CN114349996A - Super-smooth material and preparation method and application thereof - Google Patents

Super-smooth material and preparation method and application thereof Download PDF

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CN114349996A
CN114349996A CN202111467647.1A CN202111467647A CN114349996A CN 114349996 A CN114349996 A CN 114349996A CN 202111467647 A CN202111467647 A CN 202111467647A CN 114349996 A CN114349996 A CN 114349996A
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modified
polysaccharide
ultra
double
super
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于珊
张锦
鲁道欢
耿志杰
裴大婷
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Institute Of Health Medicine Guangdong Academy Of Sciences
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Institute Of Health Medicine Guangdong Academy Of Sciences
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Abstract

The invention relates to the technical field of biological materials, in particular to a super-smooth material, a preparation method and application thereof. The hydrophilic coating contains double-bond monomer modified polysaccharide with excellent biocompatibility and hydrophilicity, so that the super-smooth material has good biocompatibility and hydrophilicity, can promote the repair of micro tissue damage of a human body, and simultaneously reduces the friction force on the surface of the super-smooth material. Polysaccharide molecules are generally rich in a large number of active carboxyl groups and can form amide bonds with amino groups in the amino-containing silane coupling agent, so that the hydrophilic coating is firmly fixed on the surface of the base material, and the stability of the hydrophilic coating is improved; meanwhile, the amino-containing silane coupling agent is also helpful for improving the hydrophilicity of the hydrophilic coating and further reducing the friction coefficient of the hydrophilic coating.

Description

Super-smooth material and preparation method and application thereof
Technical Field
The invention belongs to the technical field of biological materials, and particularly relates to an ultra-smooth material, and a preparation method and application thereof.
Background
The hydrophilicity of the surface of the catheter directly influences the lubricity and biocompatibility of the catheter in use and is a very important clinical index. The surface super-smooth coating can effectively reduce the surface friction coefficient of the catheter in a humid environment, and reduce tissue damage caused by friction between the urethra and the catheter. Therefore, the modification of the surface of the catheter is an important way for improving the surface hydrophilicity of the catheter. The natural polysaccharide is biosynthesized, is a biological macromolecule positioned in cell walls, cells, intercellular spaces and outside secretory cells, participates in the life activities of organisms, has rich and various biological functions, and has important application in the field of biological materials. However, the adhesion between the biological polysaccharide and the biomaterial substrate is poor, the formed coating has poor stability, and the coating is easy to fall off from the surface of the substrate, so that the requirements of the ultra-smooth biomaterial with good biocompatibility, good hydrophilicity, small friction and small tissue damage are increasing at the present stage.
Disclosure of Invention
The present invention is directed to solving at least one of the problems of the prior art described above. Therefore, the invention provides an ultra-smooth material which has excellent hydrophilicity, good stability, low friction coefficient and biocompatibility.
The invention also provides a preparation method and application of the super-smooth material.
The invention provides a super-smooth material, which comprises a base material and a hydrophilic coating, wherein the hydrophilic coating is fixed on the surface of the base material through an amino-containing silane coupling agent, and the hydrophilic coating is formed by crosslinking and curing double-bond monomer modified polysaccharide.
The first aspect of the present invention has at least the following advantages:
the hydrophilic coating in the super-smooth material contains double-bond monomer modified polysaccharide with excellent biocompatibility and hydrophilicity, so that the super-smooth material has good biocompatibility and hydrophilicity, can promote the repair of micro tissue damage of a human body, and simultaneously reduces the friction force on the surface of the super-smooth material. Polysaccharide molecules are generally rich in a large number of active carboxyl groups and can form amide bonds with amino groups in the amino-containing silane coupling agent, so that the hydrophilic coating is firmly fixed on the surface of the base material, and the stability of the hydrophilic coating is improved; meanwhile, the amino-containing silane coupling agent is also helpful for improving the hydrophilicity of the hydrophilic coating and further reducing the friction coefficient of the hydrophilic coating. Therefore, the super-smooth material has the advantages of super-strong hydrophilicity, good surface stability and excellent biocompatibility, and meanwhile, the friction coefficient is small, so that the tissue damage can be effectively reduced, the tissue repair is promoted, and the super-smooth material has a good clinical application prospect.
Preferably, the molecular weight of the polysaccharide is 20000-1200000, preferably 50000-1000000.
Preferably, the polysaccharide is a natural polysaccharide with hydroxyl and/or carboxyl active groups on the surface, and comprises at least one of hyaluronic acid, sodium alginate and glucan.
Preferably, the double bond monomer is a monomer containing a carbon-carbon double bond, and comprises at least one of methacrylic anhydride and acrylic anhydride. The double-bond monomer modified polysaccharide comprises at least one of methacrylic anhydride modified hyaluronic acid, acrylic anhydride modified hyaluronic acid and methacrylic anhydride modified sodium alginate.
Preferably, the mass ratio of the polysaccharide to the double-bond monomer in the double-bond monomer modified polysaccharide is 1: 1 to 6, more preferably 1: 2-4, and more preferably 1: about 3.82.
Preferably, the amino-containing silane coupling agent comprises at least one of gamma-aminopropyltriethoxysilane, gamma-aminopropylmethyldiethoxysilane, gamma-aminopropyltrimethoxysilane, gamma-aminopropylmethyldimethoxysilane, N- (beta-aminoethyl) -gamma-aminopropyltrimethoxysilane, and N- (beta-aminoethyl) -gamma-aminopropylmethyldimethoxysilane.
Preferably, the crosslinking curing method comprises photocuring crosslinking and thermal crosslinking curing, and preferably photocuring crosslinking. Under the irradiation of light, unsaturated activated double bonds in the double bond monomer modified polysaccharide are crosslinked and solidified.
Preferably, the crosslinking curing is carried out in the presence of an initiator, which preferably comprises a photoinitiator.
Preferably, the photoinitiator includes at least one of α -hydroxyketone, 1- [4- (2-hydroxyethoxy) -phenyl ] -2-hydroxy-2-methyl acetone, 1-hydroxycyclohexyl phenyl ketone, benzophenone type photoinitiator, acylphosphine oxide type photoinitiator, 2' -azo-bis (2-amidinopropane) type photoinitiator.
Preferably, the substrate comprises at least one of a metal substrate and a plastic substrate; more preferably, the substrate comprises at least one of PVC, silicone rubber, polyurethane, polyacrylate, polyethylene, polypropylene.
The second part of the invention provides a preparation method of a super-smooth material, which comprises the following steps:
modifying the surface of the base material by using the amino-containing silane coupling agent to obtain a modified base material;
grafting the double-bond monomer modified polysaccharide to the surface of the modified substrate;
and crosslinking and curing the double-bond monomer modified polysaccharide to obtain the ultra-smooth material.
Preferably, the step of modifying the surface of the substrate with the amino-containing silane coupling agent is to soak the substrate in an amino-containing silane coupling agent solution, take out and dry the substrate to obtain the modified substrate.
Preferably, the amino-containing silane coupling agent solution is a solution formed by dissolving an amino-containing silane coupling agent in ethanol, water, tetrahydrofuran, propanol or other solvent capable of dissolving the amino-containing silane coupling agent. More preferably, the mass fraction of the aminosilane-containing coupling agent in the aminosilane-containing coupling agent solution is 0.2 to 8%, and still more preferably 0.5 to 5%.
Preferably, the time for soaking the base material in the amino-containing silane coupling agent solution is 0.5-1 h, and more preferably about 0.5 h.
Preferably, the step of grafting the double-bond monomer modified polysaccharide to the surface of the modified substrate is to soak the modified substrate in a double-bond monomer modified polysaccharide solution, take out and dry the double-bond monomer modified polysaccharide solution.
Preferably, the mass fraction of the double-bond monomer modified polysaccharide solution is 1-8%, and more preferably 1-5%.
Preferably, the double bond monomer-modified polysaccharide solution further contains an active substance comprising at least one of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride and N-hydroxysuccinimide, more preferably a mixture of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride and N-hydroxysuccinimide.
Preferably, the mass of the active substance accounts for 8-12%, preferably about 10% of the mass of the double-bond monomer modified polysaccharide.
Preferably, the mass ratio of the 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride to the N-hydroxysuccinimide is 7: 10-13; preferably about 7: 12.
Preferably, the soaking temperature of the modified base material in the double-bond monomer modified polysaccharide solution is 30-50 ℃, more preferably 30-40 ℃, and even more preferably about 37 ℃. The soaking time is 2-8 h, more preferably 3-6 h, and further preferably about 5 h.
Preferably, the step of crosslinking and curing is: crosslinking and curing the double-bond monomer modified polysaccharide under the action of an initiator; more preferred crosslinking and curing steps are: and (3) soaking the base material grafted with the double-bond monomer modified polysaccharide in a photoinitiator solution, taking out the base material, performing ultraviolet curing, and drying to obtain the super-smooth material.
Preferably, the ultraviolet curing time is 5-20 min, and more preferably about 10 min.
Preferably, the mass fraction of the photoinitiator solution is 0.02-0.5%, more preferably 0.05-0.2%.
Preferably, the preparation method of the double-bond monomer modified polysaccharide comprises the following steps: the polysaccharide and the double-bond monomer react to obtain the double-bond monomer modified polysaccharide.
Preferably, the preparation method of the double-bond monomer modified polysaccharide comprises the following steps:
dissolving the polysaccharide to obtain a polysaccharide solution;
mixing the polysaccharide solution and the double-bond monomer, and reacting to obtain a mixed solution;
pouring the mixed solution into ethanol, standing for precipitation, and performing solid-liquid separation to obtain a precipitate;
and dialyzing and drying the precipitate to obtain the double-bond monomer modified polysaccharide.
Preferably, the mass fraction of the polysaccharide solution is 0.5 to 5%, more preferably 1 to 3%, and still more preferably about 1%.
Preferably, the solvent used for preparing the polysaccharide solution comprises at least one of water, ethanol, tetrahydrofuran and glycol, more preferably a mixed solvent of at least two of the solvents, and further preferably a mixed solvent of tetrahydrofuran and water.
Preferably, the volume ratio of tetrahydrofuran to water is 1: 1 to 3, more preferably 1: about 2.
Preferably, the temperature of the reaction between the polysaccharide solution and the double-bond monomer is 1-6 ℃, more preferably 1-5 ℃, and even more preferably about 4 ℃. The reaction time is 8-20 h, and 8-16 h is further preferable. The pH during the reaction is 8 to 10, and more preferably 8 to 9. The pH regulator of the reaction can adopt alkali or alkaline solution commonly used in the field, such as sodium hydroxide, potassium hydroxide, ammonia water and solution thereof, and as an example, the pH regulator of the invention can adopt 3-5M sodium hydroxide solution. In the reaction process, the double-bond monomer is added into the polysaccharide solution in a slow dropwise manner.
Preferably, the temperature of standing is 1-6 ℃, more preferably 1-5 ℃, and further preferably about 4 ℃.
Preferably, the dialysis is performed by using a dialysis bag with a molecular weight of 14000 to 15000, more preferably a dialysis bag with a molecular weight of about 14000. The water is changed every 3-5 hours in the dialysis process, and more preferably every 4 hours. The dialysis time is 4-7 days, and more preferably about 5 days.
According to a third aspect of the invention, the use of the ultra-slippery material for the preparation of a medical catheter, guidewire or stent delivery system.
Preferably, the medical catheter comprises a urinary catheter, a gastric tube, an endotracheal tube or the like.
Compared with the prior art, the invention at least has the following beneficial effects:
the super-smooth material comprises a base material and a hydrophilic coating, wherein the hydrophilic coating contains double-bond monomer modified polysaccharide with excellent biocompatibility and hydrophilicity, so that the super-smooth material has good biocompatibility and hydrophilicity, can promote the repair of micro tissue damage of a human body, and simultaneously reduces the friction force on the surface of the super-smooth material. The amino-containing silane coupling agent is connected to the surface of the base material, so that the surface of the base material is provided with a large number of active amino groups, and then the active amino groups react with carboxyl groups of polysaccharide molecules to form amido bonds, so that the hydrophilic coating is firmly fixed on the surface of the base material, and the stability of the hydrophilic coating is improved; meanwhile, the amino-containing silane coupling agent is also helpful for improving the hydrophilicity of the hydrophilic coating and further reducing the friction coefficient of the hydrophilic coating. Therefore, the super-smooth material has the advantages of super-strong hydrophilicity, good surface stability and excellent biocompatibility, has a small friction coefficient, can effectively reduce tissue damage and promote tissue repair, and has a good clinical application prospect.
Drawings
The invention is further described with reference to the following figures and examples, in which:
FIG. 1 is a schematic illustration of the preparation of a super-slip material of the present invention;
FIG. 2 is a nuclear magnetic spectrum of hyaluronic acid and methacrylic anhydride modified hyaluronic acid used in the present invention, wherein HA represents hyaluronic acid and MA represents methacrylic anhydride;
FIG. 3 is a photograph of the surface water contact angle of the catheters prepared in comparative example 1 and example 1;
FIG. 4 is a graph comparing the surface stability of catheters prepared in comparative example 2 and example 1 (28 day residual);
FIG. 5 is a graph comparing the surface friction coefficients of catheters prepared in comparative example 1 and examples 1-2;
fig. 6 is a graph showing endothelial cell adhesion on the surfaces of the catheters prepared in comparative example 1 and example 1.
Detailed Description
The concept and technical effects of the present invention will be clearly and completely described below in conjunction with the embodiments to fully understand the objects, features and effects of the present invention. It is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments, and those skilled in the art can obtain other embodiments without inventive effort based on the embodiments of the present invention, and all embodiments are within the protection scope of the present invention.
Example 1
The method comprises the following steps: and cleaning the surface of the common medical catheter by using absolute ethyl alcohol and drying. A 0.5 wt.% solution of gamma-aminopropyltrimethoxysilane in absolute ethanol was prepared. And soaking the catheter in the solution for half an hour, taking out and drying to obtain the silane modified catheter.
Step two: methacrylic anhydride modified hyaluronic acid was used to prepare an aqueous solution having a concentration of 2 wt.%. Adding a mixture of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride and N-hydroxysuccinimide (the mass ratio of the 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride to the N-hydroxysuccinimide is 7:12, and the total amount is 10 percent of the mass of the methacrylic anhydride modified hyaluronic acid) to form an activation system. And (3) soaking the catheter modified by silane obtained in the step one in the silane modified catheter, reacting for 5 hours at 37 ℃, taking out and drying.
Step three: an aqueous solution of photoinitiator 1- [4- (2-hydroxyethoxy) -phenyl ] -2-hydroxy-2-methyl acetone was prepared at a concentration of 0.05 wt.%. And D, soaking the catheter obtained in the step two in the water, taking out the catheter, curing the catheter for 10 minutes by using ultraviolet light, and drying the catheter to obtain the ultra-smooth catheter.
Example 2
The method comprises the following steps: and cleaning the surface of the common medical catheter by using absolute ethyl alcohol and drying. A 0.5 wt.% solution of gamma-aminopropyltrimethoxysilane in absolute ethanol was prepared. And soaking the catheter in the solution for half an hour, taking out and drying to obtain the silane modified catheter.
Step two: methacrylic anhydride modified sodium alginate is adopted to prepare an aqueous solution with the concentration of 2 wt.%. Adding a mixture of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride and N-hydroxysuccinimide (the mass ratio of the 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride to the N-hydroxysuccinimide is 7:12, and the total amount is 10 percent of the mass of the methacrylic anhydride modified sodium alginate). And (3) soaking the catheter modified by silane obtained in the step one in the silane modified catheter, reacting for 5 hours at 37 ℃, taking out and drying.
Step three: an aqueous solution of photoinitiator 1-hydroxycyclohexyl phenyl ketone was prepared at a concentration of 0.1 wt.%. And D, soaking the catheter obtained in the step two in the water, taking out the catheter, curing the catheter for 10 minutes by using ultraviolet light, and drying the catheter to obtain the ultra-smooth catheter.
Comparative example 1
Cleaning a common medical catheter by absolute ethyl alcohol and drying.
Comparative example 2
This comparative example differs from example 1 in that: the surface of the catheter is modified without using an amino-containing silane coupling agent, and the specific process comprises the following steps:
the method comprises the following steps: cleaning a common medical catheter by absolute ethyl alcohol and drying. Methacrylic anhydride modified hyaluronic acid was used to prepare an aqueous solution having a concentration of 1 wt.%. And adding a mixture of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride and N-hydroxysuccinimide (the mass ratio of the 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride to the N-hydroxysuccinimide is 7:12, and the total mass is 10 percent of the mass of the methacrylic anhydride modified hyaluronic acid) to form an activation system. The catheter was directly immersed in the solution and reacted at 37 ℃ for 5 hours. Taking out and drying.
Step two: an aqueous solution of photoinitiator 1- [4- (2-hydroxyethoxy) -phenyl ] -2-hydroxy-2-methyl acetone was prepared at a concentration of 0.05 wt.%. And (3) soaking the catheter obtained in the step one in the solution, taking out the catheter, curing the catheter for 10 minutes by using ultraviolet light, and drying the catheter to obtain the catheter which is not modified by silane.
The preparation method of the methacrylic anhydride modified hyaluronic acid comprises the following steps: 1g of hyaluronic acid was dissolved in 100mL of a mixed solvent (DMF: water ═ 1:2, v: v) with stirring. And after full dissolution, cooling to 4 ℃ in an ice water bath, and adjusting the pH to 8-9 by using 5M sodium hydroxide. Slowly dropwise adding 3.7mL of methacrylic anhydride, stirring overnight at 4 ℃, and keeping the pH value stable between 8 and 9. The reacted solution was poured into 1L of anhydrous ethanol and allowed to stand overnight at 4 ℃ to complete the precipitation of the product. Centrifuging, dissolving the precipitate in ultrapure water again, dialyzing with dialysis bag with molecular weight of 14000, changing water every 4 hours, dialyzing for 5 days, and lyophilizing to obtain methacrylic anhydride modified hyaluronic acid.
The preparation method of the methacrylic anhydride modified sodium alginate comprises the following steps: 1g of sodium alginate was dissolved in 100mL of a mixed solvent (DMF: water ═ 1:2, v: v) with stirring. And after full dissolution, cooling to 4 ℃ in an ice water bath, and adjusting the pH to 8-9 by using 5M sodium hydroxide. Slowly dropwise adding 3.7mL of methacrylic anhydride, stirring overnight at 4 ℃, and keeping the pH value stable between 8 and 9. The reacted solution was poured into 1L of anhydrous ethanol and allowed to stand overnight at 4 ℃ to complete the precipitation of the product. Centrifuging, dissolving the precipitate in ultrapure water again, dialyzing with dialysis bag with molecular weight of 14000, changing water every 4 hours, dialyzing for 5 days, and lyophilizing to obtain methacrylic anhydride modified sodium alginate.
Test examples
The surface properties of the catheters prepared in examples 1-2 and comparative examples 1-2 and the structure of methacrylic anhydride modified hyaluronic acid were tested in this test example.
Wherein, the hydrophilicity test method of the surface of the catheter is a contact angle test method, and the test result is shown in figure 3;
the method for testing the residual performance of the surface of the catheter comprises the steps of preparing 0, 0.2, 0.4, 0.6, 0.8 and 1.0mg/ml methacrylic anhydride modified hyaluronic acid, drawing a standard curve by utilizing an ultraviolet absorption peak at 196nm, respectively putting the catheters of example 1 and comparative example 2 into normal saline for soaking for 28 days, testing the absorbance of the solution at 196nm, and obtaining the residual mass according to the standard curve, wherein the test result is shown in figure 4;
the test method of the friction performance of the surface of the catheter is to measure the friction coefficient between the surface of the catheter and the pig yellow larynx (simulated urethra) by using a friction wear testing machine, and the test result is shown in figure 5;
the method for testing the cell adhesion performance on the surface of the catheter comprises the steps of inoculating endothelial cells on the surface of the modified catheter material, observing the cell morphology through fluorescent staining after culturing, and testing results are shown in fig. 6.
FIG. 2 shows the preparation of methacrylic anhydride modified hyaluronic acid1H NMR spectrum showed that-CH-CH in methacrylic anhydride was observed at chemical shift δ of 5.5 to 6.5ppm, as compared with unmodified hyaluronic acid2The characteristic peak of hydrogen of the group shows that methacrylic anhydride and hyaluronic acid are subjected to chemical reaction, and carbon-carbon double bonds are successfully introduced into hyaluronic acid to obtain methacrylic anhydride modified hyaluronic acid so as to ensure that the subsequent ultraviolet curing reaction is successfully carried out.
As shown in fig. 3, the surface of the ultra-smooth catheter prepared in example 1 of the present invention has excellent hydrophilicity, and the contact angle of water is 22.3 °, whereas the contact angle of the surface of the unmodified medical catheter in comparative example 1 is 91.2 °, and the surface of the ultra-smooth catheter exhibits hydrophobic property. Therefore, the surface of the medical catheter is modified by the aminosilane coupling agent, the methacrylic anhydride modified hyaluronic acid is grafted and fixed on the surface of the catheter, the methacrylic anhydride modified hyaluronic acid is crosslinked and cured on the surface of the catheter to form a hydrophilic coating, the change of the surface of the catheter from hydrophobicity to hydrophilicity is realized, the water contact angle is reduced from the original 91.2 degrees to 22.3 degrees, the water contact angle is reduced by 68.9 degrees, and the hydrophilicity is obviously improved. And the hydrophilic property is an important clinical index of the medical material, and the improvement of the hydrophilicity can reduce the friction coefficient to a certain extent and reduce the tissue damage.
FIG. 4 is a graph of 28-day coating residue for example 1 and comparative example 2 of the present invention, and it can be seen from FIG. 4 that the coating residue on the surface of the ultra-smooth catheter prepared in example 1 was more than 90%, while the coating residue on the catheter prepared in comparative example 2 without modification with the aminosilane-containing coupling agent was only about 10%. Therefore, the catheter is modified by the amino-containing silane coupling agent, and the double-bond monomer modified polysaccharide is grafted and fixed on the surface of the catheter, so that the hydrophilic coating has good adhesive force with the base material, has good stability and is not easy to damage.
As shown in FIG. 5, the friction coefficients of the surfaces of the catheters prepared in examples 1-2 of the present invention are all below 0.1, the surfaces are ultra-smooth, and the damage of the tissues during the use process can be effectively reduced, while the friction coefficient of the surface of the catheter unmodified in comparative example 1 is more than 0.6, which is more than 6 times of that of the catheters prepared in examples 1-2 of the present invention, the surface is rough, and the damage to the tissues is large.
As shown in fig. 6, compared with the unmodified catheter surface (comparative example 1), the number of endothelial cells adhered to the surface of the ultra-smooth catheter prepared in example 1 of the present invention is significantly less, which indicates that the surface of the ultra-smooth catheter prepared in example 1 of the present invention is smooth, the adhesion of endothelial cells is effectively reduced, and the damage to tissues during the use process is less. Therefore, as shown in a preparation schematic diagram of the ultra-smooth material shown in fig. 1, amino groups are introduced into the catheter modified by the amino-containing silane coupling agent, carboxylic acid in double-bond modified polysaccharide and the amino-containing silane coupling agent are grafted and fixed on the surface of the catheter through an amino-carboxyl reaction, and the ultra-smooth material is obtained through curing under ultraviolet illumination. The obtained super-smooth material has good hydrophilicity, adhesive force, stability and ultralow friction coefficient, obviously reduces tissue damage and has good clinical application prospect.
The embodiments of the present invention have been described in detail with reference to the accompanying drawings, but the present invention is not limited to the above embodiments, and various changes can be made within the knowledge of those skilled in the art without departing from the gist of the present invention. Furthermore, the embodiments of the present invention and the features of the embodiments may be combined with each other without conflict.

Claims (10)

1. The super-smooth material is characterized by comprising a base material and a hydrophilic coating, wherein the hydrophilic coating is fixed on the surface of the base material through an amino-containing silane coupling agent, and the hydrophilic coating is formed by crosslinking and curing double-bond monomer modified polysaccharide.
2. The ultra-smooth material of claim 1, wherein the polysaccharide is a natural polysaccharide having hydroxyl and/or carboxyl reactive groups on the surface.
3. The ultra-smooth material of claim 1 wherein the double bond monomer is a carbon-carbon double bond containing monomer.
4. The ultra-smooth material of any one of claims 1 to 3, wherein the double-bond monomer-modified polysaccharide comprises at least one of methacrylic anhydride-modified hyaluronic acid, acrylic anhydride-modified hyaluronic acid, methacrylic anhydride-modified sodium alginate.
5. The super-slip material according to claim 1, wherein the mass ratio of the polysaccharide to the double bond monomer in the double bond monomer modified polysaccharide is 1: 1 to 6.
6. The ultra-smooth material of claim 1, wherein the amino-containing silane coupling agent comprises at least one of gamma-aminopropyltriethoxysilane, gamma-aminopropylmethyldiethoxysilane, gamma-aminopropyltrimethoxysilane, gamma-aminopropylmethyldimethoxysilane, N- (beta-aminoethyl) -gamma-aminopropyltrimethoxysilane, N- (beta-aminoethyl) -gamma-aminopropylmethyldimethoxysilane.
7. The ultra-smooth material of claim 1 wherein the cross-linking and curing method comprises photo-curing cross-linking, thermal cross-linking and curing.
8. The ultra-smooth material of claim 1 wherein the substrate comprises at least one of a metal substrate, a plastic substrate.
9. The method for preparing a super-slip material as claimed in any one of claims 1 to 8, comprising the steps of:
modifying the surface of the base material by using the amino-containing silane coupling agent to obtain a modified base material;
grafting the double-bond monomer modified polysaccharide to the surface of the modified substrate;
and crosslinking and curing the double-bond monomer modified polysaccharide to obtain the ultra-smooth material.
10. Use of the ultra-slippery material of any of claims 1 to 8 for the preparation of a medical catheter, guidewire or stent delivery system.
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* Cited by examiner, † Cited by third party
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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4828616A (en) * 1986-08-28 1989-05-09 Nippon Paint Co., Ltd. Surface treatment chemical for forming a hydrophilic coating
CN105879116A (en) * 2016-05-24 2016-08-24 南京理工大学 Low-friction high-wear resistance bionic artificial joint and preparation method thereof
CN106821564A (en) * 2016-12-29 2017-06-13 凯斯蒂南京医疗器械有限公司 A kind of dual balloon catheter support
CN110975017A (en) * 2019-11-14 2020-04-10 北京迪玛克医药科技有限公司 Photocurable hydrophilic coating material for interventional instrument, and preparation method and application thereof
CN111671983A (en) * 2020-06-12 2020-09-18 深圳清华大学研究院 Biomedical material and preparation method thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4828616A (en) * 1986-08-28 1989-05-09 Nippon Paint Co., Ltd. Surface treatment chemical for forming a hydrophilic coating
CN105879116A (en) * 2016-05-24 2016-08-24 南京理工大学 Low-friction high-wear resistance bionic artificial joint and preparation method thereof
CN106821564A (en) * 2016-12-29 2017-06-13 凯斯蒂南京医疗器械有限公司 A kind of dual balloon catheter support
CN110975017A (en) * 2019-11-14 2020-04-10 北京迪玛克医药科技有限公司 Photocurable hydrophilic coating material for interventional instrument, and preparation method and application thereof
CN111671983A (en) * 2020-06-12 2020-09-18 深圳清华大学研究院 Biomedical material and preparation method thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
刘彦: "透明质酸对聚乙烯醇膜表面亲水性修饰的研究", 《中国优秀硕士学位论文全文数据库 医药卫生科技辑》 *

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114712568A (en) * 2022-06-07 2022-07-08 中国人民解放军总医院第一医学中心 Surface modified silicone rubber stomach tube and preparation method thereof
CN115120785A (en) * 2022-08-09 2022-09-30 北京化工大学 Medical catheter with polysaccharide coating and preparation method thereof
CN115779159A (en) * 2022-12-01 2023-03-14 中山大学 High-strength-toughness wear-resistant hydrophilic lubricating coating grafted on surface of medical instrument and preparation method thereof
CN115779159B (en) * 2022-12-01 2024-01-16 中山大学 High-strength and high-toughness wear-resistant hydrophilic lubricating coating grafted on surface of medical instrument and preparation method thereof
CN116218002A (en) * 2022-12-21 2023-06-06 厦门为正生物科技股份有限公司 Dextran modified PDMS, preparation method and microfluidic chip
CN116813381A (en) * 2023-07-03 2023-09-29 化学与精细化工广东省实验室潮州分中心 Biological ceramic surface bioactive coating and preparation method thereof
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Application publication date: 20220415