CN110016089B

CN110016089B - Amino-rich catechol amine compound and preparation method thereof, amino-rich surface modified product, material and dip-coating method thereof

Info

Publication number: CN110016089B
Application number: CN201910309688.4A
Authority: CN
Inventors: 杨志禄; 乔峰; 黄楠; 涂秋芬; 夏俊秋; 邱华; 高鹏
Original assignee: Southwest Jiaotong University
Current assignee: Dongguan Peoples Hospital
Priority date: 2019-04-17
Filing date: 2019-04-17
Publication date: 2020-06-16
Anticipated expiration: 2039-04-17
Also published as: CN110016089A

Abstract

The invention relates to the technical field of materials science, in particular to an amino-rich catechol amine compound and a preparation method thereof. Also provides a catecholamine-based rich amine surface modification product, which comprises a mixture of an alkaline buffer solution and a rich amine-based catecholamine compound, wherein the dosage ratio of the rich amine-based catecholamine compound to the alkaline buffer solution is 0.01-100 mg: 1mL, the amino-rich catechol amine compound is obtained by the reaction of a carboxyl-containing plant polyphenol compound and an amino-rich molecule. The coating formed by the surface modified product has good broad-spectrum adhesion performance and stable chemical performance under the conditions of strong acid and strong alkali, and can further react with various functional compounds to endow the coating with new performance. Also provided are materials having a surface coating and methods of dip coating catecholamine-based, rich amine-based coatings on the surface of the materials.

Description

Amino-rich catechol amine compound and preparation method thereof, amino-rich surface modified product, material and dip-coating method thereof

Technical Field

The invention relates to the technical field of materials science, in particular to a rich amino catechol amine compound and a preparation method thereof, a rich amino surface modified product, a material and a dip-coating method thereof.

Background

At present, for many fields such as modern chemistry, medicine, biology, and material science, the chemical modification method of different material surfaces plays a very important role in enhancing their functions. The existing methods for functionally modifying the surface of a material are various, such as self-assembled monomolecular layers, functionalized silane (such as silane coupling agent), LB (Langmuir-Blodgett) ultrathin molecular film deposition, layer-by-layer self-assembly, molecular glue technology, genetically engineered surface-bound polypeptide and the like. These methods are widely used in research but are limited in their wide use by requirements for chemical modification between the interface modifier and the substrate (e.g. alkanol on noble metal, silane on oxide), use of complex means and limitations on substrate size and shape (LB deposition) and the need for multi-step deposition (layer-by-layer self-assembly and genetically engineered surface-bound polypeptides).

In 1981, Waite and Tanzer et al discovered that catechol structure plays an important role in adhesion of mussels on different rough wet surfaces, and the important discovery leads researchers to carry out long-term research on adhesion of mussels and the action mechanism of the mussels. Researches show that dopa and lysine structures play a main role in adhesion of the mussels, the mussel adhesion foot protein Mefp-5 contains 30% of dopa, and researchers design a plurality of mussel bionic catecholamine coatings. However, the conventional catecholamine coatings, such as polydopamine coatings, have the following disadvantages: (1) the chemical stability of the polydopamine coating is poor, and the polydopamine coating is easy to disintegrate under extreme conditions such as strong acid, strong base and strong salt; (2) the amine group density on the surface of the polydopamine coating is low, which is not beneficial to the further function modification related to the amine group.

In view of this, the present application is specifically made.

Disclosure of Invention

The invention provides an amino-rich catechol amine compound which can be dip-coated on the surface of a material to obtain a coating which has strong adhesion and good chemical stability and can be further subjected to functional change.

The invention provides a preparation method of a rich amino catechol amine compound, which can prepare the rich amino catechol amine compound provided by the invention.

The invention provides a catecholamine-based rich amine-based surface modified product, which aims to solve the problems that the existing catecholamine coating such as polydopamine coating is poor in chemical stability and difficult to further functionally change, and endows the coating with good adhesion performance.

The invention also provides a material with a coating on the surface, and the surface of the material is not easy to deteriorate and damage in an extreme environment, so the material has good performance, long service life and high use safety, and can be applied to the field of chemistry or medicine.

The invention also provides a method for dip-coating the material surface with the catecholamine-based rich amine coating, and the material with the coating on the surface can be obtained.

The invention is realized by the following steps:

an amine compound rich in amino catecholamine is prepared by reacting plant polyphenol compound containing carboxyl with amine-rich molecule.

A method for preparing an amine-rich catechol compound comprises the following steps:

placing the carboxyl-containing plant polyphenol compound and the rich amino-group molecules in an acid buffer solution for complete reaction, and then dialyzing and freeze-drying to obtain the rich amino-group catechol amine compound, wherein the molar ratio of carboxyl in the carboxyl-containing plant polyphenol compound participating in the reaction to amino in the rich amino-group molecules participating in the reaction is 0.01-10: 1, and the concentration of the carboxyl-containing plant polyphenol compound in the acid buffer solution is 0.01-100 mg/ml.

A catecholamine-based rich amine surface modification product comprises an alkaline buffer solution and the rich amino catecholamine compound or the rich amino catecholamine compound prepared by the method, wherein the dosage ratio of the rich amino catecholamine compound to the alkaline buffer solution is 0.01-100 mg: 1mL, the amino-rich catechol amine compound is obtained by the reaction of a carboxyl-containing plant polyphenol compound and an amino-rich molecule.

A method of dip coating a catecholamine-based rich amine-based coating on a material surface, comprising:

placing a substrate material in the mixture obtained by mixing the alkaline buffer solution and the amine-rich catechol compound to react for at least 0.5h to obtain a primary sample, wherein the ratio of the amine-rich catechol compound to the alkaline buffer solution is 0.5-1.5 mg: 1 mL.

The primary sample was washed and dried.

A material with a coating on the surface is prepared by the method.

The invention has the beneficial effects that: the amine-rich catechol amine compound obtained through the design can be mixed with an alkaline buffer solution, and a base material is placed in the mixed solution, so that the surface of the base material is covered with an amine-rich coating, and the coating has strong adhesion performance and stable chemical performance, is not easy to disintegrate under extreme conditions, and can be applied to almost any type of materials or substrate materials in shapes. And the formed coating is rich in amine groups, so that the coating has wide reactivity.

According to the present invention, the method for producing the rich aminocatechol amine compound designed above can produce the rich aminocatechol amine compound provided by the present invention.

According to the catecholamine-based rich amine surface modification product obtained through the design, when the product is used, the alkaline buffer solution and the rich amine catecholamine compound are mixed, the substrate material to be surface-modified is immersed in the mixture of the alkaline buffer solution and the rich amine catecholamine compound obtained through the reaction of the carboxyl-containing plant polyphenol compound and the rich amine molecule, and the rich amine catecholamine-based catecholamine compound is mixed with the alkaline buffer solution to form the catecholamine-rich amine adhesive coating. Due to the characteristic of rich amine groups of the coating formed by the surface modified product, the surface modified product has wide reactivity, and can react with carboxyl compounds, NHS, succinic anhydride and carbonyl compounds, such as polyethylene glycol grafted on 316LSS for biological decontamination; the antibacterial polypeptide is grafted on the surface of the PVC for the antibacterial function; the surface of the cobalt-chromium-nickel alloy bracket is grafted with heparin for anticoagulation and the like, and the coating has different functions after reacting with substances with different properties.

According to the method for dip-coating the catecholamine-based rich amine-based coating on the surface of the material, which is designed by the invention, the coating provided by the invention can be dip-coated on the surface of the substrate material to form a catecholamine-based rich amine adhesive coating.

The material with the coating on the surface is prepared by adopting the method for dip-coating the catecholamine-based rich amine-based coating on the surface of the material. The surface of the material is not easy to deteriorate and damage in extreme environment, so the material has good performance, long service life and high use safety, and can be applied to the field of chemistry or medicine.

Drawings

In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are required to be used in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and for those skilled in the art, other related drawings can be obtained according to the drawings without inventive efforts.

FIG. 1 is a graph showing the amount of amine groups on the surface of HAP rich amino catecholamine and pDA coatings;

FIG. 2 is an AFM image of HAP rich amino catecholamine and pDA coatings after soaking under different conditions.

Detailed Description

In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.

The present invention provides a catecholamine-based rich amine-based surface-modified product, a material, and a method for dip coating the same.

An amine compound rich in amino catecholamine is prepared by reacting plant polyphenol compound containing carboxyl with amine-rich molecule. The amino-rich catecholamine compound can form a catecholamine rich amine adhesive coating after being mixed with an alkaline buffer solution, the coating has strong adhesive property and stable chemical property, is not easy to disintegrate under extreme conditions, and can be applied to almost any type of materials or substrate materials in shapes.

Preferably, in order to ensure that the raw materials involved in the reaction are not too wasted, the molar ratio of the carboxyl in the carboxyl-containing plant polyphenol compound involved in the reaction to the amino in the amine-rich molecules involved in the reaction is 0.14-0.33: 1.

Preferably, in order to improve the reaction efficiency of the carboxyl in the carboxyl-containing plant polyphenol compound and the rich amine group molecules participating in the reaction, the concentration of the carboxyl-containing plant polyphenol compound in the acid buffer solution is 0.5-1.5 mg/ml.

Preferably, the carboxyl-containing plant polyphenol compound and the amine-rich molecule are completely reacted in the acid buffer solution for at least 0.5 h. The reaction lasts for at least 0.5h, which ensures that the two substances are basically reacted completely.

Preferably, the plant polyphenol compound containing carboxyl and the rich amine group molecule are placed in an acid buffer solution for dialysis after complete reaction, and the dialysis is placed in a dialysis bag for dialysis for at least 0.5 h. The dialysis in the dialysis bag for at least 0.5h can ensure that the amine compound rich in amino group obtained by the reaction is separated from other substances to ensure higher purity of the amine compound rich in amino group. Preferably, the dialysis times in the dialysis bag are 6 times and 3 hours each time in order to ensure complete separation of the amine compound rich in amino groups obtained by the reaction from other substances on the premise of ensuring high efficiency.

Preferably, the acidic buffer comprises MES buffer, citric acid-sodium hydroxide-hydrochloric acid buffer, or disodium hydrogen phosphate-sodium dihydrogen phosphate buffer. The above acidic buffer is a relatively common and readily available acidic buffer, and it should be noted that the acidic buffer referred to in the present invention is not limited to the above. The MES buffer is 2- (N-morpholine) ethanesulfonic acid buffer.

A catecholamine-based rich amine surface modification product comprises a mixture of an alkaline buffer solution and a rich amine-based catecholamine compound, wherein the dosage ratio of the rich amine-based catecholamine compound to the alkaline buffer solution is 0.01-100 mg: 1mL, the amino-rich catechol amine compound is obtained by the reaction of a carboxyl-containing plant polyphenol compound and an amino-rich molecule.

According to the catecholamine-based rich amine surface modification product, the alkaline buffer solution and the rich amine-based catecholamine compound are stored separately before use, when the product is used, the alkaline buffer solution is mixed with the rich amine-based catecholamine compound, and the rich amine-based catecholamine compound obtained by the reaction of the carboxyl-containing plant polyphenol compound and the rich amine-based molecules is mixed with the alkaline buffer solution to form the catecholamine-rich amine adhesive coating. Due to the characteristic of rich amine groups of the coating formed by the surface modified product, the surface modified product has wide reactivity, and can react with carboxyl compounds, NHS, succinic anhydride and carbonyl compounds, such as polyethylene glycol grafted on 316LSS for biological decontamination; the antibacterial polypeptide is grafted on the surface of the PVC for the antibacterial function; the surface of the cobalt-chromium-nickel alloy bracket is grafted with heparin for anticoagulation and the like, and the surface modified product has different functions after reacting with substances with different properties.

Preferably, in order to ensure that the coating formed by the surface modified product has stronger adhesive capacity and more stable chemical performance, the ratio of the amine compound rich in amino group catechol to the alkaline buffer solution is 0.5-1.5 mg: 1 mL.

Preferably, the plant polyphenol compound having carboxyl groups includes at least one of caffeic acid, hydrogenated caffeic acid, gallic acid, tannic acid, ferulic acid, 2, 3-dihydroxybenzoic acid and 3, 4-dihydroxybenzoic acid. The above-mentioned several plant polyphenol compounds containing carboxyl are relatively common and easily available compounds, and it should be noted that the plant polyphenol compounds containing carboxyl referred to in the present invention are not limited to the above-mentioned several compounds.

Preferably, the amine-rich molecule comprises at least one of polyallylamine, polyvinylamine, polylysine, and chitosan. The amine-rich molecules are relatively common and easily available, and it should be noted that the amine-rich molecules referred to in the present invention are not limited to the above-mentioned molecules.

Preferably, the alkaline buffer solution comprises sodium carbonate-sodium bicarbonate buffer, PBS buffer or Tris-HCl buffer. The alkaline buffer is a common and easily available alkaline buffer, and it should be noted that the alkaline buffer referred to in the present invention is not limited to the above. PBS buffer solution is phosphate buffer solution, and Tris-HCl buffer solution is Tris buffer solution.

s1, placing the substrate material in the mixture of the alkaline buffer solution and the rich amino catechol amine compound to react for at least 0.5h to obtain a primary sample, wherein the ratio of the rich amino catechol amine compound to the alkaline buffer solution is 0.01-100 mg: 1 mL.

Firstly, cleaning a substrate material with a surface to be modified, and drying the substrate material for later use; the dosage ratio of the amino-rich catecholamine compound to the alkaline buffer solution is 0.01-100 mg: 1mL, wherein the ratio of the amine-rich catechol amine compound to the alkaline buffer solution is 0.5-1.5 mg: 1 mL.

Preferably, the alkaline buffer solution comprises sodium carbonate-sodium bicarbonate buffer, PBS buffer or Tris-HCl buffer. The alkaline buffer is a common and easily available alkaline buffer, and it should be noted that the alkaline buffer referred to in the present invention is not limited to the above. PBS buffer solution is phosphate buffer solution, and Tris-HCl buffer solution is Tris buffer solution. Specifically, the pH value of the alkaline buffer solution is 8-10.

And then placing the clean and dry substrate material into a mixture of the alkaline buffer solution and the rich amino catechol amine compound for reaction for at least 0.5h, wherein the alkaline buffer solution and the rich amino catechol amine compound can be mixed in advance.

Alternatively, if the mixture is not mixed in advance, the clean and dry substrate material may be placed in an alkaline buffer solution, and then the amino-rich catecholamine compound may be added to the alkaline buffer solution for at least 0.5 h.

In order to avoid wasting the dip-coating time, the reaction time is preferably 0.5-48 h.

Further preferably, in order to ensure that the performance of the surface coating of the substrate material is better after the reaction is finished, the reaction temperature is controlled to be 4-37 ℃ in the reaction process.

S2, the primary sample is dried after being washed.

Specifically, the primary sample is immersed in deionized water and washed, and dried under an inert gas atmosphere, in the present invention, the inert gas may be either an element in group 0 of the periodic table or nitrogen, and in practical use, nitrogen with a lower cost is preferable.

Further, the base material may include a metal material, an inorganic material, or a polymer material. It should be noted that the base material in the present invention is not limited to the above materials.

Specifically, the metal material includes, but is not limited to, stainless steel, cobalt-based alloys, titanium and its alloys, nickel titanium alloys, platinum and its alloys, magnesium and its alloys, iron and its alloys, zinc and its alloys, and noble metals such as gold and silver.

Inorganic materials including, but not limited to, titanium oxide and its nanotubes, carbon materials, silicon dioxide, hydroxyapatite and calcium phosphate silicon nitride, silicon carbide, aluminosilicates, bioglass, titanium nitride, and the like.

The polymer material matrix includes, but is not limited to, dacron, polyethylene, polyvinyl chloride, polytetrafluoroethylene, polyurethane, polystyrene, polyvinyl alcohol, polypropylene, polyoxymethylene, polycarbonate, polymethyl methacrylate, polylactic acid, polycaprolactone, polyamide, epoxy resin, silicone rubber, and the like.

The material with the surface coating is prepared by adopting the method for dip-coating the catecholamine-based rich amine-based coating on the surface of the material. The surface of the material is not easy to deteriorate and damage in extreme environment, so that the material has good performance, long service life and high use safety, and can be applied to the field of chemistry or medicine.

The catecholamine-based rich amine-based surface modification product, the coating and the preparation method thereof, the material with the coating on the surface and the dip coating method thereof provided by the invention are specifically described below with reference to specific examples.

Example 1

The embodiment provides a catecholamine-rich catecholamine compound, a preparation method thereof, a catecholamine-based rich amine surface modification product, a material and a dip coating method thereof.

A method for preparing an amine compound rich in amino catechol comprises the following steps: adding hydrogenated caffeic acid and polyallylamine into MES buffer solution according to the molar ratio of carboxyl to amino of 0.2:1, reacting for 12 hours to obtain mixed solution, placing the mixed solution into a dialysis bag, dialyzing for 3 hours for 6 times, and freeze-drying the dialyzed solution to obtain the amine compound rich in amino groups.

A catecholamine-based rich amine-based surface-modified product comprising two components: PBS buffer solution and rich amine group catecholamine compound, the dosage ratio of the rich amine group catecholamine compound to the PBS buffer solution is 1 mg: 1 mL. The amine compound rich in amino catechol is obtained by the reaction of hydrogenated caffeic acid and polyallylamine.

and mixing the rich amino catechol amine compound with a PBS buffer solution to obtain a mixture, wherein the ratio of the usage amount of the rich amino catechol amine compound to the usage amount of the PBS buffer solution is 1 mg: 1 mL.

And (3) placing the substrate material with the cleaned and dried surface into the mixture, and reacting for 24 hours at 37 ℃ to obtain a primary sample. And then soaking and cleaning the primary sample by using deionized water, and drying in a nitrogen atmosphere to obtain the material with the surface coating.

Example 2

This example is substantially the same as example 1 except that the carboxyl group-containing plant polyphenol compound is tannic acid and the basic buffer is Tris-HCl.

Example 3

This example is essentially the same as example 1, except that the rich amino molecule is chitosan and the alkaline buffer is Tris-HCl.

Example 4

This example is substantially the same as example 1 except that the carboxyl group-containing plant polyphenol compound is caffeic acid and the rich amino molecule is polylysine.

Example 5

This example is substantially the same as example 1, except that the carboxyl group-containing plant polyphenol compound is gallic acid and the rich amine group molecule is polyvinylamine.

Example 6

This example is substantially the same as example 1 except that the carboxyl group-containing plant polyphenol compound is 3, 4-dihydroxybenzoic acid.

Example 7

This example is substantially the same as example 1 except that the ratio of the amount of the aminocatechol-rich amine compound to the amount of the PBS buffer was 0.5 mg: 1 mL.

In the preparation of the aminocatechol-rich amine compound, the molar ratio of the carboxyl groups in the hydrogenated caffeic acid involved in the reaction to the amine groups in the polyallylamine involved in the reaction was 0.14: 1. The concentration of the hydrogenated caffeic acid in PBS buffer was 0.5 mg/ml.

Example 8

This example is essentially the same as example 1 except that the ratio of the amount of the aminocatechol-rich amine compound to the amount of the PBS buffer was 1.5 mg: 1 mL.

In the preparation of the aminocatechol-rich amine compound, the molar ratio of the carboxyl group in the hydrogenated caffeic acid involved in the reaction to the amine group in the polyallylamine involved in the reaction was 0.33: 1. The concentration of the hydrogenated caffeic acid in PBS buffer was 1.5 mg/ml.

Example 9

This example is substantially the same as example 1 except that the ratio of the amount of the aminocatechol-rich amine compound to the amount of the PBS buffer was 0.8 mg: 1 mL.

In the preparation of the aminocatechol-rich amine compound, the molar ratio of the carboxyl group in the hydrogenated caffeic acid involved in the reaction to the amine group in the polyallylamine involved in the reaction was 0.17: 1. The concentration of the hydrogenated caffeic acid in PBS buffer was 1.2 mg/ml.

Example 10

This example is substantially the same as example 1 except that the ratio of the amount of the aminocatechol-rich amine compound to the amount of the PBS buffer was 1.3 mg: 1 mL.

In the preparation of the aminocatechol-rich amine compound, the molar ratio of the carboxyl groups in the hydrogenated caffeic acid involved in the reaction to the amine groups in the polyallylamine involved in the reaction was 0.28: 1. The concentration of the hydrogenated caffeic acid in PBS buffer was 0.7 mg/ml.

Example 11

A method for preparing an amine compound rich in amino catechol comprises the following steps: ferulic acid and polyvinylamine are added into a citric acid-sodium hydroxide-hydrochloric acid buffer solution according to the molar ratio of carboxyl to amino of 0.01:1 to react for 0.5 hour to obtain a mixed solution, the mixed solution is placed into a dialysis bag to be dialyzed for 1 time for 0.5 hour each time, and then the solution obtained by dialysis is frozen and dried to obtain the amino-rich catechol amine compound.

A catecholamine-based rich amine-based surface-modified product comprises two compositions of a sodium carbonate-sodium bicarbonate buffer and a rich aminocatecholamine compound, wherein the ratio of the amount of the rich aminocatecholamine compound to the amount of the sodium carbonate-sodium bicarbonate buffer is 0.01 mg: 1 mL. The amino-rich catechol amine compound is obtained by reacting ferulic acid with polyvinylamine.

mixing the prepared rich amino catechol amine compound with a sodium carbonate-sodium bicarbonate buffer solution to obtain a mixture, wherein the dosage ratio of the rich amino catechol amine compound to the sodium carbonate-sodium bicarbonate buffer solution is 0.01 mg: 1 mL.

And (3) placing the substrate material with the cleaned and dried surface into the mixture, and reacting for 0.5h at 4 ℃ to obtain a primary sample. And then soaking and cleaning the primary sample by using deionized water, and drying in a nitrogen atmosphere to obtain the material with the surface coating.

Example 12

The embodiment provides a catecholamine-based rich amine surface modified product, a coating, a preparation method of the coating, a material with the coating on the surface and a dip coating method of the material.

A method for preparing an amine compound rich in amino catechol comprises the following steps: adding 2, 3-dihydroxybenzoic acid and polylysine into disodium hydrogen phosphate-sodium dihydrogen phosphate buffer solution according to the molar ratio of carboxyl to amino of 10:1, reacting for 2 hours to obtain a mixed solution, placing the mixed solution into a dialysis bag, dialyzing for 1 time and 2 hours each time, and freeze-drying the dialyzed solution to obtain the amino-rich catechol amine compound.

A catecholamine-based rich amine-based surface-modified product comprising two components: the sodium carbonate-sodium bicarbonate buffer solution and the rich amino catechol amine compound, wherein the dosage ratio of the rich amino catechol amine compound to the sodium carbonate-sodium bicarbonate buffer solution is 100 mg: 1 mL. The amine compound of the rich amino catechol is obtained by the reaction of 2, 3-dihydroxy benzoic acid and polylysine.

mixing the prepared rich amino catechol amine compound with a sodium carbonate-sodium bicarbonate buffer solution to obtain a mixture, wherein the dosage ratio of the rich amino catechol amine compound to the sodium carbonate-sodium bicarbonate buffer solution is 100 mg: 1 mL.

And (3) placing the substrate material with the cleaned and dried surface into the mixture, and reacting for 2h at the temperature of 30 ℃ to obtain a primary sample. And then soaking and cleaning the primary sample by using deionized water, and drying in a nitrogen atmosphere to obtain the material with the surface coating.

Example 13

This embodiment is substantially the same as embodiment 11 except that:

the dosage ratio of the amino-rich catechol amine compound to the sodium carbonate-sodium bicarbonate buffer solution is 5 mg: 1 mL.

2, 3-dihydroxy benzoic acid and polylysine are added into a disodium hydrogen phosphate-sodium dihydrogen phosphate buffer solution according to the molar ratio of carboxyl to amino of 0.05: 1.

The dialysis times was 2 times, and the dialysis time was 1 h.

And (3) placing the substrate material with the cleaned and dried surface into the mixture, and reacting for 5 hours at 10 ℃ to obtain a primary sample.

Example 14

This embodiment is substantially the same as embodiment 11 except that:

the dosage ratio of the amino-rich catechol amine compound to the sodium carbonate-sodium bicarbonate buffer solution is 10 mg: 1 mL.

2, 3-dihydroxy benzoic acid and polylysine are added into a disodium hydrogen phosphate-sodium dihydrogen phosphate buffer solution according to the molar ratio of carboxyl to amino of 0.5: 1.

The dialysis times was 3 times, and the dialysis time was 2 hours.

And (3) placing the substrate material with the cleaned and dried surface into the mixture, and reacting for 10 hours at the temperature of 20 ℃ to obtain a primary sample.

Example 15

This embodiment is substantially the same as embodiment 11 except that:

the dosage ratio of the amino-rich catechol amine compound to the sodium carbonate-sodium bicarbonate buffer solution is 50 mg: 1 mL.

2, 3-dihydroxy benzoic acid and polylysine are added into a disodium hydrogen phosphate-sodium dihydrogen phosphate buffer solution according to the molar ratio of carboxyl to amino of 3: 1.

The dialysis times were 7 times, and the dialysis time was 2 hours.

And (3) placing the substrate material with the cleaned and dried surface into the mixture, and reacting for 2h at 25 ℃ to obtain a primary sample.

Example 16

This embodiment is substantially the same as embodiment 11 except that:

the dosage ratio of the amino-rich catechol amine compound to the sodium carbonate-sodium bicarbonate buffer solution is 80 mg: 1 mL.

2, 3-dihydroxy benzoic acid and polylysine are added into a disodium hydrogen phosphate-sodium dihydrogen phosphate buffer solution according to the molar ratio of 5:1 of carboxyl to amino.

The dialysis times was 1 time and the dialysis time was 20 hours.

And (3) placing the substrate material with the cleaned and dried surface into the mixture, and reacting for 18h at 15 ℃ to obtain a primary sample.

Example 17

This embodiment is substantially the same as embodiment 11 except that:

2, 3-dihydroxy benzoic acid and polylysine are added into a disodium hydrogen phosphate-sodium dihydrogen phosphate buffer solution according to the molar ratio of carboxyl to amino being 8: 1.

The dialysis times were 4 times, and the dialysis time was 0.5 h.

And (3) placing the substrate material with the cleaned and dried surface into the mixture, and reacting for 40h at the temperature of 7 ℃ to obtain a primary sample.

Example 18

The embodiment provides a method for dip-coating a catecholamine-based rich amine-based coating on the surface of a material, which comprises the following steps:

preparation of amino-rich catecholamine compounds: adding hydrogenated caffeic acid and polyallylamine into MES buffer solution at a molar ratio of carboxyl to amino of 0.2:1, reacting for 12 hr to obtain mixed solution, dialyzing in dialysis bag for 3 hr for 6 times, and freeze drying the dialyzed solution to obtain the amino-enriched catecholamine compound.

Placing the substrate material with the cleaned and dried surface into a PBS buffer solution, and then adding the rich amino catechol amine compound prepared in the embodiment into the PBS buffer solution, wherein the dosage ratio of the rich amino catechol amine compound to the PBS buffer solution is 1 mg: 1mL, and reacting for 2h at 35 ℃ to obtain a primary sample. And soaking and cleaning the primary sample by using deionized water, and drying in a nitrogen atmosphere to obtain the material with the surface coating, wherein the coating on the surface of the material is the catecholamine-based rich amine-based coating provided by the embodiment.

Comparative example

The comparative example provides a method of applying a polydopamine coating to a surface of a material, comprising:

and (2) putting the 316L stainless steel with the clean and dried surface into a Tris buffer solution with the pH value of 8.5, adding dopamine into the Tris buffer solution, wherein the concentration of the dopamine is 1mg/ml, and reacting for 24 hours at the temperature of 25 ℃ to obtain a primary sample. And then soaking and cleaning the primary sample by using deionized water, and drying in a nitrogen atmosphere to obtain the material with the surface coating, wherein the coating on the surface of the material is a polydopamine coating.

Experimental example 1

The coating samples (HAP and pDA) in example 1 and comparative example 1 were taken, 170uL of acid orange solution was added dropwise to the surface of the samples for sufficient reaction for 8h, after the reaction was completed, deionized water was used for washing, 170uL of NaOH solution with pH12 was added dropwise for dissociation for half an hour, and 150uL of dissociation solution was extracted for absorbance determination. Whereby the amine group density of the surface of both coatings was calculated. The results are plotted in FIG. 1.

As can be seen from FIG. 1, the surface amine group density of the HAP coating is 12nmol/cm²Much greater than 2.5nmol/cm of the surface of the pDA coating²The density of the amino groups is more beneficial to the further functional modification related to the amino groups.

Experimental example 2

The coating samples (HAP and pDA) of example 1 and comparative example 1 were taken, immersed in a strong acid (hydrochloric acid solution at pH 2), a strong base (sodium hydroxide solution at 200 mg/ml), and a strong oxidizing agent (3% hydrogen peroxide solution) for 24 hours, respectively, and the stability of the coating was observed by atomic force microscopy. The results are plotted in FIG. 2.

As can be seen from FIG. 2, after immersion in strong acid (hydrochloric acid solution pH 2), strong base (200mg/ml NaOH solution), and strong oxidizer (3% hydrogen peroxide solution) for 24 hours, the pDA coating was not stable enough to peel off and expose the surface of the 316LSS substrate; and the HAP coating is still stable after soaking. The coating formed on the surface of the material after the catecholamine-based rich amine-based surface modification product is dip-coated is good in adhesion and stable in chemical performance.

In summary, the amine-rich catechol amine compound provided by the invention can be mixed with an alkaline buffer solution, and a substrate material is placed in the mixed solution, so that the surface of the substrate material is covered with a amine-rich coating, and the coating has strong adhesion performance, stable chemical performance and difficult disintegration under extreme conditions, and can be applied to substrate materials of almost any type of materials or shapes. And the formed coating is rich in amine groups, so that the coating has wide reactivity.

The catecholamine-based rich amine surface modification product is used by mixing an alkaline buffer solution and a rich amine catecholamine compound, and immersing a substrate material to be surface modified in the mixture of the alkaline buffer solution and the rich amine catecholamine compound obtained by the reaction of a carboxyl-containing plant polyphenol compound and a rich amine molecule in the alkaline buffer solution to form a catecholamine-rich amine adhesive coating, wherein the coating has strong adhesive property, stable chemical property and difficult disintegration under extreme conditions, and can be applied to almost any type of material or substrate material in shape. Due to the characteristic of rich amine groups of the coating formed by the surface modified product, the surface modified product has wide reactivity, and can react with carboxyl compounds, NHS, succinic anhydride and carbonyl compounds, such as polyethylene glycol grafted on 316LSS for biological decontamination; the antibacterial polypeptide is grafted on the surface of the PVC for the antibacterial function; the surface of the cobalt-chromium-nickel alloy bracket is grafted with heparin for anticoagulation and the like, and the coating has different functions after reacting with substances with different properties.

The surface of the material with the coating provided by the invention is coated with the coating provided by the invention. The surface of the material is not easy to deteriorate and damage in extreme environment, so the material has good performance, long service life and high use safety, and can be applied to the field of chemistry or medicine.

The catecholamine-based rich amine-based coating provided by the invention is prepared by adopting the preparation method of the catecholamine-based rich amine-based coating provided by the invention, so that the coating has good adhesion performance to a substrate material, stable chemical performance and difficulty in disintegration under extreme conditions.

The method for dip-coating the catecholamine-based rich amine coating on the surface of the material can dip-coat the coating provided by the invention on the surface of a substrate material to form a catecholamine-based rich amine adhesive coating, the method is simple, the coating obtained by dip-coating has good adhesive property to the substrate material, stable chemical property and difficult disintegration under extreme conditions, and the surface of the material with the coating obtained by dip-coating is difficult to deteriorate and damage under extreme environments, so the material has good performance, long service life and high use safety.

The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims

1. A catecholamine-based rich amine surface modification product is characterized by comprising an alkaline buffer solution and a rich amine-based catecholamine compound, wherein the dosage ratio of the rich amine-based catecholamine compound to the alkaline buffer solution is 0.5-1.5 mg: 1 mL;

the preparation method of the amine compound rich in amino catechol comprises the following steps: placing a carboxyl-containing plant polyphenol compound and an amino-rich molecule in an acid buffer solution for complete reaction, and then dialyzing and freeze-drying to obtain an amino-rich catechol amine compound, wherein the molar ratio of carboxyl in the carboxyl-containing plant polyphenol compound participating in the reaction to amino in the amino-rich molecule participating in the reaction is 0.01-10: 1, and the concentration of the carboxyl-containing plant polyphenol compound in the acid buffer solution is 0.01-100 mg/ml;

the acidic buffer solution comprises MES buffer solution, citric acid-sodium hydroxide-hydrochloric acid buffer solution or disodium hydrogen phosphate-sodium dihydrogen phosphate buffer solution;

placing the plant polyphenol compound containing carboxyl and the amine-rich molecule in the acidic buffer solution to completely react for at least 0.5 h;

and (3) placing the plant polyphenol compound containing carboxyl and the rich amine group molecule in the acidic buffer solution for dialysis after the complete reaction, and placing the plant polyphenol compound containing carboxyl and the rich amine group molecule in a dialysis bag for dialysis for at least 0.5 h.

2. The catecholamine-based rich amine group surface modified product of claim 1, wherein the molar ratio of the carboxyl groups in the carboxyl group-containing plant polyphenol compound involved in the reaction to the amine groups in the amine group-rich molecules involved in the reaction is 0.14 to 0.33: 1.

3. A catecholamine-based rich amine-based surface modified product according to claim 1, wherein the concentration of the plant polyphenol compound containing carboxyl groups placed in the acidic buffer is 0.5 to 1.5 mg/ml.

4. A catecholamine-based rich amine-based surface-modified product as claimed in claim 1, wherein the carboxyl group-containing plant polyphenol compound comprises at least one of caffeic acid, hydrogenated caffeic acid, gallic acid, tannic acid, ferulic acid, 2, 3-dihydroxybenzoic acid and 3, 4-dihydroxybenzoic acid.

5. The catecholamine-based rich amine-based surface modification product of claim 1, wherein the amine-rich molecule comprises at least one of polyallylamine, polyvinylamine, polylysine and chitosan.

6. A catecholamine-based rich amine-based surface-modified product according to claim 1, wherein the alkaline buffer solution comprises sodium carbonate-sodium bicarbonate buffer, PBS buffer or Tris-HCl buffer.

7. A method for dip coating a catecholamine-based rich amine-based coating on a material surface, comprising:

placing a substrate material into a mixture obtained by mixing an alkaline buffer solution and an amino-rich catecholamine compound, and reacting for at least 0.5h to obtain a primary sample, wherein the ratio of the usage amount of the amino-rich catecholamine compound to the alkaline buffer solution is 0.01-100 mg: 1mL, and the preparation method of the amino-rich catechol amine compound comprises the following steps: placing a carboxyl-containing plant polyphenol compound and an amino-rich molecule in an acid buffer solution for complete reaction, and then dialyzing and freeze-drying to obtain an amino-rich catechol amine compound, wherein the molar ratio of carboxyl in the carboxyl-containing plant polyphenol compound participating in the reaction to amino in the amino-rich molecule participating in the reaction is 0.01-10: 1, and the concentration of the carboxyl-containing plant polyphenol compound in the acid buffer solution is 0.01-100 mg/ml;

the primary sample is washed and then dried,

placing the substrate material in the mixture to react at a reaction temperature of 1-99 ℃;

and placing the substrate material in the mixture for reaction for 0.5-48 h.

8. The method for dip coating a catecholamine-based rich amine-based coating on a material surface according to claim 7, wherein the ratio of the amount of the catecholamine-based rich amine compound to the amount of the alkaline buffer solution is 0.5 to 1.5 mg: 1 mL.

9. The method for dip coating a catecholamine-based rich amine-based coating on a material surface according to claim 7, wherein,

the primary sample is washed and dried as follows: the primary sample is placed in deionized water for immersion cleaning and dried under an inert gas atmosphere.

10. The method for dip coating a catecholamine-based rich amine-based coating on a material surface as claimed in claim 9, wherein the inert gas is nitrogen.

11. The method for dip coating a catecholamine-based rich amine-based coating on a material surface as claimed in claim 9, wherein the base material comprises a metallic material, an inorganic material or a polymeric material.

12. A material having a coating on a surface thereof, characterized by being produced by the method according to any one of claims 7 to 11.