CN112724737A - Dopamine ink and method and application thereof for preparing micro-nano pattern - Google Patents
Dopamine ink and method and application thereof for preparing micro-nano pattern Download PDFInfo
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
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- C09D11/02—Printing inks
- C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
- C09D11/033—Printing inks characterised by features other than the chemical nature of the binder characterised by the solvent
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- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
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- C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
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Abstract
The invention belongs to the technical field of functional micro-nano patterning, and particularly relates to dopamine ink, and a method and application thereof for preparing micro-nano patterns. The components of the dopamine ink comprise dopamine hydrochloride, tween-20, ascorbic acid, a thickening agent, an organic solvent and water. A method for preparing micro-nano patterns by using dopamine ink comprises the following steps: 1) carrying out surface modification on the printing substrate; 2) uniformly coating dopamine ink on the surface of the soft seal in a spinning mode; 3) and (3) contacting and slightly pressing the printing substrate with the soft seal to form a liquid drop array on the surface of the printing substrate, and placing the printing substrate in an ammonia atmosphere or under ultraviolet illumination to react to obtain the polydopamine micro-nano pattern. The dopamine ink has stronger air stability, utilizes ammonia gas or ultraviolet illumination to regulate and control the polymerization reaction of dopamine, and adopts an in-situ polymerization mode in micro-droplets to generate a polydopamine micro-nano patterned structure, so that the micro-droplets can be reliably and uniformly printed on a high-hydrophobicity anti-adhesion surface.
Description
Technical Field
The invention belongs to the technical field of functional micro-nano patterning, and particularly relates to dopamine ink, and a method and application thereof for preparing micro-nano patterns.
Background
The multifunctional Polydopamine (PDA) material developed by the inspiration of mussel adhesive protein is widely applied in recent ten years, PDA can be formed by self-polymerization of dopamine monomers, the reaction principle comprises oxidative polymerization, free radical polymerization, photochemical polymerization and the like, the formed PDA film can be adhered to the surfaces of various substrate materials without additional modification, and the PDA film contains various functional groups such as catechol, amine, imine and the like, so that the surface hydrophilicity of the material can be improved, the material has good biocompatibility, and other functional materials can be further prepared by adsorption fixation and secondary modification.
At present, there are various technical means for preparing the micro-nano patterned surface by the PDA, including a photoetching template method, ink-jet printing, micro-channel limited domain growth, micro-contact printing and the like. The selective growth of PDA can be controlled by preparing the micro-nano template by imprinting or self-assembly of microspheres, but the preparation and removal of the nano template need high cost and complex processes. The remaining methods are typically only capable of producing patterns >10 microns in size, and also pre-order pattern-retaining microchannels, microstamps, or photomasks, etc. The dopamine monomer solution can be directly written by using the nanoprobe and is polymerized into the PDA nano pattern in the air, but the preparation range is less than 100 microns, and the efficiency is low. Therefore, the development of a method for flexibly preparing PDA micro-nano patterns on different surfaces in large area has important application value.
Disclosure of Invention
Aiming at the problems, the invention aims to provide dopamine ink, a method for preparing a micro-nano pattern by using the dopamine ink and application of the dopamine ink, and the dopamine ink can form micro-nano droplet arrays on different surfaces by regulating and controlling dopamine ink components.
The method is simple and low in cost, and can be used for preparing large-area high-precision polydopamine random micro-nano patterns. The proportion of the dopamine ink is designed and optimized aiming at a high-hydrophobicity surface (the water contact angle is larger than 100 degrees), so that a uniform hydrophilic PDA micro-nano pattern array can be obtained with high yield.
The technical content of the invention is as follows:
the invention provides dopamine ink, which comprises components of dopamine hydrochloride, tween-20, ascorbic acid, a thickening agent, an organic solvent and water;
the thickening agent comprises high-viscosity polyol or polymer, and specifically comprises one of glycerol, ethylene glycol and polyethylene glycol;
the organic solvent comprises one of ethanol, isopropanol, n-butanol or other solvent capable of dissolving dopamine.
The organic solvent and the surfactant Tween-20 are adopted, so that the ink is more easily spread on the surface of the substrate and transferred from the surface of the micro-pattern stamp, and reliable generation of micro-droplets is realized.
According to the mass fraction, the dopamine hydrochloride accounts for 1-20 mg/mL, the tween-20 accounts for 0-6 mg/mL, the ascorbic acid accounts for 0-10 mg/mL, the thickening agent accounts for 10-200 mg/mL, the organic solvent accounts for 0-100% V/V, and the water accounts for 0-100% V/V.
The dopamine hydrochloride is a monomer for synthesizing polydopamine, and can be polymerized under oxygen, alkaline environment or 254nm ultraviolet illumination; the glycerol is a thickening agent with high viscosity, is beneficial to the transfer of ink, and the property of difficult volatilization is beneficial to the long-term stability of micro-droplets;
the thickening agent increases the content of the ink on the surface of the stamp on one hand, and on the other hand, when the stamp is in contact with the surface of the substrate, the thickening agent is favorable for transferring the ink to the surface of the substrate to form micro-droplets due to high viscosity of the thickening agent. The high boiling point and the hygroscopicity of the glycerol can ensure that the micro-droplets can keep moist for a long time in the air environment, and are beneficial to the polymerization reaction of dopamine;
the Tween-20 is a nonionic surfactant, reduces the surface tension, is beneficial to printing ink on a hydrophobic surface, and the ionic surfactant can prevent a polydopamine film from being generated and cannot be used;
the ascorbic acid is an antioxidant, can prevent dopamine from being oxidized in the air, so that the dopamine can be retained on the surface of the seal for more than 6 hours without self-polymerization reaction, and is convenient for repeated printing;
by improving the air stability of the dopamine ink, the ink does not generate self-polymerization when being coated on the surface of the seal, the printing can be repeatedly carried out for hundreds of times, the service time of the seal is prolonged, and the productivity is improved. Meanwhile, polymerization can be initiated and regulated by an external means, polymerization reaction can be selectively carried out in different areas, the polymerization time can be regulated, and the complexity of patterns can be improved.
Microarrays are difficult to print on hydrophobic surfaces due to the repellency of hydrophobic surfaces to aqueous solutions. According to the invention, through regulating and controlling the components of the dopamine ink solution, the submicron-scale micro-droplet array is successfully printed on the high-hydrophobicity surface, and the universality of the technology on different printing substrates is further improved.
The organic solvent adopts a low-volatility low-surface tension solvent, and is beneficial to coating of ink and printing on a hydrophobic surface.
The ink formula of the dopamine ink is suitable for realizing the rapid contact printing of the dopamine hydrochloride monomer on different surface energy surfaces through a silicon rubber soft seal, and also can be suitable for an atomic force microscope probe to carry out a scanning probe dip pen nanometer etching technology.
The invention also provides a method for preparing the micro-nano pattern by using the dopamine ink, which comprises the following steps:
1) cleaning and surface finishing the printing substrate;
2) uniformly spin-coating dopamine ink on the surface of the soft seal with the micro-pattern structure;
3) and (3) contacting and slightly pressing the printing substrate with the soft seal to form a liquid drop array on the surface of the printing substrate, and placing the printing substrate in an ammonia atmosphere or under ultraviolet illumination to react to obtain the polydopamine micro-nano pattern.
The printing substrate in the step 1) comprises a hydrophilic substrate, specifically a cleaned silicon wafer or glass sheet;
the surface modification comprises the modification by adopting linear PDMS or silane, and specifically comprises the following two operations:
A. surface modification with linear PDMS: carrying out plasma treatment on the silicon chip or the glass sheet, then soaking the silicon chip or the glass sheet in linear PDMS for high-temperature reaction, taking out the silicon chip or the glass sheet, washing the silicon chip or the glass sheet by using an organic solvent, and drying the silicon chip or the glass sheet by using nitrogen.
B. Surface modification with silane: carrying out plasma treatment on a silicon wafer or a glass sheet, placing the silicon wafer or the glass sheet in a dryer, adding 1H,1H,2H, 2H-perfluoro octyl trichlorosilane, vacuumizing to volatilize the trichlorosilane, taking out the trichlorosilane, baking, washing by using an organic solvent, and drying by using nitrogen.
Step 2) the soft seal comprises a silicon rubber soft seal, and the preparation of the silicon rubber soft seal comprises the following steps:
2a) preparing an inverted pyramid well micro-pattern array on the surface of a silicon wafer by utilizing photoetching and KOH wet etching, and using the array as a template for preparing a soft seal;
2b) mixing the polydimethylsiloxane prepolymer and the cross-linking agent according to the mass ratio of 10: 1-5: 1, fully mixing and stirring, then carrying out air extraction treatment until the obtained mixed viscous liquid completely does not contain bubbles, slowly pouring the viscous liquid on the surface of a silicon template, and standing and curing at a high temperature;
2c) and separating the cured PDMS from the silicon template to obtain the silicon rubber soft stamp with the micro-pattern structure.
The step 3) further initiates dopamine polymerization reaction in the micro-droplets generated by printing in alkaline atmosphere or ultraviolet irradiation to obtain a large range (> 1 cm)2) And high-flux and high-precision (the size of less than 1 mu m) polydopamine micro-nano pattern.
The method adopts an in-situ polymerization mode to enable the polydopamine film to be better adhered to different substrate surfaces, particularly to a high-hydrophobic surface with anti-adhesion performance. In addition, the size of the micro-droplets can be conveniently controlled by printing conditions, including contact time, contact pressure, ink viscosity, interface surface tension and the like, and the preparation of patterns with different sizes and gradient patterns on the same substrate can be realized. In addition, the components of the micro-droplets can be adjusted by combining the means of spraying and the like to adjust the ink composition of different areas on the surface of the stamp.
Meanwhile, the shape of the polydopamine film can be effectively regulated and controlled by regulating the size and the composition of the micro-droplets; different patterns including planes, micro-nano structure surfaces, curved surfaces, flexible substrates and the like can be printed on the surfaces of various substrates according to requirements, and the printing machine is compatible with mechanical operation of a high-precision positioning platform and has universality and practical application basis.
The invention also provides application of the polydopamine micro-nano pattern prepared by the method in preparation of polymer gel and inorganic crystal microarray
The invention also provides application of the polydopamine micro-nano pattern prepared by the method in selective adsorption and immunodetection of biomolecules.
The invention has the following beneficial effects:
according to the dopamine ink, the neutral organic solvent and the antioxidant are used as polymerization reaction solvents, so that the air stability of the dopamine ink is improved, ammonia gas or ultraviolet illumination is utilized to regulate and control the polymerization reaction of dopamine, the ink solvent is regulated, and the nonionic surfactant is added, so that micro-droplets can be reliably and uniformly printed on the high-hydrophobic anti-adhesion surface, and the universality of the technology on different printing substrates is further improved;
according to the method for preparing the micro-nano pattern by using the dopamine ink, a polydopamine micro-nano patterning structure is generated in a micro-droplet in-situ polymerization mode, a micro-droplet array is controllably generated in batches by a polymer soft stamp, high-flux preparation of high-resolution micro-nano patterns of polydopamine from submicron to tens of microns on the surfaces of various substrates is realized, the cost is low, the method is simple, good repeatability is realized, the preparation of the high-flux high-precision micro-nano array is more facilitated, and different patterns can be printed on the surfaces of various substrates according to needs;
in addition, the surface appearance (height, roughness and the like) of the polydopamine has different functions in different application aspects, and the polydopamine pattern appearance can be adjusted by changing the micro-droplet composition, so that reference is provided for regulating and controlling the polydopamine function.
Drawings
FIG. 1 is a flow chart of a process for preparing micro-nano patterns by using dopamine ink;
FIG. 2 is a schematic view of the contact angle of a surface-modified silicon wafer;
FIG. 3 is a schematic view of different inks printing micro-droplet arrays on different surfaces;
FIG. 4 is a schematic diagram of a dopamine ink and a polydopamine micro-nano pattern generated by the dopamine ink;
FIG. 5 is an analysis graph of the change of the formed polydopamine micro-nano pattern along with the height of the liquid drop;
FIG. 6 is an analysis chart of the change of the formed polydopamine micro-nano pattern along with the surface active agent;
FIG. 7 is an optical microscope photograph of a gelatin hydrogel microarray;
FIG. 8 is an optical and fluorescence microscope image of a perovskite microarray;
FIG. 9 is a fluorescence microscope photograph of an Anti-IgG fluorescently labeled protein array.
Detailed Description
The present invention is described in further detail in the following description of specific embodiments and the accompanying drawings, it is to be understood that these embodiments are merely illustrative of the present invention and are not intended to limit the scope of the invention, which is defined by the appended claims, and modifications thereof by those skilled in the art after reading this disclosure that are equivalent to the above described embodiments.
All the raw materials and reagents of the invention are conventional market raw materials and reagents unless otherwise specified.
Example 1
A dopamine ink:
5mg/mL of dopamine hydrochloride, 200.1 mg/mL of tween-L, 3mg/mL of ascorbic acid, 200mg/mL of glycerol, 90% v/v of ethanol and 10% v/v of water.
Example 2
A dopamine ink:
dopamine hydrochloride 10mg/mL, tween-200.6 mg/mL, ascorbic acid 5mg/mL, polyethylene glycol 200mg/mL, ethanol 80% v/v and water 20% v/v.
Example 3
A dopamine ink:
dopamine hydrochloride 20mg/mL, tween-205 mg/mL, ascorbic acid 10mg/mL, ethylene glycol 10mg/mL, ethanol 80% v/v and water 20% v/v.
Example 4
A dopamine ink:
15mg/mL of dopamine hydrochloride, 203 mg/mL of tween-203, 7mg/mL of ascorbic acid, 100mg/mL of glycerol, 50% v/v of isopropanol and 50% v/v of water.
Example 5
A dopamine ink:
dopamine hydrochloride 2mg/mL, glycerol 50mg/mL and water 100% v/v.
Example 6
A dopamine ink:
15mg/mL of dopamine hydrochloride, 3mg/mL of ascorbic acid, 100mg/mL of glycerol, 50% v/v of n-butanol and 50% v/v of water.
Example 7
A dopamine ink:
15mg/mL of dopamine hydrochloride, 203 mg/mL of tween-203, 7mg/mL of ascorbic acid, 100mg/mL of polyethylene glycol, 50% v/v of ethanol and 50% v/v of water.
Example 8
A method for preparing micro-nano patterns by using dopamine ink comprises the following steps:
FIG. 1 shows a flow chart of the preparation process:
1) cleaning a printing substrate silicon wafer and performing surface modification by adopting linear PDMS: carrying out surface modification: carrying out plasma treatment on a cleaned silicon wafer for 10 minutes, then soaking the silicon wafer in linear PDMS (molecular weight of 6000) to react for 24 hours at a high temperature of 100 ℃, taking out the silicon wafer and soaking the silicon wafer in toluene for 1 hour, washing the toluene with isopropanol, and drying the toluene with nitrogen;
2) uniformly spin-coating dopamine ink on the surface of the soft seal with the micro-pattern structure;
the soft stamp comprises a silicon rubber soft stamp, and the preparation method comprises the following steps:
2a) preparing an inverted pyramid well micro-pattern array on the surface of a silicon wafer by utilizing photoetching and KOH wet etching, and using the array as a template for preparing a soft seal;
2b) mixing a polydimethylsiloxane prepolymer and a cross-linking agent (a commercially available product is Dow Corning Sylgard 184) in a mass ratio of 10: 1-5: 1, fully mixing and stirring for 10min, then performing air extraction treatment, slowly pouring the mixed viscous liquid on the surface of a silicon template after the mixed viscous liquid completely does not contain bubbles, and then placing the silicon template in an oven at 70 ℃ for 2 hours to cure PDMS;
2c) and (4) separating the cured PDMS from the silicon template to obtain the silicon rubber soft seal.
3) And (3) contacting and slightly pressing the printing substrate with the soft seal to form a liquid drop array on the surface of the printing substrate, and placing the printing substrate in an ammonia atmosphere or under ultraviolet illumination to react to obtain the polydopamine micro-nano pattern.
Example 9
A method for preparing micro-nano patterns by using dopamine ink comprises the following steps:
1) cleaning a printing substrate and performing surface modification by adopting fluorine-containing silane: carrying out plasma treatment on the cleaned glass sheet for 10 minutes, placing the glass sheet in a dryer, adding 1H,1H,2H, 2H-perfluoro octyl trichlorosilane, vacuumizing to volatilize the trichlorosilane, maintaining for 3 hours, taking out the glass sheet, baking the glass sheet for 30 minutes at 1000 ℃, flushing the glass sheet with toluene, flushing the glass sheet with isopropanol, and drying the glass sheet with nitrogen;
2) uniformly spin-coating dopamine ink on the surface of the soft seal with the micro-pattern structure;
the soft stamp comprises a silicon rubber soft stamp, and the preparation method comprises the following steps:
2a) preparing an inverted pyramid well micro-pattern array on the surface of a silicon wafer by utilizing photoetching and KOH wet etching, and using the array as a template for preparing a soft seal;
2b) mixing a polydimethylsiloxane prepolymer and a cross-linking agent (a commercially available product is Dow Corning Sylgard 184) in a mass ratio of 10: 1-5: 1, fully mixing and stirring for 10min, then performing air extraction treatment, slowly pouring the mixed viscous liquid on the surface of a silicon template after the mixed viscous liquid completely does not contain bubbles, and then placing the silicon template in an oven at 70 ℃ for 2 hours to cure PDMS;
2c) and (4) separating the cured PDMS from the silicon template to obtain the silicon rubber soft seal.
3) And (3) contacting and slightly pressing the printing substrate with the soft seal to form a liquid drop array on the surface of the printing substrate, and placing the printing substrate in an ammonia atmosphere or under ultraviolet illumination to react to obtain the polydopamine micro-nano pattern.
The dopamine inks formed in the examples of the invention were tested and applied as follows:
1. printing ink on non-surface-modified surface
The ink of the embodiment 5 is adopted to spin the silicon rubber soft seal on the surface of an unmodified silicon wafer or glass sheet, and a micro-droplet array with the size of about 10-50 microns can be printed through one-time contact;
2. printing ink on surface modified surface
As can be seen from fig. 2, the surface of the silicone rubber soft stamp is relatively hydrophilic before being modified, and after the surface of the silicone rubber soft stamp is modified with linear PDMS and fluorosilane, the contact angles are respectively increased to 108.3 ° and 116.7 °, so as to form a highly hydrophobic surface;
on a highly hydrophobic surface with a contact angle of more than 100 degrees, the success rate of printing with the ink of example 5 is low;
as shown in fig. 3, fig. 3A is a microdroplet array formed by printing the dopamine ink of example 5 on a hydrophilic silicon wafer;
FIG. 3B is a graph showing the effect of dopamine ink of example 5 on the surface of a highly hydrophobic silicon wafer (linear PDMS-modified silicon wafer);
FIG. 3C is a graph of the effect of dopamine ink of example 6 on the surface of a highly hydrophobic silicon wafer (linear PDMS-modified silicon wafer);
FIG. 3D is a graph of the effect of the dopamine ink of example 1 on the surface of a highly hydrophobic silicon wafer (linear PDMS-modified silicon wafer);
as can be seen from fig. 3, the use of ethanol solvent can reduce the residue of ink around the printed dots, and the addition of surfactant can further enhance the ink transport, resulting in larger size of the printed microdroplets and more uniform array.
Fig. 4 shows a uniform microdroplet array (fig. 4A) printed on the surface of a linear PDMS-modified silicon wafer and a polydopamine micro-nano pattern (fig. 4B) obtained after the reaction, wherein the prepared microdroplets are washed to obtain a polydopamine micro-dot array with light brown to dark brown after reacting for 12 hours in an ammonia atmosphere;
the preparation of polydopamine micro-nano patterns with different micro-nano patterns can also be realized by using silicon rubber soft stamps with different micro-nano structures, as shown in fig. 4C, micro-droplet printing is carried out on the hydrophobic surface by adopting silicon rubber soft stamps with 5-micron linear patterns (with the distance of 10 microns), and a polydopamine particle array with submicron size can be obtained due to the dewetting effect of droplets.
3. Polydopamine micro-nano pattern array with various shapes can be obtained by adjusting micro-droplet reaction conditions
As shown in fig. 5, as the reaction time increases, the height and the morphology of the obtained polydopamine film change, and after the reaction is performed for 3-36 hours after the 10mM dopamine ink of example 1 is printed, a smoother film with a thickness of about 5nm can be grown into a film with a thickness of about 25nm, which is rougher, and the morphology of the polydopamine film can be adjusted by adjusting the concentration of the dopamine ink.
Printing dots with the diameter of 15 micrometers by using dopamine inks with different concentrations, and reacting in an ammonia atmosphere for 36 hours to obtain a film with the thickness of 20-30 nm and the roughness of 16.7nm by using 25mM of the dopamine ink in the embodiment 1; and the 100nM dopamine ink of example 7 forms a dense film with a thickness of 30-40 nM, and has a surface with a large number of particles with a height of 100-150 nM, and the overall roughness reaches 56.2 nM.
4. Influence of surfactants with different concentrations on polydopamine micro-nano pattern
The increase of the concentration of the surfactant can enable liquid drops to be easily diffused on the surface of the substrate, and the size of the micro-nano pattern is increased.
As shown in fig. 6, panels a-C show the change of the size and morphology of the microdots of polydopamine with the concentration of the surfactant, and increasing the concentration of the surfactant can make the droplets spread on the surface of the substrate more easily, so that the size of the pattern becomes larger. However, at the same size pattern (10 micron circle), polydopamine height decreased with increasing surfactant concentration, with the most significant change in the range around the critical micelle concentration for surfactant concentration (0.1mM to 0.5 mM).
As shown in fig. 6, panels D-E, which are plots of polydopamine microdot height versus size, all scales are 2 μm, and when the resulting microdroplet diameter is <5 μm, the polydopamine produced can reach a height of 150 nm. And when the diameter of the micro-droplet is within the range of 6-20 mu m, the height of the generated polydopamine is obviously reduced to about 100nm, which proves that the size effect has certain influence on the growth of the polydopamine.
5. Application of polydopamine micro-nano pattern
5.1 preparation of Polymer gels and perovskite arrays
As shown in example 8, a dopamine micro-droplet array is prepared on the surface of the silicon wafer modified by the linear PDMS surface by using the dopamine ink of example 2, and a polydopamine micro-array grows overnight in an ammonia atmosphere;
preparation of polymer hydrogel array: preparing gelatin water solution with mass fraction of 5%, heating to 70 deg.C to dissolve completely, collecting liquid drop, slowly rolling over polydopamine microarray and selectively adsorbing on surface, and placing at 4 deg.C to form hydrogel microarray, as shown in FIG. 7.
Preparation of perovskite array: mixing 0.1M methyl ammonium bromide (MABr) with 0.1M lead bromide (PbBr)2) Preparing a micro-droplet array according to the method, standing in a glove box for 24 hours until the solvent is volatilized and crystallized to form perovskite MAPbBr3Microarray, as in FIG. 8.
5.2 preparation of immunofluorescence detection biological Microchip
As shown in example 8, a dopamine micro-droplet array is prepared on the surface of the silicon wafer modified by the linear PDMS surface by using the dopamine ink of example 2, and a polydopamine micro-array grows overnight in an ammonia atmosphere;
preparation of IgG protein arrays: dropping the IgG protein solution on the surface of the polydopamine microarray, standing and reacting for 6 hours, and washing the surface of the silicon wafer by using a 1 XPBS solution, a Tween-20 surfactant solution and deionized water respectively.
Detection of Anti-IgG fluorescent protein array: dripping Anti-IgG fluorescent protein solution on the surface of the polydopamine microarray, shading, standing and reacting for 2 hours, and washing the surface of the silicon wafer with 1 XPBS solution, Tween-20 surfactant solution and deionized water respectively. Characterization of the resulting image using fluorescence microscopy as shown in fig. 8, it is evident that the protein selectively adsorbs to the printed poly dopamine lattice surface and that after antibody-antigen recognition a fluorescent micropattern array is produced (fig. 9).
The dopamine ink and the method for preparing the polydopamine micro-nano pattern by using the same can obtain a uniform and stable micro-nano pattern array with high yield, and the prepared surface hydrophilic and hydrophobic micro-nano pattern can be applied to preparation of polymer gel and inorganic crystal micro-arrays and selective adsorption and immunodetection of biomolecules.
Claims (9)
1. The dopamine ink is characterized by comprising dopamine hydrochloride, tween-20, ascorbic acid, a thickening agent, an organic solvent and water.
2. The dopamine ink of claim 1, wherein the thickener comprises a high viscosity polyol or polymer.
3. The dopamine ink according to claim 1, wherein the dopamine ink comprises, by mass, 1 to 20mg/mL of dopamine hydrochloride, 0 to 6mg/mL of tween-20, 0 to 10mg/mL of ascorbic acid, 10 to 200mg/mL of thickener, 0 to 100% V/V of organic solvent, and 0 to 100% V/V of water.
4. A method for preparing a micro-nano pattern by using the dopamine ink prepared according to any one of claims 1-3 is characterized by comprising the following steps:
1) carrying out surface modification on the printing substrate;
2) uniformly spin-coating dopamine ink on the surface of the soft seal with the micro-pattern structure;
3) and (3) contacting and slightly pressing the printing substrate with the soft seal to form a micro-droplet array on the surface of the printing substrate, and placing the printing substrate in an ammonia atmosphere or under ultraviolet illumination to react to obtain the polydopamine micro-nano pattern.
5. The method for preparing micro-nano patterns by using the dopamine ink as claimed in claim 4, wherein the printing substrate in the step 1) comprises a hydrophilic substrate comprising a silicon wafer or a glass sheet.
6. The method for preparing micro-nano patterns by using the dopamine ink of claim 4, wherein the surface modification in the step 1) comprises modification by using linear Polydimethylsiloxane (PDMS) or silane, and specifically comprises the following two operations:
A. surface modification with linear PDMS: carrying out plasma treatment on a silicon chip or a glass sheet, then soaking the silicon chip or the glass sheet in linear PDMS for high-temperature reaction, taking out the silicon chip or the glass sheet, washing and drying;
B. surface modification with silane: carrying out plasma treatment on a silicon wafer or a glass sheet, placing the silicon wafer or the glass sheet in a dryer, adding 1H,1H,2H, 2H-perfluoro octyl trichlorosilane, vacuumizing to volatilize the trichlorosilane, taking out, baking, washing and drying.
7. The method for preparing micro-nano patterns by using the dopamine ink according to claim 4, wherein the soft stamp in the step 2) comprises a silicon rubber soft stamp, and the preparation of the silicon rubber soft stamp comprises the following steps:
2a) preparing a micro-pattern array on the surface of a silicon wafer by utilizing photoetching and wet etching, and using the micro-pattern array as a template for preparing a soft seal;
2b) mixing and reacting the silicon rubber prepolymer with a cross-linking agent, fully mixing and stirring, then carrying out air extraction treatment until the obtained mixed viscous liquid completely does not contain bubbles, slowly pouring the viscous liquid on the surface of a silicon template, and standing and curing at a high temperature;
2c) and separating the cured PDMS from the silicon template to obtain the silicon rubber soft stamp with the micro-pattern structure.
8. The polydopamine micro-nano pattern prepared by the method according to any one of claims 4 to 7 is applied to preparation of polymer gel and inorganic crystal micro-arrays.
9. The polydopamine micro-nano pattern prepared by the method according to any one of claims 4-7 is applied to selective adsorption and immunodetection of biomolecules.
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| CN115219575B (en) * | 2022-06-28 | 2024-06-04 | 中山大学 | Stretchable electrochemical three-dimensional microelectrode and application thereof in biomolecule detection |
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| CN112724737B (en) | 2022-02-22 |
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