CN101177495A - Method for preparing biomimetic superhydrophobic surface by enzymatic biocatalysis - Google Patents

Abstract

The invention discloses a method for preparing a bionic super-hydrophobic surface by utilizing enzyme biocatalysis. The method first prepares stable and uniformly dispersed metal nanoparticles, and at the same time grafts the surface of the base material to have specific functional groups, and connects the metal nanoparticles to the surface of the base material, and then catalyzes the method by an enzyme catalyst to achieve The metal particles on the surface of the base material grow to a micron size, and finally a superhydrophobic surface is obtained through the access of hydrophobic groups. This method is environmentally friendly, simple and easy to implement, and highly controllable. The resulting surface has excellent superhydrophobic properties, and has great application prospects in the fields of microfluidic devices, antibacterial coatings, biomolecular diagnosis and detection, and biosensors.

Description

Method for preparing biomimetic superhydrophobic surface by enzymatic biocatalysis

technical field

The invention relates to a method for preparing a bionic superhydrophobic surface by using enzyme biocatalysis, and belongs to the interdisciplinary field of materials, biology, physics, chemistry and other disciplines.

Background technique

Wettability is an important physical and chemical property of a solid surface. When the contact angle between the surface of a solid and water is greater than 150 degrees, it is called a superhydrophobic material. Superhydrophobic materials have extremely broad application prospects in industrial and agricultural production and people's daily life. They can be used to prevent snow, rain, self-cleaning, anti-oxidation, prevent current conduction, and be used as microfluidic devices.

Some plants, such as lotus leaves, taro leaves, and straw leaves, have superhydrophobicity and whitening ability, which is called the lotus leaf effect. The surface superhydrophobic phenomenon produced by the lotus leaf effect provides bionic inspiration for people to construct superhydrophobic surfaces. Studies have found that the surface hydrophobicity is determined by the microstructure and chemical composition. The surface roughness combined with micron and nanometer Surface structure plays an important role in superhydrophobicity. Inspired by this phenomenon, many researchers at home and abroad have obtained superhydrophobic properties of solid surfaces by constructing microstructures and nanostructures on the surface of solid materials. Chinese Patent Publication No. 1415800 discloses a superhydrophobic, self-cleaning nanostructure surface paper. They applied silica gel, ethyl acetate and banana water on the surface of ordinary paper to prepare a superhydrophobic, white and clean nanostructure surface layer. Chinese Patent Publication No. 1379128 uses chemical vapor deposition to obtain a film with an array structure, and then sequentially treats it with hot concentrated sulfuric acid, a large amount of ultrapure water and an alcohol solution containing a hydrophobic reagent, and then heats it to obtain a super-amphiphobic film. CN1613565A discloses a method for preparing a super-hydrophobic micro-structure surface. A micro-surface with a zinc oxide structure is prepared on the surface of a glass or a silicon wafer by a wet chemical method, and then the surface is modified by molecular self-assembly to obtain a super-hydrophobic surface.

The above-mentioned currently commonly used methods generally use chemical methods, the process is complicated, a large amount of organic solvents are used, the environment is polluted, and the cost is relatively high. Applications in microfluidic devices, antimicrobial coatings, biomolecular diagnostics and detection, biosensors, etc. are largely limited. How to prepare a stable superhydrophobic surface with a green, pollution-free, simple, controllable, and easy-to-operate method is particularly important.

Contents of the invention

The purpose of the present invention is to provide a method for preparing a biomimetic superhydrophobic surface by utilizing enzyme biocatalysis.

Including the following steps:

1) 1 part by weight of metal salt, 0.1 to 100 parts by weight of sodium citrate and 100 to 50,000 parts by weight of water, heated to 20 to 200° C., and reacted for 0.1 to 10 hours to obtain a stable and uniformly dispersed metal nanoparticle solution;

2) Prepare a surface modifier solution with a concentration of 0.01-10mg/ml, immerse the base material in the solution, and carry out surface grafting reaction at 10-50°C for 0.1-10 hours to obtain a base with functional groups on the surface Material;

3) placing 1 g of the substrate material with functional groups on its surface in 0.1-100 ml of the above-mentioned metal nanoparticle solution, and reacting at 20-100° C. for 0.5-10 hours to obtain a substrate material grafted with metal nanoparticles;

4) 1 part by weight of the base material grafted with the above-mentioned metal nanoparticles, 1 part by weight of an enzyme catalyst, 100 to 10000 parts by weight of a substrate for an enzyme catalyst, and 100 to 10000 parts by weight of a metal salt are placed in 1000 to 50000 parts by weight of water, and placed in 10 to 50000 parts by weight of water. React at 40°C for 0.5 to 10 hours to obtain a base material that catalyzes the growth of metal nanoparticles;

5) Put the surface of the base material on which the above-mentioned metal nanoparticles have been catalyzed and grown in a hydrophobizing agent with a concentration of 0.01-1 M, and react at 10-40° C. for 0.5-10 hr to obtain a super-hydrophobic surface.

The metal salt is selected from chloroauric acid, chloroplatinic acid, silver nitrate, copper nitrate, copper chloride, cadmium chloride, cadmium nitrate or palladium chloride.

The surface modifier is selected from ethylenediamine, glycerinetriamine, 1,2-propylenediamine, 1,3-propylenediol, 1,3-propylenediamine, 1,4-butylenediamine, 1,2 -Butanediamine, 1,3-butanediamine, butanetriamine, aminopropyltrichlorosilane, mercaptopropyltrichlorosilane, aminopropyldimethylchlorosilane, mercaptopropyldimethylchlorosilane, mercapto Ethylamine or polyethyleneimine.

The base material is selected from polyethylene terephthalate, polylactic acid, polyglycolic acid, copolymers of polylactic acid and polyglycolic acid, polycaprolactone, polyethylene, polypropylene, polyvinyl chloride, polypropylene Dilute nitrile, nylon-66, polymethyl methacrylate, glass, silicon wafer, or polydimethylsiloxane.

The enzyme catalyst is selected from glucose oxidase, lorosinase, alcohol dehydrogenase, phosphatase or kinase.

The hydrophobizing agent is selected from the group consisting of octadecyl mercaptan, hexadecyl mercaptan, dodecyl mercaptan, octadecylamine, hexadecylamine, dodecylamine, octadecyltrichlorosilane, octadecyldimethyl Chlorosilane or Octadecylmethyldichlorosilane.

The method for preparing a biomimetic superhydrophobic surface by using enzyme biocatalysis provided by the present invention is environmentally friendly, simple and easy to implement, and has strong controllability. It has great application prospects in the fields of diagnosis and detection, biosensors and so on.

The advantages of the present invention are:

1. The method of preparing biomimetic superhydrophobic surface by enzymatic biocatalysis is carried out in a water environment without using organic solvents and does not pollute the environment;

2. Enzyme biocatalysis method to prepare biomimetic superhydrophobic surface, the degree of catalytic growth of nanoparticles is controlled by enzyme catalyst, which is highly controllable;

3. Enzyme biocatalysis method for preparing biomimetic superhydrophobic surface, which has no requirements for substrate materials and has a wide range of applications;

Detailed ways

The invention firstly prepares stable and uniformly dispersed metal nanoparticles, and at the same time grafts the surface of the base material to have specific functional groups, and connects the metal nanoparticles to the surface of the base material, and then realizes The metal particles on the surface of the base material grow to a micron size, and finally a superhydrophobic surface is obtained through the access of hydrophobic groups.

The following examples are to further illustrate the present invention, but not to limit the scope of the present invention.

Example 1:

1) Preparation of metal nanoparticles: In a 100mL single-necked flask, add 100mL of water, then add 10mg of chloroauric acid and 100mg of sodium citrate, and heat to 100°C for 1 hour under magnetic stirring to obtain stable and uniformly dispersed gold nanoparticles .

2) The PET film is ultrasonically cleaned with acetone, ethanol, and triple-distilled water respectively, and then dried to obtain a PET film with a clean surface. At 10° C., the PET film was immersed in a 10 mg/mL 1,3-butanediamine solution in isopropanol to react for 0.1 h. Then the membrane was taken out, cleaned with water, and then dried under reduced pressure to constant weight to obtain a PET membrane with free amino groups introduced into the surface.

3) In the petri dish, put the PET membrane containing free amino groups obtained in step 2), and then add 0.1mL of gold nanoparticles obtained in step 1) dropwise on the surface of the membrane, react at 20°C for 0.5hr, and wash with water repeatedly The redundant gold nanoparticles are removed to obtain the base material grafted with gold nanoparticles.

4) Put the base material grafted with gold nanoparticles obtained in step 3) into a test tube, add 10mL of water, 100mg of chloroauric acid, then add 1g of β-D-glucose and 10mg of glucose oxidase, and react at 20°C for 0.5hr . After the reaction, it is repeatedly washed with triple distilled water to obtain the base material on which the gold nanoparticles are catalyzed and grown.

5) Put the PET film obtained by the catalytic growth of gold nanoparticles in step 4) into 1 mM ethanol solution of mercaptooctadecane, react at 25° C. for 1 h, wash several times with triple distilled water, and dry at room temperature , to obtain a PET film with a superhydrophobic surface.

Example 2:

1) Preparation of metal nanoparticles: In a 100mL single-necked flask, add 100mL of water, then add 5mg of silver nitrate and 500mg of sodium citrate, and react at 20°C for 1h under magnetic stirring to obtain stable and uniformly dispersed silver nanoparticles.

2) The PET film is ultrasonically cleaned with acetone, ethanol, and triple-distilled water respectively, and then dried to obtain a PET film with a clean surface. At 50° C., the PET film was immersed in 0.01 mg/mL glycerin triamine in isopropanol solution for 10 h to react. Then the membrane was taken out, cleaned with water, and then dried under reduced pressure to constant weight to obtain a PET membrane with free amino groups introduced into the surface.

3) Put the PET membrane containing free amino groups obtained in step 2) into the petri dish, then add 10mL of silver nanoparticles obtained in step 1) dropwise on the surface of the membrane, react at 20°C for 0.5hr, and wash repeatedly with water to remove The excess silver nanoparticles are obtained as a base material grafted with silver nanoparticles.

4) Put the base material grafted with silver nanoparticles obtained in step 3) into a test tube, add 25mL of water, 100mg of silver nitrate, then add 500mg of β-D-glucose and 5mg of glucose oxidase, and react at 40°C for 0.5hr. After the reaction, it is repeatedly washed with triple distilled water to obtain the base material on which the silver nano particles are catalyzed and grown.

5) Put the PET film grown by the catalysis of the silver nanoparticles obtained in step 4) into the ethanol solution of 0.01mM mercaptooctadecane, react at 10°C for 10h, wash several times with triple distilled water, and let it air in the air at room temperature Dry to obtain a PET film with a superhydrophobic surface.

Example 3:

1) Preparation of metal nanoparticles: In a 100mL single-necked flask, add 50mL of water, then add 30mg of chloroplatinic acid and 3mg of sodium citrate, and react at 50°C for 1h under magnetic stirring to obtain stable and uniformly dispersed platinum nanoparticles.

2) The PET film is ultrasonically cleaned with acetone, ethanol, and triple-distilled water respectively, and then dried to obtain a PET film with a clean surface. At 30° C., the PET film was immersed in 1 mg/mL ethylenediamine in isopropanol solution for 5 h. Then the membrane was taken out, cleaned with water, and then dried under reduced pressure to constant weight to obtain a PET membrane with free amino groups introduced into the surface.

3) Put the PET film containing free amino groups obtained in step 2) into the petri dish, then add 10 mL of platinum nanoparticles obtained in step 1) dropwise on the surface of the film, react at 80°C for 10 hr, and wash repeatedly with water to remove excess The platinum nanoparticles were obtained to obtain the base material grafted with platinum nanoparticles.

4) Put the base material grafted with platinum nanoparticles obtained in step 3) into a test tube, add 50 mL of water, 10 g of chloroplatinic acid, 10 g of β-D-glucose and 1 mg of glucose oxidase, and react at 40° C. for 10 hr. After the reaction, it is repeatedly washed with triple distilled water to obtain a substrate material in which the platinum nanometer particles are catalyzed and grown.

5) Put the PET film grown by the catalytic growth of platinum nanoparticles obtained in step 4) into a 0.01 mM ethanol solution of mercaptooctadecane, react at 40° C. for 0.5 h, wash several times with triple distilled water, After drying, a PET film with a superhydrophobic surface was obtained.

Example 4:

Same as in Example 1, the surface modifier solution used in step 2) is a 3 mg/mL hexamethylenediamine solution in isopropanol.

Example 5:

1) Preparation of metal nanoparticles: In a 500mL single-necked flask, add 250mL of water, then add 5mg of chloroauric acid and 500mg of sodium citrate, and heat to 200°C for 0.1h under magnetic stirring to obtain stable and uniformly dispersed gold nanoparticles. particle.

2) The PET film is ultrasonically cleaned with acetone, ethanol, and triple-distilled water respectively, and then dried to obtain a PET film with a clean surface. At 25° C., the PET film was immersed in 8 mg/mL PEI in isopropanol solution for 7 h. Then the membrane was taken out, cleaned with water, and then dried under reduced pressure to constant weight to obtain a PET membrane with free amino groups introduced into the surface.

3) In the petri dish, put the PET film containing free amino groups obtained in step 2), and then add 100 mL of gold nanoparticles obtained in step 1) dropwise on the surface of the film, react at 100 ° C for 10 hr, and wash repeatedly with water to remove excess The gold nanoparticles were obtained to obtain the base material grafted with gold nanoparticles.

4) Put the base material grafted with gold nanoparticles obtained in step 3) into a test tube, add 10mL of water, 500mg of chloroauric acid, then add 500mg of β-D-glucose and 5mg of glucose oxidase, and react at 40°C for 0.5hr . After the reaction, it is repeatedly washed with triple distilled water to obtain the base material on which the gold nanoparticles are catalyzed and grown.

5) Put the PET membrane grown by the catalytic growth of gold nanoparticles obtained in step 4) into 1M ethanol solution of mercaptooctadecane, react at 20°C for 10 h, wash several times with triple distilled water, and dry in the air at room temperature , to obtain a PET film with a superhydrophobic surface.

Embodiment 6:

Same as Example 1, the base material used in the experiment is a PLA diaphragm.

Embodiment 7:

1) Preparation of metal nanoparticles: In a 100mL single-necked flask, add 100mL of water, then add 10mg of chloroauric acid and 100mg of sodium citrate, and heat to 100°C for 1 hour under magnetic stirring to obtain stable and uniformly dispersed gold nanoparticles .

2) Boil the silicon wafer in a solution of concentrated sulfuric acid/hydrogen peroxide (7:3) for 10 minutes, then ultrasonically clean it with acetone, ethanol, and triple-distilled water, and then dry it to obtain a silicon wafer with a clean surface. The silicon chip was immersed in a toluene solution of 1 mg/mL γ-aminopropyltrimethoxysilane to react for 10 h. Then take out the silicon wafer, wash it with water, and then dry it under reduced pressure to constant weight to obtain a silicon wafer with free amino groups introduced into the surface.

3) In the petri dish, put the silicon chip containing free amino groups obtained in step 2), then add 0.1mL of gold nanoparticles obtained in step 1) dropwise on the surface of the silicon chip, react at 20°C for 0.5hr, and wash repeatedly with water to remove The excess gold nanoparticles are obtained as a base material grafted with gold nanoparticles.

4) Put the base material grafted with gold nanoparticles obtained in step 3) into a test tube, add 10mL of water, 100mg of chloroauric acid, then add 1g of β-D-glucose and 10mg of glucose oxidase, and react at 20°C for 0.5hr . After the reaction, it is repeatedly washed with triple distilled water to obtain the base material on which the gold nanoparticles are catalyzed and grown.

5) Put the silicon chip grown by gold nanoparticles catalyzed in step 4) into 1 mM ethanol solution of mercaptooctadecane, react at 25° C. for 1 h, wash several times with triple distilled water, and dry in the air at room temperature. A silicon wafer with a superhydrophobic surface is obtained.

Embodiment 8:

1) Preparation of metal nanoparticles: In a 100mL single-necked flask, add 100mL of water, then add 5mg of silver nitrate and 25mg of sodium citrate, and react at 70°C for 1h under magnetic stirring to obtain stable and uniformly dispersed silver nanoparticles.

2) The PET film is ultrasonically cleaned with acetone, ethanol, and triple-distilled water respectively, and then dried to obtain a PET film with a clean surface. At 25° C., the PET film was immersed in a 5 mg/mL ethylenediamine solution in isopropanol to react for 0.5 hr. Then the membrane was taken out, cleaned with water, and then dried under reduced pressure to constant weight to obtain a PET membrane with free amino groups introduced into the surface.

3) In the petri dish, put the PET membrane containing free amino groups obtained in step 2), and then add 10 mL of silver nanoparticles obtained in step 1) dropwise on the surface of the membrane, react at 30°C for 2 hours, and wash repeatedly with water to remove The excess silver nanoparticles are obtained as a base material grafted with silver nanoparticles.

4) Put the base material grafted with silver nanoparticles obtained in step 3) into a test tube, add 25 mL of water, 100 mg of silver nitrate, 300 mg of tyrosine and 2 mg of tyrosinase, and react at 30° C. for 1.5 hr. After the reaction, it is repeatedly washed with triple distilled water to obtain the base material on which the silver nano particles are catalyzed and grown.

5) Put the PET membrane grown by the silver nanoparticles catalyzed in step 4) into 0.01mM ethanol solution of mercaptooctadecane, react at 30°C for 1.5h, wash several times with triple distilled water, After drying, a PET film with a superhydrophobic surface was obtained.

Embodiment 9:

1) Preparation of metal nanoparticles: In a 100mL single-necked flask, add 100mL of water, then add 30mg of chloroplatinic acid and 30mg of sodium citrate, and react at 110°C for 3.5h under magnetic stirring to obtain stable and uniformly dispersed platinum nanoparticles.

2) The PET film is ultrasonically cleaned with acetone, ethanol, and triple-distilled water respectively, and then dried to obtain a PET film with a clean surface. At 30°C, the PET film was immersed in a 0.1 mg/mL ethylenediamine solution in isopropanol for 1 h. Then the membrane was taken out, cleaned with water, and then dried under reduced pressure to constant weight to obtain a PET membrane with free amino groups introduced into the surface.

3) Put the PET film containing free amino groups obtained in step 2) into the petri dish, then add 10 mL of platinum nanoparticles obtained in step 1) dropwise on the surface of the film, react at 80°C for 10 hr, and wash repeatedly with water to remove excess The platinum nanoparticles were obtained to obtain the base material grafted with platinum nanoparticles.

4) Put the base material grafted with platinum nanoparticles obtained in step 3) into a test tube, add 500 mL of water, 1 g of chloroplatinic acid, 9 g of ethanol and 6 mg of alcohol dehydrogenase, and react at 25° C. for 2 hours. After the reaction, it is repeatedly washed with triple distilled water to obtain a substrate material in which the platinum nanometer particles are catalyzed and grown.

5) Put the PET film grown by the catalyst of platinum nanoparticles obtained in step 4) into 100 mM ethanol solution of dodecane, react at 40° C. for 0.5 h, wash several times with triple distilled water, and dry in the air at room temperature , to obtain a PET film with a superhydrophobic surface.

Example 10:

With embodiment 1, step 5) used hydrophobization solution is the ethanol solution of the octadecylamine of 10mM

Claims (6)

1. a method of utilizing enzymes biocatalysis to prepare biomimetic super hydrophobic surface is characterized in that comprising the steps:

1) 1 shares of metal, 0.1～100 weight part Trisodium Citrate and 100～50000 weight parts waters are heated to 20～200 ℃, and reaction 0.1～10hr obtains stable and uniform dispersive metal nanoparticle solution;

2) compound concentration is the surface modification agent solution of 0.01～10mg/ml, and base material is immersed in this solution, carries out surface grafting reaction 0.1～10 hour under 10～50 ℃, obtains the base material that the surface contains functional group;

3) base material that the above-mentioned surface of 1g is contained functional group places the above-mentioned metal nanoparticle solution of 0.1～100ml, at 20～100 ℃ of reaction 0.5～10hr down, obtains metal nanoparticle grafted base material;

4) substrate and 100～10000 shares of metal of the above-mentioned metal nanoparticle grafted base material of 1 weight part, 1 weight part enzyme catalyst, 100～10000 enzyme catalysts place 1000～50000 weight parts waters, react 0.5～10hr down at 10～40 ℃, obtain the base material that metal nanoparticle catalysis is grown up;

5) to place concentration be the hydrophobization reagent of 0.01～1M to the substrate material surface that above-mentioned metal nanoparticle catalysis is grown up, and at 10～40 ℃ of reaction 0.5～10hr down, obtains super hydrophobic surface.

2. a kind of method of utilizing enzymes biocatalysis to prepare biomimetic super hydrophobic surface according to claim 1 is characterized in that described metal-salt is selected from hydrochloro-auric acid, Platinic chloride, Silver Nitrate, cupric nitrate, cupric chloride, Cadmium chloride fine powder, cadmium nitrate or Palladous chloride.

3. a kind of method of utilizing enzymes biocatalysis to prepare biomimetic super hydrophobic surface according to claim 1, it is characterized in that described surface-modifying agent is selected from quadrol, third triamine, 1,2-propylene diamine, 1, ammediol, 1,3-propylene diamine, 1,4-butanediamine, 1,2-butanediamine, 1,3-butanediamine, fourth triamine, amine propyltrichlorosilan, mercapto propyltrichlorosilan, amine propyl-dimethyl chlorosilane, mercapto propyl-dimethyl chlorosilane, mercaptoethylamine or polymine.

4. a kind of method of utilizing enzymes biocatalysis to prepare biomimetic super hydrophobic surface according to claim 1 is characterized in that described base material is selected from the multipolymer of polyethylene terephthalate, poly(lactic acid), polyglycolic acid, poly(lactic acid) and polyglycolic acid, polycaprolactone, polyethylene, polypropylene, polyvinyl chloride, polypropylene nitrile, nylon-66, polymethylmethacrylate, glass, silicon chip or polydimethylsiloxane.

5. a kind of method of utilizing enzymes biocatalysis to prepare biomimetic super hydrophobic surface according to claim 1 is characterized in that described enzyme catalyst is selected from glucose oxidase, Lip river amino acid enzyme, ethanol dehydrogenase, phosphoesterase or kinases.

6. a kind of method of utilizing enzymes biocatalysis to prepare biomimetic super hydrophobic surface according to claim 1 is characterized in that described hydrophobization reagent is selected from stearylmercaptan, 16 mercaptan, Dodecyl Mercaptan, stearylamine, cetylamine, amino dodecane, octadecyl trichlorosilane, octadecyl dimethylchlorosilane or octadecyl methyl dichlorosilane.