A photocatalyst-mediated metal-biomolecule self-polymerization coating and its preparation process

Abstract

The present invention belongs to the field of coatings, and specifically relates to a photocatalyst-mediated metal-biomolecule self-polymerization coating and a preparation process thereof. The preparation process is as follows: (1) mixing a soluble metal salt solution, a soluble biomolecule solution and a buffer solution to obtain a mixed solution; (2) immersing a substrate with a photocatalytic effect in the mixed solution for reaction, and irradiating it with ultraviolet light to obtain the photocatalyst-mediated metal-biomolecule self-polymerization coating. The biomolecule coating prepared by this method has strong controllability, and the types of metals and biomolecules can be customized according to functions to meet the needs of different application scenarios. In addition, the coating formed by the self-polymerization of the metal and biomolecules is also scalable, and more functional customization can be achieved through methods such as secondary grafting to meet a wider range of application needs.

Description

Technical Field

[0001] The invention belongs to the field of coatings, and in particular relates to a photocatalyst-mediated metal-biomolecule self-polymerization coating and a preparation process thereof. Background Art

[0002] When photocatalytic materials are exposed to light, their valence band electrons are excited to jump to the conduction band, leaving holes in the valence band, thereby generating electron-hole pairs. These electrons and holes can react with oxygen and water in the air to generate highly oxidizing reactive oxygen species (ROS), such as hydroxyl radicals (·OH), superoxide anions (O2 - ), hydrogen peroxide (H2O2), etc. In addition, photocatalytic materials can also promote some chemical reactions through the transfer of photogenerated charges, such as photolysis of water to produce hydrogen, carbon dioxide reduction, etc. These characteristics make photocatalytic materials widely used in many fields such as environmental governance, energy development, antibacterial disinfection, etc. Especially in the field of biomedical engineering, photocatalytic materials represented by titanium oxide (TiO2), zinc oxide (ZnO), and iron oxide (Fe2O3) are widely used in cardiovascular, bone, oral, tumor and other fields.

[0003] Biomacromolecules are important components of living organisms, participating in almost all life activities of the organism, and each plays its own specific function. In recent years, biomacromolecules have been widely studied and applied in material surface modification, drug delivery, tissue engineering, biosensors, protein chips, gene therapy and bioseparation, food packaging and environmental protection due to their good biocompatibility, strong specific recognition ability, high adjustability and biological activity. Metal ions are widely present in living organisms and participate in many important life processes. Most of the life processes in which metal ions participate actually occur through the interaction between metal ions and biomacromolecules. These metal ions can cause changes in the conformation of biomacromolecules, become structural centers or produce active centers in biomacromolecules, thereby maintaining life activities. In addition, metal ions also have excellent antibacterial, antioxidant, biocatalytic, and electron transfer-promoting properties.

[0004] Therefore, how to organically combine metal ions with biological macromolecules and stably fix them on the surface of materials while ensuring that their respective functions are not affected will hopefully improve the biological properties of photocatalytic materials and achieve customization of their biological functions, which is a difficult problem that needs to be overcome urgently. Summary of the invention

[0005] In order to solve the problems existing in the prior art, the present invention provides a preparation process of a photocatalyst-mediated metal-biomolecule self-polymerization coating, the preparation process comprising the following steps:

[0006] (1) mixing a soluble metal salt solution, a soluble biomolecule solution and a buffer solution to obtain a mixed solution;

[0007] (2) Immersing a substrate having a photocatalytic effect in the mixed solution for reaction and subjecting it to ultraviolet irradiation to obtain a metal-biomolecule self-polymerization coating mediated by the photocatalyst.

[0008] Preferably, in step (1), the metal ions in the soluble metal salt solution include but are not limited to Mg 2+ , Ca 2 + , Mn 2+ , Fe 3+ , Fe 2+ 、Co 2+ 、Ni 2+ , Cu 2+ 、Zn 2+ , Sr 2+ 、Ag + , Pt + One or a combination of two or more of the following;

[0009] And / or, the concentration of the soluble metal salt solution is 0.001-10 mg / mL.

[0010] Preferably, in step (1), the soluble biomolecules include, but are not limited to, one or a combination of two or more of proteins, polypeptides, amino acids, and nucleic acids;

[0011] And / or, the concentration of the soluble biomolecule solution is 0.001-10 mg / mL.

[0012] Preferably, the protein includes, but is not limited to, one or a combination of two or more of serum albumin, lysozyme, fibrinogen, β-lactoglobulin, α-lactalbumin, and catalase;

[0013] And / or, the polypeptide includes but is not limited to one or a combination of two or more of RGD, glutathione, antimicrobial peptides, and endorphins;

[0014] and / or, the amino acids include but are not limited to one or a combination of two or more of tryptophan, cysteine, glycine, and serine;

[0015] And / or, the nucleic acid includes but is not limited to one or both of DNA and RNA.

[0016] Preferably, in step (1), the buffer solution includes but is not limited to one of acetic acid-acetate buffer, Tris-HCl buffer, hydrochloric acid solution, sodium hydroxide solution, distilled water, MES buffer, and HEPES buffer;

[0017] And / or, the pH value of the buffer solution is 2-14.

[0018] Preferably, in step (2), the substrate having a photocatalytic effect includes but is not limited to one of a metal oxide photocatalytic substrate, a sulfide photocatalytic substrate, a carbon nitride-based photocatalytic substrate, a bismuth-based photocatalytic substrate, and a polymer photocatalytic substrate.

[0019] Preferably, the metal oxide type photocatalytic substrate includes but is not limited to one of titanium dioxide, zinc oxide, iron oxide, tin oxide, zirconium oxide, tungsten oxide, copper oxide, and cerium oxide;

[0020] And / or, the sulfide-type photocatalytic substrate includes but is not limited to one of cadmium sulfide, zinc sulfide, and molybdenum sulfide;

[0021] and / or, the carbon nitride-based photocatalytic substrate includes but is not limited to graphite-phase carbon nitride;

[0022] And / or, the bismuth-based photocatalytic substrate includes but is not limited to one of bismuth oxyhalide (wherein the halogen is Cl, Br, I), bismuth vanadate, bismuth tungstate, and bismuth molybdate;

[0023] And / or, the polymer photocatalytic substrate includes but is not limited to one of a metal organic framework material, a covalent organic framework material, and a two-dimensional material MXene.

[0024] Preferably, in step (2), the reaction temperature is 5-60°C;

[0025] And / or, the wavelength of the ultraviolet irradiation is 254-365 nm, and the time of ultraviolet irradiation is 0.1-10 h.

[0026] Preferably, in step (2), the substrate having a photocatalytic effect is pre-treated by washing and drying in sequence before being immersed in the mixed solution;

[0027] And / or, the substrate having photocatalytic activity is subjected to ultrasonic cleaning and drying treatment in sequence after ultraviolet irradiation.

[0028] Based on the same technical concept, another embodiment of the present invention is to provide a photocatalyst-mediated metal-biomolecule self-polymerization coating obtained by the above-mentioned preparation process.

[0029] The beneficial effects of the present invention are:

[0030] 1. The present invention innovatively proposes a coating preparation method that utilizes the optical properties of photocatalytic materials to drive the self-polymerization of metals and biomolecules. Different from traditional biomolecular coating preparation methods such as immersion and deposition, the biomolecular coating prepared by this method is highly controllable and can be customized according to the needs to determine the types of metals and biomolecules.

[0031] 2. The coating formed by the self-polymerization of metals and biomolecules of the present invention is scalable and can be customized with more functions through methods such as secondary grafting to meet a wider range of application needs.

[0032] 3. The metal-biomolecule coating of the present invention can maintain a stable structure in PBS, meeting the requirements for the application of biomedical coatings in physiological environments.

[0033] 4. The metal-biomolecule coating of the present invention is sensitive to ultraviolet light of a specific wavelength, high-salt environment, etc., and can be quickly removed by irradiating specific ultraviolet light or soaking in a saturated sodium chloride solution. After removing the coating, the photocatalytic material substrate can be reused, thereby achieving energy-saving and environmental protection effects while reducing production costs.

[0034] 5. The metal-biomolecule coating of the present invention has good anti-coagulation properties.

[0035] 6. The present invention is based on the ultraviolet-induced photocatalytic effect and can perform micron-level patterning processing through methods such as photolithography to prepare patterned biomolecular coatings and achieve high-precision patterned integration of required customized functions.

[0036] 7. The preparation method described in the present invention belongs to a "one-pot" process with a simple process flow, strong operability and good repeatability. BRIEF DESCRIPTION OF THE DRAWINGS

[0037] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required for use in the embodiments or the description of the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative work.

[0038] Figure 1 This is a fluorescence photograph of a metal-biomolecule coating formed by self-polymerization of a part of metal and protein and stained with NHS-FITC.

[0039] Figure 2 This is a photograph of the stability results of the metal-biomolecule coating.

[0040] Figure 3 This is the XPS result of the metal-biomolecule coating formed by the self-polymerization of some metals and proteins.

[0041] Figure 4 This is a schematic diagram of the recycling of titanium dioxide substrate.

[0042] Figure 5 is a diagram showing the anticoagulant effect of metal-biomolecule coatings.

[0043] Figure 6 It is a micro-pattern of metal-molecular bio-coating. DETAILED DESCRIPTION

[0044] To make the purpose, technical solution and advantages of the present invention clearer, the technical solution of the present invention will be described in detail below. Obviously, the described embodiments are part of the embodiments of the present invention, rather than all of the embodiments. Based on the embodiments of the present invention, all other implementation methods obtained by ordinary technicians in this field without creative work belong to the scope of protection of the present invention.

[0045] Example 1

[0046] This embodiment provides a preparation process of a photocatalyst-mediated metal-biomolecule self-polymerization coating, the preparation process comprising the following steps:

[0047] (1) Mix equal volumes of 0.02 mg / mL ZnSO4 solution and 2 mg / mL BSA (bovine serum albumin) solution, and adjust the pH of the mixed solution to 4.7 with 1 M hydrochloric acid solution;

[0048] (2) The titanium dioxide substrate is first cleaned and dried, then immersed in the mixed solution, irradiated for 1.5 hours under a UV cross-linking instrument with a wavelength of 365 nm, and finally ultrasonically cleaned with deionized water for 3 minutes and naturally dried to obtain a Zn-BSA self-polymerized coating based on titanium dioxide.

[0049] Example 2

[0050] This embodiment provides a preparation process of a photocatalyst-mediated metal-biomolecule self-polymerization coating, the preparation process comprising the following steps:

[0051] (1) Mix equal volumes of 1 mg / mL CuCl2 solution and 2 mg / mL LZM (lysozyme) solution, and adjust the pH of the mixed solution to 11 with 1 M sodium hydroxide solution;

[0052] (2) The g-C3N4 (graphite carbon nitride) substrate is first cleaned and dried, then immersed in the mixed solution, irradiated for 1.5 h under a UV crosslinker with a wavelength of 365 nm, and finally ultrasonically cleaned with deionized water for 3 min and naturally dried to obtain a Cu-LZM self-polymerized coating based on g-C3N4.

[0053] Example 3

[0054] This embodiment provides a preparation process of a photocatalyst-mediated metal-biomolecule self-polymerization coating, the preparation process comprising the following steps:

[0055] (1) Mix equal volumes of 5 mg / mL MnSO4 solution and 2 mg / mL β-Lg solution, and adjust the pH of the mixed solution to 5.2 with 1 M sodium hydroxide solution;

[0056] (2) MOFs (metal organic framework materials) are dispersed in the mixed solution, irradiated for 1.5 h under a UV crosslinker with a wavelength of 365 nm, ultrasonically cleaned for 3 min with deionized water, and dried naturally to obtain a Mn-β-Lg self-polymerized coating based on MOFs.

[0057] Example 4

[0058] This embodiment provides a preparation process of a photocatalyst-mediated metal-biomolecule self-polymerization coating, the preparation process comprising the following steps:

[0059] (1) Mix equal volumes of 2 mg / mL CuCl2 solution and 10 mg / mL L-Cys (L-cysteine) solution;

[0060] (2) Titanium dioxide is dispersed in the mixed solution, irradiated for 3 hours under a UV crosslinker with a wavelength of 365 nm, ultrasonically cleaned for 3 minutes with deionized water, and dried naturally to obtain a Cu-L-Cys self-polymerized coating based on titanium dioxide.

[0061] Effect verification example

[0062] Figure 1 This is a fluorescence photo of a metal-biomolecule coating formed by the self-polymerization of a part of metal and protein and stained with NHS-FITC. Figure 1 It can be explained that the preparation process of the present invention can make metal and biological molecules self-polymerize to form a stable coating, and the coating can be specifically labeled with NHS-FITC to show fluorescence, indicating that the coating contains amino groups and can be modified secondary.

[0063] Figure 2 This is a photo of the stability results of metal-biomolecule coatings. Figure 2 It can be seen that the biomolecular coating of Zn-BSA prepared by the preparation method of the present invention can still maintain structural stability after being immersed in PBS for 20 days, meeting the requirements of the application of biomedical coatings in physiological environments.

[0064] Figure 3 This is the XPS result of the metal-biomolecule coating formed by the self-polymerization of some metals and proteins. Figure 3 The results show that the metal-biomolecule coating prepared by the preparation method of the present invention has a higher density and blocks the Ti peak of the titanium dioxide substrate.

[0065] Figure 4 This is a schematic diagram of the recycling of titanium dioxide substrate. Figure 4 In the present invention, the biomolecular coating of Zn-BSA is first prepared by the preparation method described in the present invention, and then the coating is degraded after being irradiated with ultraviolet light of a wavelength of 254 nm for 2 hours or immersed in a saturated sodium chloride solution for 15 minutes. This confirms that the metal-biomolecular coating prepared by the preparation method described in the present invention can be degraded in a specific response manner, thereby reducing the photocatalytic substrate for recycling, which has good economic benefits.

[0066] Figure 5 This is a diagram of the anticoagulation effect of the metal-biomolecule coating. The platelet-rich slurry separated by whole blood centrifugation is contacted with and adheres to the metal-biomolecule coating. A large number of platelets adhere to the titanium dioxide substrate, and the pseudopodia are extended to show a spreading state, and the platelets are activated; while only a small number of platelets adhere to the Cu-BSA coating prepared by the preparation method of the present invention, and the platelets do not extend pseudopodia, indicating that the metal-biomolecule coating has a good anticoagulation effect.

[0067] Figure 6 It is a micro pattern of metal-molecular bio-coating. It is proved that the preparation method of the present invention can be used to process the coating in micron-level patterning through photolithography and other methods to prepare patterned bio-molecular coatings and realize high-precision pattern integration of required customized functions.

[0068] The above is only a specific embodiment of the present invention, but the protection scope of the present invention is not limited thereto. Any person skilled in the art can easily think of changes or substitutions within the technical scope disclosed by the present invention, which should be included in the protection scope of the present invention. Therefore, the protection scope of the present invention should be based on the protection scope of the claims.

Claims

1. A process for preparing a photocatalyst-mediated metal-biomolecule self-polymerization coating, characterized in that: The preparation process comprises the following steps: (1) Mixing a soluble metal salt solution, a soluble biomolecule solution and a buffer solution to obtain a mixed solution; wherein: The soluble biomolecules include one or a combination of two or more of proteins, polypeptides, amino acids, and nucleic acids; The protein includes one or a combination of two or more of serum albumin, lysozyme, fibrinogen, β-lactoglobulin, α-lactalbumin, and catalase; And / or, the polypeptide includes one or a combination of two or more of RGD, glutathione, antimicrobial peptides, and endorphins; And / or, the amino acids include one or a combination of two or more of tryptophan, cysteine, glycine, and serine; And / or, the nucleic acid comprises one or both of DNA and RNA; (2) Immersing a substrate having a photocatalytic effect in the mixed solution for reaction and subjecting it to ultraviolet irradiation to obtain a metal-biomolecule self-polymerization coating mediated by the photocatalyst.

2. The process for preparing a photocatalyst-mediated metal-biomolecule self-polymerization coating according to claim 1, characterized in that: In step (1), the metal ions in the soluble metal salt solution include Mg 2+ , Ca 2+ , Mn 2+ , Fe 3+ , Fe 2+ 、Co 2+ 、Ni 2+ , Cu 2+ 、Zn 2+ , Sr 2+ 、Ag + , Pt + One or a combination of two or more of the following; And / or, the concentration of the soluble metal salt solution is 0.001-10 mg / mL.

3. The process for preparing a photocatalyst-mediated metal-biomolecule self-polymerization coating according to claim 1, characterized in that: In step (1), the concentration of the soluble biomolecule solution is 0.001-10 mg / mL.

4. The process for preparing a photocatalyst-mediated metal-biomolecule self-polymerization coating according to claim 1, characterized in that: In step (1), the buffer solution includes one of acetic acid-acetate buffer, Tris-HCl buffer, hydrochloric acid solution, sodium hydroxide solution, distilled water, MES buffer, and HEPES buffer; And / or, the pH value of the buffer solution is 2-14.

5. The process for preparing a photocatalyst-mediated metal-biomolecule self-polymerization coating according to claim 1, characterized in that: In step (2), the substrate having a photocatalytic effect includes one of a metal oxide photocatalytic substrate, a sulfide photocatalytic substrate, a carbon nitride-based photocatalytic substrate, a bismuth-based photocatalytic substrate, and a polymer-based photocatalytic substrate.

6. The process for preparing a photocatalyst-mediated metal-biomolecule self-polymerization coating according to claim 5, characterized in that: The metal oxide photocatalytic substrate includes one of titanium dioxide, zinc oxide, iron oxide, tin oxide, zirconium oxide, tungsten oxide, copper oxide, and cerium oxide; And / or, the sulfide-type photocatalytic substrate includes one of cadmium sulfide, zinc sulfide, and molybdenum sulfide; and / or, the carbon nitride-based photocatalytic substrate comprises graphite-phase carbon nitride; And / or, the bismuth-based photocatalytic substrate includes one of bismuth oxyhalide, bismuth vanadate, bismuth tungstate, and bismuth molybdate; And / or, the polymer photocatalytic substrate includes one of a metal organic framework material, a covalent organic framework material, and a two-dimensional material MXene.

7. The process for preparing a photocatalyst-mediated metal-biomolecule self-polymerization coating according to claim 1, characterized in that: In step (2), the reaction temperature is 5-60°C; And / or, the wavelength of the ultraviolet irradiation is 254-365 nm, and the time of ultraviolet irradiation is 0.1-10 h.

8. The process for preparing a photocatalyst-mediated metal-biomolecule self-polymerization coating according to claim 1, characterized in that: In step (2), the substrate having a photocatalytic effect is pre-treated by washing and drying in sequence before being immersed in the mixed solution; And / or, the substrate having photocatalytic activity is subjected to ultrasonic cleaning and drying treatment in sequence after ultraviolet irradiation.

9. The photocatalyst-mediated metal-biomolecule self-polymerization coating obtained by the preparation process according to any one of claims 1 to 8.

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