3. The method according to claim 1, wherein the hydrophilic polymer is contained in the hydrophilic polymer solution in an amount of 0.05 to 10 mg/ml.
4. A medical device, which is characterized by comprising the modified SEBS material prepared by the method of any one of claims 1-3.
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