WO2018213997A1 - 一种可变形的刺激响应材料及其制备方法和刺激响应柔性微电极阵列 - Google Patents

一种可变形的刺激响应材料及其制备方法和刺激响应柔性微电极阵列 Download PDF

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WO2018213997A1
WO2018213997A1 PCT/CN2017/085377 CN2017085377W WO2018213997A1 WO 2018213997 A1 WO2018213997 A1 WO 2018213997A1 CN 2017085377 W CN2017085377 W CN 2017085377W WO 2018213997 A1 WO2018213997 A1 WO 2018213997A1
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responsive material
stimuli
deformable
responsive
substrate
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French (fr)
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杜学敏
崔欢庆
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Shenzhen Institute of Advanced Technology of CAS
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Shenzhen Institute of Advanced Technology of CAS
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
    • C08F220/285—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing a polyether chain in the alcohol moiety
    • C08F220/286—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing a polyether chain in the alcohol moiety and containing polyethylene oxide in the alcohol moiety, e.g. methoxy polyethylene glycol (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
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    • C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
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    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/52—Amides or imides
    • C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/36—Amides or imides
    • C08F222/38—Amides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/22—Expanded, porous or hollow particles
    • C08K7/24—Expanded, porous or hollow particles inorganic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/10—Homopolymers or copolymers of methacrylic acid esters
    • C08L33/12—Homopolymers or copolymers of methyl methacrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/24—Homopolymers or copolymers of amides or imides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L5/00—Compositions of polysaccharides or of their derivatives not provided for in groups C08L1/00 or C08L3/00
    • C08L5/12—Agar or agar-agar, i.e. mixture of agarose and agaropectin; Derivatives thereof

Definitions

  • the invention relates to the field of biomedical engineering technology, in particular to a deformable stimuli responsive material, a preparation method thereof and a stimuli-responsive flexible microelectrode array.
  • Flexible microelectrode arrays help patients with functional reconstruction by applying pulsed current stimulation to specific nerve tissue, and are now widely used in medical devices such as cochlear implants and artificial retinas.
  • the flexible microelectrode array acts as a direct contact point between the prosthesis and the nerve, and plays a key role in the function of the nerve electrical stimulation of the prosthesis.
  • the degree of fit of the microelectrode array to the nerve tissue or organ determines the effectiveness of the electrical stimulation.
  • the nerve tissue or organ is often an irregular curved surface, and the conventional planar electrode is not in good contact with it, resulting in low stimulation efficiency and decreased stability. Therefore, the development of a shape-controllable flexible microelectrode array is of great significance for the long-term stability of the implant and for improving the stimulation efficiency.
  • the conventional electrode processing method is to impart a certain curvature to the electrode by means of hot pressing, but the method is prone to breakage and causes a certain degree of damage to the electrode. How to give a certain curvature to the flexible electrode array without using the electrode in a simple manner has become an urgent problem to be solved.
  • the shape memory polymer shape memory function to shape flexible electrodes by temperature triggering.
  • the trigger temperature of the shape memory polymer is close to 100 ° C, the trigger temperature is too high, and no chemical modification is applied between the response layer and the flexible microelectrode array substrate, and the stratification of the response layer and the flexible substrate is apt to occur. Defects limit their practical application.
  • the present invention provides a deformable stimuli-responsive material that can be transformed from a planar two-dimensional structure into a three-dimensional structure under external stimuli, and modified to the back of the planar flexible microelectrode array.
  • the three-dimensional deformation of the flexible microelectrode array can be realized by external stimulation, and the controllable shaping and curvature of the conventional planar flexible microelectrode array can be precisely controlled by adjusting the thickness or cross-linking degree of the deformable stimuli-responsive material. .
  • the present invention provides a deformable stimuli responsive material having a local Young's modulus difference, the deformable stimuli responsive material being a thermally responsive material, light At least one of a thermally responsive material, a magnetocaloric responsive material, an electrothermally responsive material, a moisture responsive material, and a pH responsive material is constructed, the deformable responsive material being at temperature, light, magnetism, electricity, humidity, pH Under one or more external stimulus conditions, the planar two-dimensional structure can be transformed into a three-dimensional structure.
  • the deformable stimuli-responsive material provided by the invention has a local Young's modulus difference, and after a certain external stimulus, different Young's modulus regions will swell or shrink to different degrees, thereby realizing the material from the planar two-dimensional structure. It transforms into a three-dimensional structure such as a spiral shape, a hollow tubular shape, or a cylindrical shape.
  • the degree of difference in the local Young's modulus difference is in the range of 0.0001 Pa to 2000 GPa. Further, the degree of difference is in the range of 10 Pa to 100 KPa.
  • the deformable stimuli-responsive material has the same composition as a whole, and the sub-region There are different degrees of crosslinking, which are formed by differences in the degree of crosslinking of different regions. Specifically, it can be obtained by irradiating a pre-polymerized liquid sub-region of a deformable stimuli-responsive material having the same composition to different degrees.
  • the different degrees of irradiation can be achieved by adjusting the irradiation dose (including the irradiation power and the irradiation time), or selecting partial area irradiation, and partial areas are not irradiated.
  • the same component composition may include only one type of stimuli-responsive material, or may include two or more types of stimuli-responsive materials.
  • the type of the stimuli-responsive material may also be A variety of, such as can contain both thermally responsive materials and humidity responsive materials. Among them, the shape of the region in which the degree of crosslinking is different is not limited.
  • the deformable stimuli-responsive material sub-regions have different compositional compositions, the local Young's modulus differences being formed by differences in mechanical properties of the different components.
  • the different component compositions include multiple groups, ie two or more groups. Specifically, it can be obtained by sub-regional polymerization molding of a plurality of sets of deformable responsive material pre-polymerized liquids having different compositions.
  • the plurality of groups may be two or more groups, and the two groups may be included as an example, and may include a group A prepolymerization liquid and a group B prepolymerization liquid, wherein the group A prepolymerization liquid and the group B prepolymerization liquid may each include only
  • a stimuli-responsive material may also be composed of two or more types of stimuli-responsive materials.
  • the types of stimuli-responsive materials may also be various, such as a thermally responsive material and a moisture-responsive material. Among them, the shape in which the components constitute different regions is not limited.
  • the deformable stimuli-responsive material has the same composition as a whole, and the deformable stimuli-responsive material is provided with an oriented microstructure, the local Young's modulus difference Formed by the aligned arrangement of the microstructures, the microstructures comprising pits, protrusions or micro-nano materials comprising at least one of graphene, carbon nanotubes, glass fibers, nanoparticles.
  • the deformable stimuli-responsive material sub-region has a different composition
  • the deformable stimuli-responsive material is provided with an oriented micro-structure, the local Young's modulus The difference is formed by the alignment of the microstructures and the differences in mechanical properties of the different components, the microstructures comprising pits, bumps or micro-nano materials, including graphene, carbon nano At least one of a tube, a glass fiber, and a nanoparticle.
  • the pit has a depth of 10 nm to 5 cm, and the height of the protrusion is 10 nm to 5 cm; further, the pit has a depth of 1 ⁇ m to 5 mm, and the height of the protrusion is 1 ⁇ m to 5 mm.
  • the pits or protrusions may be formed by photolithography.
  • the micro-nano material may be oriented by external force induction, and the nanoparticles may be inorganic nanoparticles or organic nanoparticles, such as may be ferroferric oxide nanoparticles.
  • the three-dimensional structure comprises a cylinder, a spiral shape, and a hollow tubular structure.
  • the thermally responsive material is a temperature sensitive polymer, which may be selected from at least one of poly(N-isopropylacrylamide), poly(N-n-propylacrylamide), poly (N-cyclopropyl acrylamide), poly(N-isopropyl methacrylamide), poly(N-ethyl acrylamide), poly(N-acryloyloxy-N-propylpiperazine), Poly(N-(L)-(1-hydroxymethyl)propylmethacrylamide), poly[N-(2-methacryloyloxyethyl)pyrrolidone], poly[N-(3-acryloyl) Oxypropyl propyl pyrrolidone], poly[N-(3-methacryloxypropyl)pyrrolidone], poly[N-(2-acryloxypropyl)pyrrolidone], poly[N-(1-methyl) -2-acryloyloxyethyl)pyrrolidone], poly(2-alkyl-2-
  • the photothermally responsive material is a nanoparticle having a photothermal effect added to the thermally responsive material, that is, a nanoparticle having a photothermal effect and a thermally responsive material
  • the photothermal effect nanoparticle is selected from the following materials: At least one of: gold nanorods, gold nanoshells, gold nanocage, hollow gold nanospheres, palladium nanosheets, palladium@silver, palladium@silica, carbon nanotubes, graphene, reduced graphene oxide, Carbon black, black phosphorus, copper sulfide, phthalocyanine green, polyaniline, And the products of the above substances after various chemical modifications.
  • the magnetocaloric responsive material is a nanoparticle having a magnetocaloric effect added to the thermally responsive material, that is, a nanoparticle having a magnetocaloric effect and a thermally responsive material, and the nanoparticle having the magnetocaloric effect is selected from the following materials: At least one of: Fe 3 O 4 , LaFeCoSi, GdSiGe, LaFe 11.6 Si 1.4 C 0.2 H 0.7 , La(Fe, Si) 13 , NiMnGa, MnCoGe 0.99 In 0.01 , MnCo 0.98 Cr 0.02 Ge and the like.
  • the electrothermally responsive material is a material having an electrocaloric effect added to the thermally responsive material, that is, a nanoparticle having a electrocaloric effect and a thermally responsive material, wherein the electrothermal effect is selected from at least one of the following substances: One type: graphite, carbon black, carbon nanotubes, carbon fiber, aluminum-doped zinc oxide, calcium-doped strontium chromate, antimony-doped tin dioxide, conductive metal materials (eg, gold, silver, platinum, copper, rhodium, palladium, chromium Etc.), indium tin oxide, transparent conductive oxide, polyacetylene, polyaniline, polypyrrole, and the like.
  • One type graphite, carbon black, carbon nanotubes, carbon fiber, aluminum-doped zinc oxide, calcium-doped strontium chromate, antimony-doped tin dioxide, conductive metal materials (eg, gold, silver, platinum, copper, rhodium, pal
  • the humidity responsive material is a mixture of two types of materials, one of which is a polymer containing a large amount of hydrophilic groups, and the polymer is at least one selected from the group consisting of agarose and fiber. , polyvinyl alcohol, chitosan, starch, polyacrylamide, polyvinylpyrrolidone, hyaluronic acid, sodium hyaluronate, sodium polystyrene sulfonate, polyhydroxyethyl methacrylate, polyethylene glycol, poly Butylene glycol, polyethylene glycol methacrylate, polyethylene glycol acrylate, gelatin, alginic acid, collagen, poly-L-lysine, poly-L-glutamic acid, hydroxypropyl methylcellulose, hydroxyl Ethylcellulose, carboxymethylcellulose, carboxyvinyl polymers, and derivatives thereof.
  • the other type is a polyester containing a large amount of a carbonyl group
  • a polyester may be selected from at least one of polymethyl methacrylate, polyethyl methacrylate, poly-tert-butyl methacrylate, Polymethyl acrylate, polyethyl acrylate, polyvinyl pyridine, polycarbonate, polyimide, hydroxymethyl cellulose, cellulose acetate, nylon, poly(vinyl terephthalate), polyphosphate Nitrile, perfluorosulfonic acid, polyethylene, polystyrene, phenolic resin, and derivatives of the above.
  • the pH responsive material is at least one selected from the group consisting of a carboxyl group, a pyridine, a pyrrolidine, a piperazine, a sulfonic acid, a morpholine, a phosphate, a tertiary amine, and the like, and specifically may be the following At least one of: polyacrylic acid, poly-L-glutamic acid, polyhistidine, polyaspartic acid, poly[(2-dimethylamino)ethyl methacrylate], polymethacrylic acid, poly Ethyl acrylate, polyacrylic acid, polyethylene and benzoic acid, polyitaconic acid, polyethylene glycol acrylate phosphate, polyethylene glycol methacrylate phosphoric acid, polyethylene phosphate, poly(4-vinyl-phenyl Phosphoric acid), polyvinylsulfonic acid, poly(4-styrenesulfonic acid), polyvinylbenzeneboronic acid,
  • the present invention does not have strict requirements for the selection of specific stimuli-responsive materials, the choice of which depends on the desired effect of the end use and use.
  • the selection of photothermal nanoparticles in a photothermal response material often depends on the wavelength band of the light source used in the actual application process, such as gold nanorods or carbon nanotubes for near-infrared light, and redox for visible light.
  • Graphene the wavelength band of the light source used in the actual application process, such as gold nanorods or carbon nanotubes for near-infrared light, and redox for visible light.
  • Graphene Graphene.
  • the photothermal nanoparticles used in the photothermal response hydrogel layer usually have at least one excited absorption peak in the near-infrared light-visible spectrum of 400-1200 nm, and the photothermal nanoparticles can also assist some up-conversion nanoparticles. To effectively adjust the excitation wavelength.
  • the choice of the thermally responsive material often depends on the trigger temperature required in the actual application process.
  • the minimum critical solution temperature of the selected thermal response material should be lower than the actual trigger temperature.
  • the minimum critical solution temperature of each thermal response material can be changed by specific The substituents are either selected or copolymerized with other temperature sensitive or non-thermosensitive polymers for effective conditioning.
  • the deformable stimuli-responsive material provided by the first aspect of the present invention can be transformed into a three-dimensional structure from a planar two-dimensional structure under external stimuli of temperature, light, magnetism, electricity, humidity, and pH.
  • the present invention provides a method of preparing a deformable stimuli-responsive material comprising the steps of:
  • the pre-polymer comprising a pre-polymer of at least one of a thermally responsive material, a photothermal responsive material, a magnetocaloric responsive material, an electrothermal responsive material, and a pH responsive material;
  • the prepolymerized liquid is injected into the mold, and then a reticle having a specific structure is placed on the upper surface of the mold, and the prepolymerized portion of the exposed portion and the exposed portion are uniformly polymerized and formed by irradiation polymerization.
  • a deformed stimuli-responsive material having a local Young's modulus difference the deformable stimuli-responsive material having the same composition as a whole, and the sub-regions having different degrees of cross-linking
  • the degree of crosslinking of the exposed portion is greater than the degree of crosslinking of the occluded portion, the local Young's modulus difference being formed by the difference in the degree of crosslinking of the different regions.
  • the degree of cross-linking of the exposed portion is higher than that of the occluded portion, and the difference in Young's modulus of such a region causes a small-range stress accumulation of the obtained sample after external stimulation, driving the sample from a planar two-dimensional structure to a complex three-dimensional structure. Structural transformation.
  • the present invention provides a method of preparing a deformable stimuli-responsive material comprising the steps of:
  • the pre-polymerization liquid comprising at least at least one of a thermally responsive material, a photothermal responsive material, a magnetocaloric responsive material, an electrothermal responsive material, and a pH responsive material a prepolymer;
  • One part of the pre-polymerization liquid is injected into the mold, and then a reticle having a specific structure is placed on the upper surface of the mold, and the part to be exposed is formed by irradiation polymerization, and when the occlusion portion is not polymerized, Removing the occluded portion of the unpolymerized prepolymerized liquid with water, and then injecting another portion of the prepolymerized liquid into the mold, and after radiation polymerization, obtaining a deformable stimuli responsive material, the deformable stimuli responsive material There is a local Young's modulus difference, the deformable stimuli-responsive material sub-regions having different compositional compositions, the local Young's modulus differences being formed by differences in the different mechanical properties of the different components.
  • the mold is composed of two glass sheets and a polytetrafluoroethylene frame having a certain thickness sandwiched therebetween.
  • the specific structure of the reticle having a specific structure may be specifically set according to a shape of a region having a different degree of cross-linking or a shape of a region having a different composition.
  • the structure setting can be various, and the present invention is not particularly limited as long as it can constitute a local Young's modulus difference.
  • the present invention provides a method of preparing a deformable stimuli-responsive material comprising the steps of:
  • the pre-polymer comprising a pre-polymer of at least one of a thermally responsive material, a photothermal responsive material, a magnetocaloric responsive material, an electrothermal responsive material, and a pH responsive material;
  • the microstructure comprising pits, protrusions or micro-nano materials, and then placing a frame on the substrate to form a mold, the pre-polymerization
  • the liquid is injected into the mold, and after radiation polymerization, a deformable stimuli-responsive material is obtained, the deformable stimuli-responsive material having a local Young's modulus difference, and the deformable stimuli-responsive material as a whole has the same group Dividing the composition, and the deformable responsiveness material is provided with aligned microstructures, the local Young's modulus difference being formed by the orientation of the microstructures, the micro-nano materials including graphene, carbon nano At least one of a tube, a glass fiber, and a nanoparticle.
  • the present invention provides a method of preparing a deformable stimuli-responsive material comprising the steps of:
  • the pre-polymerization liquid comprising at least at least one of a thermally responsive material, a photothermal responsive material, a magnetocaloric responsive material, an electrothermal responsive material, and a pH responsive material a prepolymer;
  • the prepolymerization liquid is injected into the mold, and then a reticle having a specific structure is placed on the upper surface of the mold, and the portion to be exposed is formed by irradiation polymerization, and the occlusion portion is not polymerized, and the occlusion is removed by water.
  • the deformable stimuli-responsive material sub-region has different component composition, the bureau
  • the Young's modulus difference is formed by the orientation of the microstructure and the difference in mechanical properties of the different components, the micro-nano material comprising at least one of graphene, carbon nanotubes, glass fibers, and nanoparticles.
  • the pre-polymerization liquid containing the magnetic nanoparticles may be injected into the mold, and an external magnetic field is applied around the mold to adjust the direction of the magnetic field so that the magnetic nanoparticles are along a certain The orientation is oriented.
  • the frame for forming the mold may be a Teflon frame.
  • the prepolymerization liquid simultaneously contains a nanoparticle having a photothermal effect and a prepolymer of a thermally responsive material; when an electric heating is to be obtained In the responsive material, the prepolymer has both an electrothermal effect nanoparticle and a thermally responsive material prepolymer; when the magnetocaloric responsive material is to be obtained, the prepolymer has both a magnetocaloric effect and a nanoparticle and Thermally responsive material prepolymer.
  • the invention also provides a method for preparing a deformable stimuli-responsive material, comprising the steps of:
  • a polymer containing a large amount of hydrophilic groups and a polyester polymer containing a large amount of a carbonyl group are separately dissolved in a solvent, and then uniformly mixed in a certain mass ratio to obtain a humidity-responsive material solution;
  • the solvent may be dimethyl
  • An organic solvent such as formamide
  • the micro/nano materials may be aligned on the substrate by external force induction, and the frame for forming the mold may be a Teflon frame.
  • the preparation method of the deformable stimuli-responsive material provided by the invention is simple, convenient and low in cost.
  • the present invention provides a stimuli-responsive flexible microelectrode array comprising a flexible substrate, an electrode structure disposed on one side of the flexible substrate, and a stimuli-responsive layer disposed on the other side of the flexible substrate,
  • the material of the stimuli-responsive layer is the above-described deformable stimuli-responsive material of the present invention.
  • the stimulation response layer has a local Young's modulus difference, and the degree of difference in the local Young's modulus difference is in the range of 0.0001 Pa to 2000 GPa. Further, the degree of difference is in the range of 10 Pa to 100 KPa.
  • the flexible substrate has a thickness of from 1 ⁇ m to 5 mm, further from 5 ⁇ m to 100 ⁇ m; and the stimuli-responsive layer has a thickness of from 1 ⁇ m to 1 cm, further from 50 ⁇ m to 1 mm.
  • the flexible substrate is made of polyimide, parylene or polydimethylsiloxane.
  • the weight percentages of the photothermal nanoparticles, the magnetocaloric nanoparticles, and the electrothermal nanoparticles are 0.01% to 20%, respectively.
  • An aligning microstructure is disposed in the stimuli-responsive layer, the microstructure comprises a pit, a protrusion or a micro-nano material, and the micro-nano material comprises at least at least a graphene, a carbon nanotube, a glass fiber, and a nano particle.
  • the pit has a depth of 10 nm to 5 cm, and the height of the protrusion is 10 nm to 5 cm; further, the pit has a depth of 1 ⁇ m to 5 mm, and the height of the protrusion is 1 ⁇ m to 5 mm.
  • the stimuli-responsive layer is formed on the surface of the flexible substrate by surface chemical grafting or physical coating.
  • the above-mentioned stimuli-responsive flexible microelectrode array of the present invention can be prepared by surface chemical grafting or physical coating, as follows:
  • the substrate of the flexible microelectrode array is a polyimide substrate, it is immersed in an aqueous solution of ethylenediamine to react for 1-2 hours, so that a large amount of amino groups are formed on the surface of the flexible electrode substrate, An aminated flexible microelectrode array; when the substrate of the flexible microelectrode array is a parylene substrate or a polydimethylsiloxane substrate, the flexible microelectrode array is placed in a plasma surface cleaner with oxygen Plasma (plasma) bombards the substrate for 2-5 min, causing a large amount of hydroxyl groups to form on the surface of the substrate, resulting in a hydroxylated flexible microelectrode array.
  • Plasma Plasma
  • the pre-polymerization liquid containing the deformable stimuli-responsive material is disposed on the surface of the chemically modified flexible microelectrode array in a specific manner: a pre-polymerization liquid containing a deformable stimuli-responsive material Inject into the mold, the mold consists of two pieces of glass, a chemically modified flexible microelectrode array, and a Teflon frame with a certain thickness sandwiched therebetween.
  • the stimuli-responsive layer when it has directionally arranged pits or protrusions, it can be obtained by injecting a pre-polymerized liquid containing a deformable stimuli-responsive material into the mold and performing different degrees of irradiation, or It is obtained by lithographically forming a directional pit or protrusion on the surface of the glass sheet at the bottom of the mold.
  • the different degrees of irradiation can be achieved by adjusting the irradiation dose (including the irradiation power and the irradiation time), or selecting partial area irradiation, and partial areas are not irradiated.
  • This method is mainly suitable for humidity responsive materials.
  • the flexible microelectrode array is tiled onto a glass sheet surface, and then the micro/nano material is aligned on the back side of the electrode, and the polytetrafluoroethylene frame having a certain thickness is attached to the glass sheet and fixed by the clip, and then the humidity responsive material solution is applied.
  • the humidity responsive material solution is applied.
  • a stimuli-responsive layer on the back surface of the flexible microelectrode was formed, that is, the stimuli-responsive flexible microelectrode array was obtained.
  • the humidity responsive material solution is prepared by taking a polymer containing a large amount of hydrophilic groups and a polyester polymer containing a large amount of carbonyl groups, respectively dissolving the two in a solvent, and then uniformly mixing them in a certain mass ratio to obtain The humidity responsive material solution; the mass fraction of the solute in the solution ranges from 0.1 wt% to 5 wt%, and the solvent may be an organic solvent such as dimethylformamide.
  • the stimuli-responsive flexible microelectrode array provided by the invention can realize the three-dimensional deformation of the flexible microelectrode array by external stimulation, and further control the shape of the flexible microelectrode array by adjusting the thickness or the degree of crosslinking of the stimuli response layer. Adjustment, whereby the present invention can effectively adjust the shape of the flexible microelectrode to match various irregular tissues or organs, and has great biomedical significance.
  • the preparation process of the stimuli response layer of the present invention does not cause any damage to the electrode itself, and the photothermal effect and the magnetocaloric effect of the nanoparticles can realize the remote driving deformation of the response material itself and the electrode, and the surface chemical grafting method is adopted.
  • the combination of the stimuli response layer and the flexible microelectrode array can greatly increase the adhesion between the two and avoid the occurrence of delamination.
  • FIG. 1 is a schematic view showing a preparation process of a deformable stimuli-responsive material in Embodiment 1 of the present invention
  • FIG. 2 is a schematic structural view of a stimuli-responsive flexible microelectrode array in Embodiment 7 of the present invention.
  • Figure 3 is a deformation diagram of a stimuli-responsive flexible microelectrode array in Example 7 of the present invention.
  • FIG. 4 is a deformation diagram of a stimuli-responsive flexible microelectrode array in Embodiment 8 of the present invention.
  • Figure 5 is a graph showing the deformation of a stimuli-responsive flexible microelectrode array in Example 9 of the present invention.
  • a deformable stimuli responsive material comprising a thermally responsive material, poly acryl amide, said deformable stimuli responsive material having a local Young's modulus difference, said local Young's modulus The difference is brought about by the difference in the degree of cross-linking of the region, which is a thermally responsive hydrogel having a thickness of 1 mm.
  • the preparation method of the deformable stimulation response material comprises the following steps:
  • the prepolymerized liquid is injected into a mold consisting of two glass sheets and a polytetrafluoroethylene frame having a certain thickness sandwiched therebetween, and then a photomask having a specific structure is used. (The line angle of the reticle is 90°) is placed on the upper surface of the mold, and the sample is placed in an ice bath for ultraviolet irradiation for 10 minutes. After the pre-polymerization of the portion to be shielded and the irradiated portion is polymerized, the sample is immersed in the sample.
  • the unreacted prepolymerized liquid is removed in deionized water for 24 hours to obtain the deformable stimuli-responsive material, which is substantially a thermally responsive hydrogel, and the deformable stimuli-responsive material has the same composition as a whole, and is divided into The regions have different degrees of cross-linking, wherein the degree of crosslinking of the irradiated portions is higher than the occluded portions, and the difference in the local Young's modulus is formed by the difference in the degree of cross-linking of the different regions.
  • the photothermal reaction hydrogel obtained in Example 1 of the present invention was placed in an aqueous solution at 45 ° C, and the hydrogel gradually changed from transparent to opaque milky white, and began to shrink, gradually bending to form a three-dimensional hollow tubular structure, and the hydrogel was placed.
  • the aqueous solution at 25 ° C the hollow tubular hydrogel gradually returns to the original planar structure, and thus it can be seen that the thermally responsive hydrogel obtained in the present embodiment can achieve controllable adjustment of its shape.
  • a deformable stimuli responsive material consisting of a photothermally responsive material composed of two different components of A and B, wherein a part of the deformable stimuli-responsive material is composed of a photothermal response material composed of a group A, and a partial region is composed of a group B.
  • the photothermally responsive material is composed of a composition, in particular, the group A comprises a temperature sensitive polymer (specifically polyisopropyl acrylamide and poly(N-ethyl acrylamide)) and photothermal nanoparticles (specifically gold nanorods)
  • the group B is configured to include a temperature-sensitive polymer (specifically, poly(N-ethyl acrylamide)) and photothermal nanoparticles (specifically, gold nanorods), in the two groups A and B, the photothermal nanometer
  • the content of the particles is 5% by weight, and the deformable stimuli-responsive material has a local Young's modulus difference, and the local Young's modulus difference is composed of the mechanical properties of the materials of the two groups of A and B.
  • the difference is that the deformable stimuli-responsive material is a photothermally responsive hydrogel having a thickness of 300 ⁇ m.
  • the preparation method of the deformable stimulation response material comprises the following steps:
  • a deformable stimuli-responsive material is substantially a photothermally responsive hydrogel.
  • the photothermal reaction hydrogel obtained in Example 2 of the present invention was placed in an aqueous solution at 25 ° C, and a photothermal reaction hydrogel was irradiated by a near-infrared laser with a power of 5 W.
  • the hydrogel gradually changed from a transparent shape to an opaque milky white color. And begin to shrink and bend to form a three-dimensional cylindrical structure.
  • the curvature of the hydrogel can be effectively adjusted.
  • the cylindrical hydrogel gradually returns to the original planar structure, thereby obtaining the obtained light heat.
  • the controlled hydrogel can achieve a controlled adjustment of its shape.
  • a deformable stimuli responsive material specifically comprising a temperature sensitive polymer (specifically polyisopropyl acrylamide) and magnetocaloric nanoparticles (specifically triiron tetroxide), the magnetocaloric nanoparticles having a weight percentage of 5 %, the deformable stimuli-responsive material has a local Young's modulus difference, the local Young's modulus difference being brought about by the directional arrangement of the ferroferric oxide nanoparticles, the deformable stimuli-responsive material being a thickness of 500 ⁇ m Magnetocaloric response to hydrogels.
  • a temperature sensitive polymer specifically polyisopropyl acrylamide
  • magnetocaloric nanoparticles specifically triiron tetroxide
  • the deformable stimuli-responsive material is prepared by an external magnetic field, such that the rigid ferroferric oxide nanoparticles are aligned along the long axis in the prepolymerization of isopropylacrylamide, and then formed into a composite gel by irradiation polymerization.
  • the orientation of the rigid ferroferric oxide in the flexible hydrogel material brings about the difference of the local Young's modulus.
  • the magnetocaloric hydrogel obtained in the present embodiment is placed in an aqueous solution at 25 ° C, and the container is placed in an alternating magnetic field of 0.05-1.2 MHz.
  • the magnetic nanoparticles absorb a large amount of electromagnetic wave energy, and the ferrite generates energy loss.
  • electromagnetic energy is converted into heat, its temperature rises, the hydrogel gradually turns into milky white, and begins to shrink, bending to form a three-dimensional cylindrical structure.
  • the strength of the alternating magnetic field the curvature of the hydrogel can be effectively adjusted, and the magnetic field is removed.
  • the cylindrical hydrogel is gradually restored to the original planar structure, whereby it can be seen that the magnetocaloric hydrogel obtained in the present embodiment can achieve a controllable adjustment of its shape.
  • a deformable stimuli responsive material consisting of an electrothermally responsive material, specifically comprising a temperature sensitive polymer (specifically poly[oligo(ethylene glycol) monomethyl methacrylate methacrylate]) and electrothermal nanoparticles (specifically carbon) Black), the electrothermal nanoparticle has a weight percentage of 10%, and the deformable stimuli-responsive material has a local Young's modulus difference, and the local Young's modulus difference is determined by a microstructure (micro-pit or micro-protrusion)
  • the orientation of the deformable responsive material is an electrothermally responsive hydrogel having a thickness of 100 ⁇ m.
  • the preparation method of the deformable stimulation response material comprises the following steps:
  • the electrothermally-responsive hydrogel obtained in the embodiment of the present invention is placed in an aqueous solution at 25 ° C, and the container is placed in an applied electric field of 5 V with an electrode spacing of 50 mm.
  • the carbon black converts part of the electric energy into heat to raise the temperature of the self, and when the temperature exceeds At the lowest critical solution temperature of poly[oligo(ethylene glycol) monomethyl ether methacrylate], the hydrogel gradually turns milky white and begins to shrink, bending to form a three-dimensional helical structure, by adjusting the strength of the applied electric field.
  • the curvature of the hydrogel can be effectively adjusted.
  • the spiral hydrogel gradually returns to the original planar structure, and thus the electrothermally-responsive hydrogel obtained in the present embodiment can achieve controllable adjustment of its shape.
  • a deformable stimuli responsive material consisting of a humidity responsive material and a nano material, specifically comprising a polymer containing a large amount of hydrophilic groups (specifically agarose) and a polyester containing a large amount of carbonyl groups (specifically polymethacrylic acid) a methyl ester), wherein the nanomaterial is aligned carbon nanotubes, the nanoparticle has a weight percentage of 5%, and the deformable stimuli-responsive material has a local Young's modulus difference, and the local Young's modulus difference Brought by the orientation of the carbon nanotubes, the deformable stimuli-responsive material is a humidity-responsive film having a thickness of 20 ⁇ m.
  • the preparation method of the deformable stimulation response material comprises the following steps:
  • the film was placed in a constant temperature and humidity chamber with a humidity of 50% and a temperature of 25 ° C.
  • the agarose swollen film was bent to form a hollow tubular structure, and the film was transferred to a constant temperature and humidity chamber having a humidity of 20% and a temperature of 25 ° C.
  • the moisture volatilization returns to the initial flat structure, and the response rate of the film can be effectively adjusted by adjusting the test moisture content, so that the humidity-responsive film obtained in the embodiment can realize the controllable adjustment of its shape.
  • a deformable stimuli responsive material comprising a pH responsive material, polymethyl methacrylate, said deformable stimuli responsive material having a local Young's modulus difference, said local Young's modulus difference being The difference in the degree of cross-linking of the region brings the deformable stimuli-responsive material to a pH-responsive hydrogel having a thickness of 5 mm.
  • the preparation method of the deformable stimulation response material comprises the following steps:
  • the reacted pre-polymerization liquid obtains the deformable stimuli-responsive material, which is substantially a pH-responsive hydrogel, and the deformable stimuli-responsive material has the same composition as a whole, and the sub-regions have different cross-linking. Degree, wherein the degree of crosslinking of the irradiated portion is higher than the occluded portion, and the difference in the local Young's modulus is formed by the difference in the degree of crosslinking of the different regions.
  • a stimuli-responsive flexible microelectrode array comprising a polyimide substrate, an electrode structure disposed on one side of the substrate, and a stimuli-responsive layer having a local Young's modulus difference grafted on the other side of the substrate,
  • the thickness of the polyimide substrate is 10 ⁇ m
  • the thickness of the stimuli-responsive layer is 500 ⁇ m
  • the material of the stimuli-responsive layer is a deformable stimuli-responsive material
  • the variability of the stimuli-responsive material is a temperature-sensitive polymer (polyisopropyl)
  • the partial Young's modulus difference of the acrylamide is caused by the difference in the degree of cross-linking of the regions.
  • the method for preparing the stimuli-responsive flexible microelectrode array comprises the following steps:
  • the flexible microelectrode array was immersed in 1.65mol/L aqueous solution of ethylenediamine for 2h. After treatment with amines, the imine ring in the segment was broken to form amide, which caused a large amount of amino groups on the surface of the substrate. After the end, it is repeatedly washed with deionized water for 4-5 times, and naturally dried to obtain an aminated flexible microelectrode array;
  • the prepolymerized liquid is injected into a mold consisting of two glass sheets, a chemically modified flexible microelectrode array, and a polytetrafluoroethylene frame having a certain thickness sandwiched therebetween, and then a photomask having a specific structure ( The line angle of the reticle is 0°) placed on the upper surface of the mold, and the sample is placed in an ice bath for ultraviolet irradiation for 10 minutes. After the pre-polymerization of the occluded portion and the irradiated portion is polymerized, the sample is immersed in the sample. The unreacted prepolymerized liquid was removed in ionic water for 24 hours to obtain a stimuli-responsive layer formed on the back surface of the electrode, that is, a stimuli-responsive flexible microelectrode array was obtained.
  • FIG. 2 is a schematic structural view (disassembly diagram) of a stimuli-responsive flexible microelectrode array in Embodiment 7 of the present invention; wherein, 10 For the substrate, 201 is the stimulus response layer and 202 is the difference in local Young's modulus.
  • the electrode structure is on the other side surface of the substrate 10 (not shown).
  • the stimulating response flexible microelectrode array obtained in the present embodiment was placed in an aqueous solution at 45 ° C, and the hydrogel layer gradually changed from transparent to opaque milky white, and the hydrogel layer began to shrink, and the planar flexible microelectrode was bent to form a three-dimensional shape.
  • the cylindrical structure (as shown in FIG. 3) stimulates the flexible electrode to be in an aqueous solution at 25° C., and the cylindrical flexible electrode is gradually restored to the original planar structure, thereby showing that the stimuli-responsive flexible microelectrode array obtained in the present embodiment can be Achieve controllable adjustment of its shape.
  • a stimuli-responsive flexible microelectrode array comprising a polyimide substrate, an electrode structure disposed on one side of the substrate, and a stimuli-responsive layer having a local Young's modulus difference grafted on the other side of the substrate,
  • the thickness of the polyimide substrate is 500 ⁇ m
  • the thickness of the stimuli-responsive layer is 5 mm
  • the material of the stimuli-responsive layer is a deformable stimuli-responsive material composed of a photothermally responsive material composed of two different components of A and B.
  • the deformable stimuli-responsive material is partially composed of a photo-thermally responsive material composed of a group A, and a portion of the region is composed of a photo-thermally responsive material composed of a group B.
  • the group A comprises a temperature-sensitive polymer (specifically, polyisopropylate).
  • group B consists of comprising a temperature sensitive polymer (specifically poly(N-ethyl acrylamide)) and Photothermal nanoparticles (specifically, gold nanorods)
  • the photothermal nanoparticles have a weight percentage of 5%
  • the deformable stimuli-responsive material has a local Young's modulus difference.
  • the local Young's modulus difference is determined by The difference in mechanical properties of the materials composed of different components of A and B groups is brought about by the difference.
  • the method for preparing the stimuli-responsive flexible microelectrode array comprises the following steps:
  • the flexible microelectrode array was immersed in 1.65mol/L aqueous solution of ethylenediamine for 2h. After treatment with amines, the imine ring in the segment was broken to form amide, which caused a large amount of amino groups on the surface of the substrate. After the end, it is repeatedly washed with deionized water for 4-5 times, and naturally dried to obtain an aminated flexible microelectrode array;
  • prepolymer B Gold nanorods (5wt%), uniformly mixed to obtain prepolymer B; the prepolymer A is injected into the mold, the mold consists of two pieces of glass, a chemically modified flexible microelectrode array and a sandwich A polytetrafluoroethylene frame of thickness is formed, and then a photomask plate having a specific structure (the line angle of the reticle is 45°) is placed on the upper surface of the mold, and then the sample is placed in an ice bath for ultraviolet exposure for 5 min. After the reaction, rinse off the prepolymerized solution A in the unexposed irradiation area with deionized water; then add the prepolymerized solution B to the mold, and then sample the sample.
  • the prepolymer A is injected into the mold, the mold consists of two pieces of glass, a chemically modified flexible microelectrode array and a sandwich A polytetrafluoroethylene frame of thickness is formed, and then a photomask plate having a specific structure
  • the sample After being exposed to ultraviolet exposure for 5 min in an ice bath, after the reaction is finished, the sample is immersed in deionized water for 24 hours to remove the unreacted prepolymerized liquid B to obtain a stimuli-responsive layer formed on the back surface of the electrode, that is, a stimulating response flexible microelectrode is obtained.
  • Array After being exposed to ultraviolet exposure for 5 min in an ice bath, after the reaction is finished, the sample is immersed in deionized water for 24 hours to remove the unreacted prepolymerized liquid B to obtain a stimuli-responsive layer formed on the back surface of the electrode, that is, a stimulating response flexible microelectrode is obtained.
  • Array After being exposed to ultraviolet exposure for 5 min in an ice bath, after the reaction is finished, the sample is immersed in deionized water for 24 hours to remove the unreacted prepolymerized liquid B to obtain a stimuli-responsive layer formed on the back surface of the electrode, that is, a stimulating response flexible microelectrode is
  • the stimuli-responsive flexible microelectrode array obtained in the present embodiment was placed in an aqueous solution at 25 ° C, and a photothermal response hydrogel layer was irradiated by a near-infrared laser with a power of 5 W.
  • the hydrogel layer gradually changed from a transparent shape to an opaque milky white layer.
  • the planar flexible microelectrode array gradually changes into a three-dimensional spiral structure (as shown in FIG. 4), and after stopping the illumination, the spiral flexible electrode gradually returns to the original planar structure.
  • a stimuli-responsive flexible microelectrode array comprising a polyimide substrate, an electrode structure disposed on one side of the substrate, and a stimuli-responsive layer having a local Young's modulus difference grafted on the other side of the substrate,
  • the thickness of the polyimide substrate is 5 ⁇ m
  • the thickness of the stimuli-responsive layer is 100 ⁇ m
  • the material of the stimuli-responsive layer is a deformable stimuli-responsive material, including a temperature-sensitive polymer (polyisopropylacrylamide) and electrothermal nanoparticles. (Carbon black), wherein the photothermal nanoparticles have a weight percentage of 10%, and the local Young's modulus difference is caused by the orientation of the microstructures (microprojections).
  • the method for preparing the stimuli-responsive flexible microelectrode array comprises the following steps:
  • the flexible microelectrode array was immersed in 1.65mol/L aqueous solution of ethylenediamine for 2h. After treatment with amines, the imine ring in the segment was broken to form amide, which caused a large amount of amino groups on the surface of the substrate. After the end, it is repeatedly washed with deionized water for 4-5 times, and naturally dried to obtain an aminated flexible microelectrode array;
  • the prepolymerized solution is obtained after the solution is uniformly mixed; the prepolymerized solution is injected into the mold, and the mold is composed of two pieces of glass, a chemically modified flexible microelectrode array and a certain thickness sandwiched therebetween
  • the composition of the PTFE frame, the sample was placed in an ice bath for ultraviolet irradiation for 5 min, and a polytetrafluoroethylene frame of the same size and thickness of 5 ⁇ m was added to the original Teflon frame after polymerization and formed thereon.
  • a photomask plate with a specific structure was placed on the surface of the slide (the line angle of the reticle was 90°), the prepolymerization liquid was injected into the mold, and the sample was placed in an ice bath for ultraviolet irradiation for 5 min, and the irradiation region was polymerized to block part of the film. Polymerization, the surface forms a directional array of raised microstructures, resulting in a stimuli-responsive layer formed on the back side of the electrode, i.e., a stimulus-responsive flexible microelectrode array.
  • the stimuli-responsive flexible microelectrode array obtained in the present embodiment was placed in an aqueous solution at 25 ° C, and the container was placed in an applied electric field of 5 V with an electrode spacing of 50 mm.
  • the carbon black converts part of the electric energy into heat to increase its temperature, and when the temperature exceeds At the lowest critical solution temperature of poly[oligo(ethylene glycol) monomethyl ether methacrylate], the hydrogel layer begins to shrink, and the planar flexible microelectrode array gradually becomes a hollow tubular structure (as shown in Figure 5). It is shown that after the electric field is withdrawn, the hollow tubular flexible electrode is gradually restored to the original planar structure, so that the stimuli-responsive flexible microelectrode array obtained in the present embodiment can realize the controllable adjustment of its shape.
  • a stimuli-responsive flexible microelectrode array comprising a polydimethylsiloxane substrate, an electrode structure disposed on one side of the substrate, and a stimulus having a local Young's modulus difference grafted on the other side of the substrate
  • the thickness of the polydimethylsiloxane substrate is 5 ⁇ m
  • the thickness of the stimuli-responsive layer is 100 ⁇ m
  • the material of the stimuli-responsive layer is a deformable stimuli-responsive material, including a temperature-sensitive polymer (poly(trimerization) Ethylene glycol) monomethyl ether methacrylate) and photothermal nanoparticles (reduced graphene oxide), wherein the photothermal nanoparticles have a weight percentage of 0.01%
  • the local Young's modulus difference is The difference in the degree of regional cross-linking.
  • the method for preparing the stimuli-responsive flexible microelectrode array comprises the following steps:
  • the flexible microelectrode array is placed in a plasma surface cleaning machine, and the substrate is bombarded with oxygen plasma for 2 min to form a large amount of hydroxyl groups on the surface of the polydimethylsiloxane substrate to obtain a hydroxylated flexible microelectrode array;
  • the propyl acrylate was injected into the system and reacted for 1 hour in a N 2 atmosphere. After the reaction was completed, the mixture was washed three times with n-hexane and deionized water to obtain a chemically modified flexible microelectrode array.
  • the tetrafluoroethylene frame is composed, and then a photomask plate having a specific structure (the line angle of the reticle is 90°) is placed on the upper surface of the mold, and the sample is placed in an ice bath for ultraviolet irradiation for 10 minutes, and the portion to be shielded and the spokes are to be shielded.
  • the sample is immersed in deionized water for 24 hours to remove the unreacted prepolymerized liquid, thereby obtaining a stimuli response layer formed on the back surface of the electrode, that is, a stimuli-responsive flexible microelectrode array is obtained.
  • the stimulating response flexible microelectrode array obtained in the present embodiment was placed in an aqueous solution at 25 ° C, and a photothermal response hydrogel layer was irradiated by a near-infrared laser with a power of 5 W, and the planar flexible microelectrode array was gradually changed into a hollow tubular structure. After the illumination is stopped, the hollow tubular flexible electrode is gradually restored to the original planar structure.
  • a stimuli-responsive flexible microelectrode array comprising a parylene substrate, an electrode structure disposed on one side of the substrate, and a stimulus response layer having a local Young's modulus difference grafted on the other side of the substrate,
  • the thickness of the parylene substrate is 5 ⁇ m
  • the thickness of the stimuli-responsive layer is 100 ⁇ m
  • the material of the stimuli-responsive layer is a deformable stimuli-responsive material, including a temperature-sensitive polymer (poly(triethylene glycol) monomethyl) Ether methacrylate) and photothermal nanoparticles (reduced graphene oxide), wherein the photothermal nanoparticles have a weight percentage of 0.5%
  • the local Young's modulus difference is determined by the difference in the degree of cross-linking of the regions bring.
  • the method for preparing the stimuli-responsive flexible microelectrode array comprises the following steps:
  • the flexible microelectrode array is placed in a plasma surface cleaning machine, and the substrate is bombarded with oxygen plasma for 2 min to form a large amount of hydroxyl groups on the surface of the polydimethylsiloxane substrate to obtain a hydroxylated flexible microelectrode array;
  • the propyl acrylate was injected into the system and reacted for 1 hour in a N 2 atmosphere. After the reaction was completed, the mixture was washed three times with n-hexane and deionized water to obtain a chemically modified flexible microelectrode array.
  • a tetrafluoroethylene frame is formed, and then a photomask plate having a specific structure (the line angle of the reticle is 45°) is placed on the upper surface of the mold, and the sample is placed in an ice bath for ultraviolet irradiation for 10 minutes, and the portion to be shielded and the spokes are to be shielded.
  • the sample is immersed in deionized water for 24 hours to remove the unreacted prepolymerized liquid, thereby obtaining a stimuli response layer formed on the back surface of the electrode, that is, a stimuli-responsive flexible microelectrode array is obtained.
  • the stimulating response three-dimensional flexible microelectrode array obtained in the present embodiment was placed in an aqueous solution at 25 ° C, and a photothermal response hydrogel layer was irradiated by a near-infrared laser with a power of 5 W, and the planar flexible microelectrode array was gradually spiraled. Structure, after stopping the illumination, the spiral flexible electrode gradually returns to the original planar structure.
  • a stimuli-responsive flexible microelectrode array comprising a parylene substrate, an electrode structure disposed on one side of the substrate, and a stimulus response layer having a local Young's modulus difference grafted on the other side of the substrate,
  • the thickness of the parylene substrate is 5 ⁇ m
  • the thickness of the stimuli-responsive layer is 100 ⁇ m
  • the material of the stimuli-responsive layer is a deformable stimuli-responsive material, including a temperature-sensitive polymer (polyisopropylacrylamide) and photothermal nano The particles (carbon nanotubes), wherein the photothermal nanoparticles have a weight percentage of 0.5%, and the local Young's modulus difference is caused by a difference in the degree of cross-linking of the regions.
  • the method for preparing the stimuli-responsive flexible microelectrode array comprises the following steps:
  • the flexible microelectrode array is placed in a plasma surface cleaning machine, and the substrate is bombarded with oxygen plasma for 2 min to form a large amount of hydroxyl groups on the surface of the parylene substrate to obtain a hydroxylated flexible microelectrode array;
  • the propyl acrylate was injected into the system and reacted for 1 hour in a N 2 atmosphere. After the reaction was completed, the mixture was washed three times with n-hexane and deionized water to obtain a chemically modified flexible microelectrode array.
  • the mold is composed of two glass sheets, a chemically modified flexible microelectrode array, and a Teflon frame with a certain thickness sandwiched therebetween.
  • a photomask plate having a specific structure (the line angle of the reticle is 90°) is placed on the upper surface of the mold, and the sample is placed in an ice bath for ultraviolet irradiation for 10 minutes, to be shielded.
  • the sample is immersed in deionized water for 24 hours to remove the unreacted prepolymerized liquid, thereby obtaining a stimuli response layer formed on the back surface of the electrode, that is, a stimuli-responsive flexible microelectrode array is obtained.
  • the stimulating response flexible microelectrode array obtained in the present embodiment was placed in an aqueous solution at 25 ° C, and the photothermal response hydrogel layer was irradiated by a fluorescent lamp with a power of 5 W.
  • the hydrogel layer began to gradually shrink, and the planar flexible microelectrode array was driven.
  • the hollow tubular structure is gradually bent to adjust the curvature of the flexible microelectrode array by adjusting the illumination intensity. After the illumination is stopped, the hollow tubular flexible electrode is gradually restored to the original planar structure.
  • a stimuli-responsive flexible microelectrode array comprising a parylene substrate, an electrode structure disposed on one side of the substrate, and a stimulus response layer having a local Young's modulus difference grafted on the other side of the substrate,
  • the thickness of the parylene substrate is 5 ⁇ m
  • the thickness of the stimuli-responsive layer is 100 ⁇ m
  • the material of the stimuli-responsive layer is a deformable stimuli-responsive material, including a temperature-sensitive polymer (polyisopropylacrylamide) and photothermal nano The particles (carbon nanotubes), wherein the photothermal nanoparticles have a weight percentage of 0.5%, and the local Young's modulus difference is caused by a difference in the degree of cross-linking of the regions.
  • the method for preparing the stimuli-responsive flexible microelectrode array comprises the following steps:
  • the flexible microelectrode array is placed in a plasma surface cleaning machine, and the substrate is bombarded with oxygen plasma for 2 min to form a large amount of hydroxyl groups on the surface of the parylene substrate to obtain a hydroxylated flexible microelectrode array;
  • the propyl acrylate was injected into the system and reacted for 1 hour in a N 2 atmosphere. After the reaction was completed, the mixture was washed three times with n-hexane and deionized water to obtain a chemically modified flexible microelectrode array.
  • the mold is composed of two glass sheets, a chemically modified flexible microelectrode array, and a Teflon frame with a certain thickness sandwiched therebetween.
  • a photomask plate having a specific structure (the line angle of the reticle is 0°) is placed on the upper surface of the mold, and the sample is placed in an ice bath for ultraviolet irradiation for 10 minutes, and the prepolymerized portion of the portion to be shielded and the irradiated portion is irradiated.
  • the sample was immersed in deionized water for 24 hours to remove the unreacted prepolymerized liquid to obtain a stimuli-responsive layer formed on the back surface of the electrode, that is, a stimuli-responsive flexible microelectrode array was obtained.
  • the stimulating response flexible microelectrode array obtained in the present embodiment was placed in an aqueous solution at 25 ° C, and the photothermal response hydrogel layer was irradiated by a fluorescent lamp with a power of 5 W.
  • the hydrogel layer began to gradually shrink, and the planar flexible microelectrode array was driven.
  • the curved three-dimensional cylindrical structure is gradually formed, and the curvature of the flexible microelectrode array can be effectively adjusted by adjusting the illumination intensity. After the illumination is stopped, the cylindrical flexible electrode is gradually restored to the original planar structure.
  • a stimuli-responsive flexible microelectrode array comprising a polyimide substrate, an electrode structure disposed on one side of the substrate, and a stimuli-responsive layer having a local Young's modulus difference grafted on the other side of the substrate,
  • the thickness of the polyimide substrate is 5 ⁇ m
  • the thickness of the stimuli-responsive layer is 10 ⁇ m
  • the material of the stimuli-responsive layer is a deformable stimuli-responsive material, including wet a responsive material (composite of agarose and polymethyl methacrylate) and photothermal nanoparticles (aligned carbon nanotubes), wherein the photothermal nanoparticles have a weight percentage of 0.5%, the local portion
  • the Young's modulus difference is caused by the alignment of the carbon nanotubes.
  • the method for preparing the stimuli-responsive flexible microelectrode array comprises the following steps:
  • the flexible microelectrode array was immersed in 1.65mol/L aqueous solution of ethylenediamine for 2h. After treatment with amines, the imine ring in the segment was broken to form amide, which caused a large amount of amino groups on the surface of the substrate. After the end, it is repeatedly washed with deionized water for 4-5 times, and naturally dried to obtain an aminated flexible microelectrode array;
  • a piece of wet filter paper was placed on a hot plate at 45 ° C for 5 minutes. After most of the moisture was removed, the stimuli-responsive flexible microelectrode array obtained in this example was placed on a 45 ° C filter paper, and the humidity response layer was swollen with water, along vertical. Bending (long axis) in the direction in which the carbon nanotubes are aligned, forming a three-dimensional cylindrical structure. After the water is completely volatilized, the cylindrical flexible electrode gradually returns to the original planar structure.
  • a stimuli-responsive flexible microelectrode array comprising a polyimide substrate, an electrode structure disposed on one side of the substrate, and a stimuli-responsive layer having a local Young's modulus difference grafted on the other side of the substrate,
  • the thickness of the polyimide substrate is 5 ⁇ m
  • the thickness of the stimuli-responsive layer is 500 ⁇ m
  • the material of the stimuli-responsive layer is a deformable stimuli-responsive material, including a pH-responsive material (polydimethyl methacrylate hydrogel)
  • the local Young's modulus difference is caused by the difference in the degree of cross-linking of the regions.
  • the method for preparing the stimuli-responsive flexible microelectrode array comprises the following steps:
  • the flexible microelectrode array was immersed in 1.65mol/L aqueous solution of ethylenediamine for 2h. After treatment with amines, the imine ring in the segment was broken to form amide, which caused a large amount of amino groups on the surface of the substrate. After the end, it is repeatedly washed with deionized water for 4-5 times, and naturally dried to obtain an aminated flexible microelectrode array;
  • the prepolymerization liquid is injected into the mold, and the mold is composed of two glass sheets, a chemically modified flexible microelectrode array, and a Teflon frame with a certain thickness sandwiched therebetween, and then a photomask having a specific structure ( The line angle of the reticle is 90°) is placed on the upper surface of the mold, and the sample is placed in an ice bath for ultraviolet irradiation for 10 minutes. After the pre-polymerization of the occluded portion and the irradiated portion is polymerized, the sample is immersed in the sample. The unreacted prepolymerized liquid was removed in ionic water for 24 hours to obtain a stimuli-responsive layer formed on the back surface of the electrode, that is, a stimuli-responsive flexible microelectrode array was obtained.
  • the stimulation-responsive flexible microelectrode array obtained in the present embodiment is placed in an aqueous solution of sodium hydroxide having a pH of 10, and the stimulating response layer gradually changes from transparent to opaque milky white, and the planar flexible microelectrode array gradually becomes a hollow tubular structure.
  • a stimuli-responsive flexible microelectrode array comprising a polyimide substrate, an electrode structure disposed on one side of the substrate, and a stimuli-responsive layer having a local Young's modulus difference grafted on the other side of the substrate,
  • the thickness of the polyimide substrate is 5 ⁇ m
  • the thickness of the stimuli-responsive layer is 500 ⁇ m
  • the material of the stimuli-responsive layer is a deformable stimuli-responsive material, including a magnetocaloric responsive material (polyisopropylacrylamide@Fe 3 O 4 ) Hydrogel)
  • the local Young's modulus difference is brought about by the directional alignment of the orientation of the micro-nano materials.
  • the method for preparing the stimuli-responsive flexible microelectrode array comprises the following steps:
  • the flexible microelectrode array was immersed in 1.65mol/L aqueous solution of ethylenediamine for 2h. After treatment with amines, the imine ring in the segment was broken to form amide, which caused a large amount of amino groups on the surface of the substrate. After the end, it is repeatedly washed with deionized water for 4-5 times, and naturally dried to obtain an aminated flexible microelectrode array;
  • Fluoroethylene frame composition an external magnetic field is applied near the mold, and the direction of the applied magnetic field is adjusted so that the ferroferric oxide is aligned along the long axis at 45°, and then the sample is placed in an ice bath for ultraviolet irradiation for 10 min, to be blocked. After the prepolymerized solution of the irradiated portion is uniformly polymerized, the sample is immersed in deionized water for 24 hours to remove the unreacted prepolymerized liquid, thereby obtaining a stimuli response layer formed on the back surface of the electrode, that is, a stimulating response flexible microelectrode array is obtained.
  • the stimulating response flexible microelectrode array obtained in the present embodiment is placed in an aqueous solution of 25 ° C and placed in an alternating magnetic field of 0.05-1.2 MHz.
  • the magnetic nanoparticles absorb a large amount of electromagnetic wave energy, and the ferrite generates energy loss, and part of the electromagnetic energy
  • the conversion to heat can raise the temperature of the self.
  • the temperature is close to the phase transition temperature of polyisopropylacrylamide, the hydrogel network begins to shrink and form a three-dimensional spiral structure.
  • the magnetic field is removed, the temperature of the system decreases, and the spiral shape
  • the flexible electrode is gradually restored to the original planar structure.

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Abstract

一种可变形的刺激响应材料及其制备方法和刺激响应柔性微电极阵列，所述可变形的刺激响应材料具有局部杨氏模量差异，所述可变形的刺激响应材料由热响应材料、光热响应材料、磁热响应材料、电热响应材料、湿度响应材料和pH响应材料中的至少一种构成，所述可变形的刺激响应材料在温度、光、磁、电、湿度、pH中的一种或多种外界刺激条件下，可由平面二维结构转变成三维结构。将该材料修饰到平面柔性微电极阵列的背面，即可通过外界刺激实现柔性微电极阵列的三维形变，且进一步通过调节可变形的刺激响应材料的厚度或交联度等即可实现对传统平面柔性微电极阵列的可控塑形与曲率精准调控。

Description

一种可变形的刺激响应材料及其制备方法和刺激响应柔性微电极阵列 技术领域
本发明涉及生物医学工程技术领域，特别是涉及一种可变形的刺激响应材料及其制备方法和刺激响应柔性微电极阵列。
背景技术
柔性微电极阵列通过向特定的神经组织施加脉冲式电流刺激来帮助患者进行功能重建，现已在人工耳蜗、人造视网膜等医疗器械中得到广泛应用。柔性微电极阵列作为假体与神经的直接接触点，对发挥假体的神经电刺激功能起着关键性的作用。微电极阵列与神经组织或器官的贴合程度决定了电刺激的有效性。然而，神经组织或器官往往是一个不规则的曲面，传统的平面电极与其接触不好，导致刺激效率低，稳定性下降。因此，研发形状可控式柔性微电极阵列对于植入物的长期稳定性以及改善刺激效率意义重大。传统电极加工的方法是通过热压的形式来赋予电极一定曲率，但该方法容易出现断线的情况，对电极造成一定程度的破坏。如何使用简易的方式在不破坏电极的前提下赋予柔性电极阵列一定的曲率成为了一个亟待解决的难题。
有研究者从电极微加工的角度出发，利用加工过程中的应力聚集成功实现了平面电极由二维结构向三维结构的转变，该工作最大的亮点在于不仅通过横向的压缩应力实现了电极整体由平面结构向圆柱型结构的转变，更通过局部拉伸应力实现了刺激点位的向外弯曲，大大提高了电极与神经组织间的接触面积。然而该电极设计与微加工工艺相当复杂，对设备以及环境洁净度要求相当高，这些因素都阻碍了其进一步向市场的推广。
近期也有研究者利用形状记忆聚合物形状记忆的功能通过温度触发来为柔性电极塑形。然而，所述形状记忆聚合物的触发温度接近100℃，触发温度过高，同时响应层与柔性微电极阵列基底之间没有采用任何化学修饰，容易出现响应层与柔性基底分层的现象，上述缺陷限制了其实际应用。
发明内容
鉴于此，本发明提供了一种可变形的刺激响应材料，该可变形的刺激响应材料在外界刺激下，可由平面二维结构转变成三维结构，将其修饰到平面柔性微电极阵列的背面，即可通过外界刺激实现柔性微电极阵列的三维形变，且进一步通过调节可变形的刺激响应材料的厚度或交联度等即可实现对传统平面柔性微电极阵列的可控塑形与曲率精准调控。
具体地，第一方面，本发明提供了一种可变形的刺激响应材料，所述可变形的刺激响应材料具有局部杨氏模量差异，所述可变形的刺激响应材料由热响应材料、光热响应材料、磁热响应材料、电热响应材料、湿度响应材料和pH响应材料中的至少一种刺激响应材料构成，所述可变形的刺激响应材料在温度、光、磁、电、湿度、pH中的一种或多种外界刺激条件下，可由平面二维结构转变成三维结构。
本发明提供的可变形的刺激响应材料，由于具有局部杨氏模量差异，经过特定的外界刺激后，不同杨氏模量的区域会发生不同程度溶胀或收缩，从而实现材料由平面二维结构向螺旋形、空心管状、圆柱形等三维结构转变。
所述局部杨氏模量差异的差异程度在0.0001Pa-2000Gpa范围内。进一步地，差异程度在10Pa-100KPa范围内。
本发明一实施方式中，所述可变形的刺激响应材料整体具有相同的组分构成，且分区域 具有不同的交联度，所述局部杨氏模量差异由不同区域的交联度差异形成。具体可通过将一具有相同组分构成的可变形的刺激响应材料预聚液分区域进行不同程度的辐照得到。所述不同辐照程度可以通过调整辐照剂量(包括辐照功率和辐照时间)实现，或选择部分区域辐照，部分区域不辐照实现。该实施方式中，所述相同的组分构成可以只包含一种刺激响应材料，也可以是包含两种或两种以上的刺激响应材料，当为多种时，刺激响应材料的类型也可以是多种，如可以同时包含热响应材料和湿度响应材料。其中，交联度不同的区域的形状不限。
本发明另一实施方式中，所述可变形的刺激响应材料分区域具有不同的组分构成，所述局部杨氏模量差异由所述不同组分构成的不同力学性能差异形成。所述不同的组分构成包括多组，即两组或两组以上。具体可通过将多组具有不同组分构成的可变形的刺激响应材料预聚液分区域聚合成型得到。所述多组可以是两组或两组以上，以两组为例，可以包括A组预聚液和B组预聚液，其中，A组预聚液和B组预聚液均可以只包含一种刺激响应材料，也可以是包含两种或两种以上的刺激响应材料，当为多种时，刺激响应材料的类型也可以是多种，如可以同时包含热响应材料和湿度响应材料。其中，组分构成不同的区域的形状不限。
本发明另一实施方式中，所述可变形的刺激响应材料整体具有相同的组分构成，且所述可变形的刺激响应材料中设置有定向排列的微结构，所述局部杨氏模量差异由所述微结构的定向排列形成，所述微结构包括凹坑、凸起或微纳米材料，所述微纳米材料包括石墨烯、碳纳米管、玻璃纤维、纳米颗粒中的至少一种。
本发明另一实施方式中，所述可变形的刺激响应材料分区域具有不同的组分构成，且所述可变形的刺激响应材料中设置有定向排列的微结构，所述局部杨氏模量差异由所述微结构的定向排列、以及所述不同组分构成的不同力学性能差异形成，所述微结构包括凹坑、凸起或微纳米材料，所述微纳米材料包括石墨烯、碳纳米管、玻璃纤维、纳米颗粒中的至少一种。
所述凹坑的深度为10nm-5cm，所述凸起的高度为10nm-5cm；进一步地，所述凹坑的深度为1μm-5mm，所述凸起的高度为1μm-5mm。
所述凹坑或凸起可通过光刻形成。所述微纳米材料可通过外力诱导实现定向排列，所述纳米颗粒可以是无机纳米颗粒，也可以是有机纳米颗粒，如可以是四氧化三铁纳米颗粒等。
其中，所述三维结构包括圆柱体、螺旋形、空心管状结构。
可选地，所述热响应材料为温敏性聚合物，可选自以下物质中的至少一种：聚(N-异丙基丙烯酰胺)、聚(N-正丙基丙烯酰胺)、聚(N-环丙基丙烯酰胺)、聚(N-异丙基甲基丙烯酰胺)、聚(N-乙基丙烯酰胺)、聚(N-丙烯酰氧基-N-丙基哌嗪)、聚(N-(L)-(1-羟甲基)丙基甲基丙烯酰胺)、聚[N-(2-甲基丙烯酰氧乙基)吡咯烷酮]、聚[N-(3-丙烯酰氧丙基)吡咯烷酮]、聚[N-(3-甲基丙烯酰氧丙基)吡咯烷酮]、聚[N-(2-丙烯酰氧丙基)吡咯烷酮]、聚[N-(1-甲基-2-丙烯酰氧乙基)吡咯烷酮]、聚(2-烷基-2-唑啉)、聚(2-乙基-2-唑啉)、聚(2-异丙基-2-唑啉)、聚(2-正丙基-2-唑啉)、聚甲基丙烯酸二甲氨乙酯、聚(N-乙烯基环己内酰胺)、聚丙烯酰吡咯烷、聚甲基乙烯基醚、聚甲氧基乙基乙烯基醚、聚乙氧基乙基乙烯基醚、聚乙氧基乙氧基乙烯基醚、聚环氧丙烷、聚[低聚(乙二醇)单甲醚甲基丙烯酸酯]、聚有机膦腈、弹性蛋白样多肽、以及含上述单元的共聚物或衍生物。
可选地，所述光热响应材料是在热响应材料中添加了具有光热效应的纳米粒子，即同时包含具有光热效应的纳米粒子和热响应材料，这些具有光热效应的纳米粒子选自以下物质中的至少一种：金纳米棒、金纳米壳层、金纳米笼、空心金纳米球、钯纳米片、钯@银、钯@二氧化硅、碳纳米管、石墨烯、还原氧化石墨烯、炭黑、黑磷、硫化铜、吲哚菁绿、聚苯胺、 以及上述物质经过各种化学修饰后的产物。
可选地，所述磁热响应材料是在热响应材料中添加了具有磁热效应的纳米粒子，即同时包含具有磁热效应的纳米粒子和热响应材料，这些具有磁热效应的纳米粒子选自以下物质中的至少一种：Fe3O4、LaFeCoSi、GdSiGe、LaFe11.6Si1.4C0.2H0.7、La(Fe,Si)13、NiMnGa、MnCoGe0.99In0.01、MnCo0.98Cr0.02Ge等。
可选地，所述电热响应材料是在热响应材料中添加了具有电热效应的材料，即同时包含具有电热效应的纳米粒子和热响应材料，这些具有电热效应的材料选自以下物质中的至少一种：石墨、碳黑、碳纳米管、碳纤维、掺铝氧化锌、掺钙铬酸镧、掺锑二氧化锡、导电金属材料(如：金、银、铂、铜、铑、钯、铬等)、氧化铟锡、透明导电氧化物、聚乙炔、聚苯胺、聚吡咯等。
可选地，所述湿度响应材料由以下两类物质混合而成，其中一类为含有大量亲水基团的高分子，这类高分子选自以下物质中的至少一种：琼脂糖、纤维素、聚乙烯醇、壳聚糖、淀粉、聚丙烯酰胺、聚乙烯吡咯烷酮、透明质酸、透明质酸钠、聚苯乙烯磺酸钠、聚甲基丙烯酸羟乙酯、聚乙二醇、聚丁二醇、聚乙二醇甲基丙烯酸酯、聚乙二醇丙烯酸酯、明胶、海藻酸、胶原、聚L-赖氨酸、聚L-谷胺酸、羟丙基甲基纤维素、羟乙基纤维素、羧甲基纤维素、羧乙烯聚合物以及它们的衍生物。另一类为含有大量羰基的聚酯类，这类聚酯可选自以下物质中的至少一种：聚甲基丙烯酸甲酯、聚甲基丙烯酸乙酯、聚甲基丙烯酸叔丁基酯、聚丙烯酸甲酯、聚丙烯酸乙酯、聚乙烯基吡啶、聚碳酸酯、聚酰亚胺、羟甲基纤维素、醋酸纤维素、尼龙、聚(乙烯基对苯二甲酸酯)、聚磷腈、全氟磺酸、聚乙烯、聚苯乙烯、酚醛树脂、以及上述物质的衍生物。
可选地，所述pH响应材料选自含有羧基、吡啶、吡咯烷、哌嗪、磺酸、吗啉、磷酸盐、叔胺等基团的物质中的至少一种，具体可以是下述物质中的至少一种：聚丙烯酸、聚L-谷氨酸、聚组氨酸、聚天冬氨酸、聚[(2-二甲基氨基)甲基丙烯酸乙酯]、聚甲基丙烯酸、聚乙基丙烯酸、聚丙基丙烯酸、聚乙烯及苯甲酸、聚衣康酸、聚乙二醇丙烯酸酯磷酸、聚乙二醇甲基丙烯酸酯磷酸、聚乙烯磷酸、聚(4-乙烯基-苯基磷酸)、聚乙烯磺酸、聚(4-苯乙烯磺酸)、聚乙烯苯硼酸、聚甲基丙烯酸二甲氨基乙酯、聚甲基丙烯酸二乙氨基乙酯、聚(N-乙基吡咯烷甲基丙烯酸酯)、聚(2-乙烯基吡啶)、聚(N-丙烯酰基-N-烯基哌嗪)、聚丙烯酰吗啉、聚(4-乙烯基吡啶)、聚乙烯亚胺树状大分子、聚乙烯醇、预氧化丙烯腈等、壳聚糖、海藻酸、羧甲基纤维素、玻璃酸、以及含上述单元的衍生物和共聚物。
本发明对具体的刺激响应材料的选择没有严格要求，其选择取决于最终用途及用途所期望的效果。例如，对于光热响应材料中的光热纳米粒子的选择来说，往往取决于实际应用过程中所采用光源的波段，比如近红外光可选用金纳米棒或碳纳米管，可见光则选用氧化还原石墨烯。用于光热响应水凝胶层中的光热纳米粒子通常在400-1200nm的近红外光-可见光谱中具有至少一个激发的吸收峰，光热纳米粒子往往也可以辅助一些上转换纳米粒子，来有效调节激发波长。而热响应材料的选择往往取决于实际应用过程中所需要的触发温度，所选热响应材料的最低临界溶解温度应该低于实际触发温度，每种热响应材料的最低临界溶解温度能够通过改变特定取代基或选择和其他温敏性或非温敏性聚合物的共聚来进行有效调节。
本发明第一方面提供的可变形的刺激响应材料，在温度、光、磁、电、湿度、pH外界刺激下，可由平面二维结构转变成三维结构。
第二方面，本发明提供了一种可变形的刺激响应材料的制备方法，包括以下步骤：
取可变形的刺激响应材料的预聚液，所述预聚液包括热响应材料、光热响应材料、磁热响应材料、电热响应材料和pH响应材料中的至少一种的预聚体；
将所述预聚液注入模具中，然后将具有特定结构的掩模版置于所述模具上表面，采用辐照聚合的方式，待遮挡部分与曝露部分的预聚液均聚合成型后，得到可变形的刺激响应材料，所述可变形的刺激响应材料具有局部杨氏模量差异，所述可变形的刺激响应材料整体具有相同的组分构成，且分区域具有不同的交联度，所述曝露部分的交联度大于所述遮挡部分的交联度，所述局部杨氏模量差异由不同区域的交联度差异形成。
本实施方式中，曝露部分的交联度要高于遮挡部分，这样的区域杨氏模量的差异使得所得样品经外界刺激后会形成小范围应力聚集，驱动样品由平面二维结构向复杂三维结构转变。
以及，本发明提供了一种可变形的刺激响应材料的制备方法，包括以下步骤：
取两份具有不同组分构成的可变形的刺激响应材料的预聚液，所述预聚液包括热响应材料、光热响应材料、磁热响应材料、电热响应材料和pH响应材料中的至少一种的预聚体；
将其中一份所述预聚液注入模具中，然后将具有特定结构的掩模版置于所述模具上表面，采用辐照聚合的方式，待曝露部分聚合成型，而遮挡部分未聚合成型时，用水除去所述遮挡部分未聚合的预聚液，然后将另一份所述预聚液注入上述模具中，经辐照聚合后，得到可变形的刺激响应材料，所述可变形的刺激响应材料具有局部杨氏模量差异，所述可变形的刺激响应材料分区域具有不同的组分构成，所述局部杨氏模量差异由所述不同组分构成的不同力学性能差异形成。
本发明上述制备方法中，所述模具由两片玻璃片以及夹在中间的具有一定厚度的聚四氟乙烯框组成。其中，所述具有特定结构的掩模版，其特定结构可根据预设定的交联度不同的区域的形状或组分不同的区域的形状而具体设定。其结构设定可多样，本发明不作特殊限定，只要能构成局部杨氏模量差异即可。
以及本发明提供了一种可变形的刺激响应材料的制备方法，包括以下步骤：
取可变形的刺激响应材料的预聚液，所述预聚液包括热响应材料、光热响应材料、磁热响应材料、电热响应材料和pH响应材料中的至少一种的预聚体；
取基底，在所述基底上形成定向排列的微结构，所述微结构包括凹坑、凸起或微纳米材料，然后将一框体置于所述基底上，形成模具，将所述预聚液注入所述模具中，经辐照聚合后，得到可变形的刺激响应材料，所述可变形的刺激响应材料具有局部杨氏模量差异，所述可变形的刺激响应材料整体具有相同的组分构成，且所述可变形的刺激响应材料中设有定向排列的微结构，所述局部杨氏模量差异由所述微结构的定向排列形成，所述微纳米材料包括石墨烯、碳纳米管、玻璃纤维、纳米颗粒中的至少一种。
以及，本发明提供了一种可变形的刺激响应材料的制备方法，包括以下步骤：
取两份具有不同组分构成的可变形的刺激响应材料的预聚液，所述预聚液包括热响应材料、光热响应材料、磁热响应材料、电热响应材料和pH响应材料中的至少一种的预聚体；
取基底，在所述基底上形成定向排列的微结构，所述微结构包括凹坑、凸起或微纳米材料，然后将一框体置于所述基底上，形成模具，将其中一份所述预聚液注入模具中，然后将具有特定结构的掩模版置于所述模具上表面，采用辐照聚合的方式，待曝露部分聚合成型，而遮挡部分未聚合成型时，用水除去所述遮挡部分未聚合的预聚液，然后将另一份所述预聚液注入上述模具中，经辐照聚合后，得到可变形的刺激响应材料，所述可变形的刺激响应材料具有局部杨氏模量差异，所述可变形的刺激响应材料分区域具有不同的组分构成，所述局 部杨氏模量差异由所述微结构的定向排列和所述不同组分构成的不同力学性能差异形成，所述微纳米材料包括石墨烯、碳纳米管、玻璃纤维、纳米颗粒中的至少一种。
上述制备方法中，当纳米颗粒为磁性纳米颗粒时，也可将含有磁性纳米颗粒的预聚液，注入模具后，在所述模具周围施加一外加磁场，调整磁场方向使得磁性纳米颗粒沿某一方向定向排列。上述制备方法中，用于形成模具的框体可以是聚四氟乙烯框。
需要说明的是，本发明上述的几种制备方法中，当要获得光热响应材料时，所述预聚液中同时包含具有光热效应的纳米粒子和热响应材料预聚体；当要获得电热响应材料时，所述预聚液中同时包含具有电热效应的纳米粒子和热响应材料预聚体；当要获得磁热响应材料时，所述预聚液中同时包含具有磁热效应的纳米粒子和热响应材料预聚体。
本发明还提供了一种可变形的刺激响应材料的制备方法，包括以下步骤：
取含有大量亲水基团的高分子和含有大量羰基的聚酯类聚合物，将两者分别溶于溶剂中，然后以一定质量比混合均匀，得到湿度响应材料溶液；溶剂可为二甲基甲酰胺等有机溶剂；
取基底，将微纳米材料在所述基底上定向排列，然后将一框体置于所述基底上，形成模具，将上述湿度响应材料溶液注入模具中，经流延成膜后得到可变形的刺激响应材料，所述可变形的刺激响应材料具有局部杨氏模量差异，所述局部杨氏模量差异由微纳米材料的定向排列形成，所述微纳米材料包括石墨烯、碳纳米管、玻璃纤维、纳米颗粒中的至少一种。
其中，可以通过外力诱导使微纳米材料在基底上定向排列，用于形成模具的框体可以是聚四氟乙烯框。
本发明提供的可变形的刺激响应材料的制备方法操作简单、方便，成本低。
另一方面，本发明还提供了一种刺激响应柔性微电极阵列，包括柔性基底，设置在所述柔性基底一侧的电极结构，以及设置在所述柔性基底另一侧的刺激响应层，所述刺激响应层的材料为本发明上述的可变形的刺激响应材料。所述刺激响应层具有局部杨氏模量差异，所述局部杨氏模量差异的差异程度在0.0001Pa-2000Gpa范围内。进一步地，差异程度在10Pa-100KPa范围内。
其中，所述柔性基底的厚度为1μm-5mm，进一步地为5μm-100μm；所述刺激响应层的厚度为1μm-1cm，进一步地为50μm-1mm。可选地，所述柔性基底为聚酰亚胺、聚对二甲苯或聚二甲基硅氧烷材质。所述刺激响应层中，光热纳米粒子、磁热纳米粒子、电热纳米粒子的重量百分比含量分别为0.01％～20％。
所述刺激响应层中设置有定向排列的微结构，所述微结构包括凹坑、凸起或微纳米材料，所述微纳米材料包括石墨烯、碳纳米管、玻璃纤维、纳米颗粒中的至少一种。所述凹坑的深度为10nm-5cm，所述凸起的高度为10nm-5cm；进一步地，所述凹坑的深度为1μm-5mm，所述凸起的高度为1μm-5mm。
所述刺激响应层通过表面化学接枝或物理涂覆的方式形成在所述柔性基底表面。
本发明上述的刺激响应柔性微电极阵列可采用表面化学接枝法或物理涂覆法制备得到，具体如下：
一、表面化学接枝法
(1)取普通柔性微电极阵列，将所述柔性微电极阵列的基底进行表面氨基化或羟基化处理；
(2)将氨基化或羟基化的柔性电极与三氯硅烷基丙基甲基丙稀酸酯反应，使得柔性电极基底表面单分子层组装上一层含双键的丙稀酸酯官能团，得到化学修饰后的柔性微电极阵列；
(3)将含有可变形的刺激响应材料的预聚液设置于所述化学修饰后的柔性微电极阵列表面，采用本发明第二方面任意一种制备方法，得到形成在柔性微电极背面的刺激响应层，即得到所述刺激响应柔性微电极阵列。
所述步骤(1)中，当所述柔性微电极阵列的基底为聚酰亚胺基底时，将其浸没在乙二胺的水溶液中反应1-2h，使得柔性电极基底表面形成大量氨基，得到氨基化的柔性微电极阵列；当所述柔性微电极阵列的基底为聚对二甲苯基底或聚二甲基硅氧烷基底时，将柔性微电极阵列置于等离子体表面清洗机中，用氧气plasma(等离子体)轰击基底2-5min，使得基底表面形成大量羟基，得到羟基化的柔性微电极阵列。
所述步骤(3)中，将含有可变形的刺激响应材料的预聚液设置于所述化学修饰后的柔性微电极阵列表面的具体方式为：将含有可变形的刺激响应材料的预聚液注入模具中，模具由两片玻璃片、化学修饰后的柔性微电极阵列以及夹在中间的具有一定厚度的聚四氟乙烯框组成。
上述制备方法中，当所述刺激响应层具有定向排列的凹坑或凸起时，可以通过将含有可变形的刺激响应材料的预聚液注入模具后进行不同程度的辐照得到，也可以通过预先在模具底部的玻璃片表面光刻形成定向排列的凹坑或凸起而得到。所述不同辐照程度可以通过调整辐照剂量(包括辐照功率和辐照时间)实现，或选择部分区域辐照，部分区域不辐照实现。
二、物理涂敷法
该方法主要适用于湿度响应材料。将柔性微电极阵列平铺到一玻璃片表面，随后将微纳米材料在电极背面进行定向排列，再将具有一定厚度的聚四氟乙烯框紧贴玻璃片并用夹子固定，随后将湿度响应材料溶液注入模具中，经流延成膜后，并于80℃烘干48h，形成在柔性微电极背面的刺激响应层，即得到所述刺激响应柔性微电极阵列。
所述湿度响应材料溶液按以下方式制备：取含有大量亲水基团的高分子和含有大量羰基的聚酯类聚合物，将两者分别溶于溶剂中，然后以一定质量比混合均匀，得到湿度响应材料溶液；溶液中溶质的质量分数范围为0.1wt％-5wt％，溶剂可为二甲基甲酰胺等有机溶剂。
本发明提供的刺激响应柔性微电极阵列，通过外界刺激即可实现柔性微电极阵列的三维形变，进一步通过调节刺激响应层的厚度或交联度即可实现对柔性微电极阵列的形状进行可控调节，由此本发明可以有效调节柔性微电极的形状去匹配各种不规则的组织或器官，具有重大的生物医学意义。此外，本发明刺激响应层的制备过程对电极本身不会造成任何程度的破坏，结合光热效应、磁热效应纳米粒子能够实现响应材料本身与电极的远程驱动形变，且采用表面化学接枝的方法将刺激响应层与柔性微电极阵列结合起来，能够大大增加两者之间的粘附力，避免分层脱离现象的发生。
本发明的优点将会在下面的说明书中部分阐明，一部分根据说明书是显而易见的，或者可以通过本发明实施例的实施而获知。
附图说明
图1是本发明实施例1中可变形刺激响应材料的制备过程示意图；
图2是本发明实施例7中的刺激响应柔性微电极阵列的结构示意图；
图3是本发明实施例7中刺激响应柔性微电极阵列的形变图；
图4是本发明实施例8中刺激响应柔性微电极阵列的形变图；
图5是本发明实施例9中刺激响应柔性微电极阵列的形变图。
具体实施方式
以下所述是本发明实施例的优选实施方式，应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明实施例原理的前提下，还可以做出若干改进和润饰，这些改进和润饰也视为本发明实施例的保护范围。
实施例1
一种可变形刺激响应材料，其由热响应材料构成，所述热响应材料为聚异丙基丙烯酰胺，所述可变形刺激响应材料具有局部杨氏模量差异，所述局部杨氏模量差异由区域交联度的差异带来，所述可变形刺激响应材料为一厚度为1mm热响应水凝胶。
该可变形刺激响应材料的制备方法，包括以下步骤：
(1)将0.9156g异丙基丙烯酰胺，97mg甲叉双丙烯酰胺溶于10mL的水中混合均匀，随后加入光引发剂二乙氧基苯乙酮125μL，待溶液混合均匀后即得到预聚液；
(2)如图1所示，将预聚液注入模具中，所述模具由两片玻璃片以及夹在中间的具有一定厚度的聚四氟乙烯框组成，然后将具有特定结构的光掩模版(掩模版的线条角度为90°)置于所述模具上表面，将样品置于冰浴中紫外辐照10min，待遮挡部分与辐照部分的预聚液均聚合成型后，将样品浸泡在去离子水中24h去除未反应完的预聚液，即得到所述可变形的刺激响应材料，实质为热响应水凝胶，所述可变形的刺激响应材料整体具有相同的组分构成，且分区域具有不同的交联度，其中辐照部分的交联度高于遮挡部分，所述局部杨氏模量的差异由不同区域的交联度差异形成。
将本发明实施例1所得光热响应水凝胶置于45℃水溶液中，水凝胶由透明状逐步变为不透明的乳白色，并开始收缩，逐渐弯曲形成三维空心管状结构，将水凝胶放置于25℃水溶液中，空心管状的水凝胶逐步恢复至初始的平面结构，由此可见本实施例所得热响应水凝胶可以实现自身形状的可控调节。
实施例2
一种可变形刺激响应材料，其由A、B两组不同组分构成的光热响应材料构成，即可变形刺激响应材料部分区域由A组构成的光热响应材料构成，部分区域由B组构成的光热响应材料构成，具体地，A组构成包括温敏聚合物(具体为聚异丙基丙烯酰胺和聚(N-乙基丙烯酰胺))和光热纳米粒子(具体为金纳米棒)，B组构成为包括温敏聚合物(具体为聚(N-乙基丙烯酰胺))和光热纳米粒子(具体为金纳米棒)，A、B两组构成中，所述光热纳米粒子的重量百分比含量均为5％，所述可变形刺激响应材料具有局部杨氏模量差异，所述局部杨氏模量差异由A、B两组不同组分构成的材料本身的力学性质的差异带来，所述可变形刺激响应材料为一厚度为300μm光热响应水凝胶。
该可变形刺激响应材料的制备方法，包括以下步骤：
(1)将0.9156g异丙基丙烯酰胺，97mg甲叉双丙烯酰胺溶于5mL的水中，随后加入5mL金纳米棒(4mmol/L)溶液，混合均匀，加入光引发剂二乙氧基苯乙酮125μL，待溶液混合均匀后得到预聚液A；将0.9156g N-乙基丙烯酰胺,97mg甲叉双丙烯酰胺溶于5mL的水中，加入光引发剂二乙氧基苯乙酮125μL，及加入一定量的金纳米棒(5wt％)，混合均匀得到预聚液B；
(2)将预聚液A注入模具中，所述模具由两片玻璃片以及夹在中间的具有一定厚度的聚四氟乙烯框组成，然后将具有特定结构的光掩模版(掩模版的线条角度为0°)置于所述模具 上表面，然后将样品置于冰浴中紫外辐照5min，反应结束后用去离子水冲洗掉未辐照区域的预聚液A；
(3)再向模具中加入预聚液B，然后将样品置于冰浴中紫外辐照5min，反应结束后，将样品浸泡在去离子水中24h去除未反应完的预聚液B，得到所述可变形的刺激响应材料，其实质为光热响应水凝胶。
将本发明实施例2所得光热响应水凝胶置于25℃水溶液中，采用功率为5W的近红外光激光器去照射光热响应水凝胶，水凝胶由透明状逐步变为不透明的乳白色，并开始收缩，弯曲形成三维圆柱体结构，通过调节光照强度能够有效调节水凝胶的曲率，停止光照后，圆柱体状的水凝胶逐步恢复至初始的平面结构，由此可见所得光热响应水凝胶可以实现自身形状的可控调节。
实施例3
一种可变形刺激响应材料，具体包括温敏聚合物(具体为聚异丙基丙烯酰胺)和磁热纳米粒子(具体为四氧化三铁)，所述磁热纳米粒子的重量百分比含量为5％，所述可变形刺激响应材料具有局部杨氏模量差异，所述局部杨氏模量差异由四氧化三铁纳米粒子的定向排列带来，所述可变形刺激响应材料为一厚度为500μm磁热响应水凝胶。
该可变形刺激响应材料的制备是通过外部磁场的调控，使得刚性的四氧化三铁纳米粒子在异丙基丙烯酰胺的预聚液中沿长轴定向排列，随后通过辐照聚合形成复合凝胶，刚性四氧化三铁在柔性水凝胶材料中的定向排列带来局部杨氏模量的差异，具体制备过程如下：
(1)将0.9156g异丙基丙烯酰胺，97mg甲叉双丙烯酰胺溶于5mL的水溶液中，随后加入5mL四氧化三铁(4mmol/L)溶液，混合均匀，加入光引发剂二乙氧基苯乙酮125μL，待溶液混合均匀后得到预聚液；
(2)将预聚液注入模具中，所述模具由两片玻璃片以及夹在中间的具有一定厚度的聚四氟乙烯框组成，在模具附近施加一外加磁场，调节外加磁场的方向使得四氧化三铁粒子沿长轴定向排列，随后将样品置于冰浴中紫外辐照5min，反应结束后将样品浸泡在去离子水中24h去除未反应完的单体，得到所述可变形刺激响应材料。
将本发实施例所得磁热响应水凝胶置于25℃水溶液中，将容器置于0.05-1.2MHz的交变磁场中，磁性纳米颗粒吸收大量电磁波能量，铁氧体发生能量损耗，将部分电磁能转化为热能使自身温度升高，水凝胶逐步变为乳白色，并开始收缩，弯曲形成三维圆柱体结构，通过调节交变磁场的强度能够有效调节水凝胶的曲率，撤出磁场后，圆柱体状的水凝胶逐步恢复至初始的平面结构，由此可见本实施例所得磁热响应水凝胶可以实现自身形状的可控调节。
实施例4
一种可变形刺激响应材料，其由电热响应材料构成，具体包括温敏聚合物(具体为聚[低聚(乙二醇)单甲醚甲基丙烯酸酯])和电热纳米粒子(具体为碳黑)，所述电热纳米粒子的重量百分比含量为10％，所述可变形刺激响应材料具有局部杨氏模量差异，所述局部杨氏模量差异由微结构(微坑或微凸起)的定向排列带来，所述可变形刺激响应材料为一厚度为100μm电热响应水凝胶。
该可变形刺激响应材料的制备方法，包括以下步骤：
(1)将光刻胶AZ5214旋涂到经丙酮、异丙醇、乙醇清洗过的硅片表面，通过特定结构 的光掩模版(掩模版的线条角度为45°)经一次光刻或二次结构反转与显影后形成深度或高度为5微米的定向排列微坑或微凸起结构。
(2)将0.9156g低聚(乙二醇)单甲醚甲基丙烯酸酯，97mg甲叉双丙烯酰胺溶于5mL的水溶液中，随后加入5mL炭黑(8mmol/L)溶液，混合均匀，加入光引发剂二乙氧基苯乙酮125μL，待溶液混合均匀后得到预聚液；
(3)将预聚液注入模具中，所述模具由两片玻璃片，夹在中间的具有一定厚度的聚四氟乙烯框，以及位于聚四氟乙烯框下面且具有定向排列微结构的硅片组成，随后将样品置于冰浴中紫外辐照5min，反应结束后将样品浸泡在去离子水中24h去除未反应完的单体，得到所述可变形刺激响应材料。
将本发实施例所得电热响应水凝胶置于25℃水溶液中，将容器置于5V的外加电场中，电极间距为50mm，炭黑将部分电能转化为热能使自身温度升高，当温度超过聚[低聚(乙二醇)单甲醚甲基丙烯酸酯])的最低临界溶解温度时，水凝胶逐步变为乳白色，并开始收缩，弯曲形成三维螺旋状结构，通过调节外加电场的强度能够有效调节水凝胶的曲率，撤出电场后，螺旋状的水凝胶逐步恢复至初始的平面结构，由此可见本实施例所得电热响应水凝胶可以实现自身形状的可控调节。
实施例5
一种可变形刺激响应材料，其由湿度响应材料与纳米材料构成，具体包括含有大量亲水基团的高分子(具体为琼脂糖)和含有大量羰基的聚酯类(具体为聚甲基丙烯酸甲酯)，所述纳米材料为定向排列碳纳米管，所述纳米粒子的重量百分比含量为5％，所述可变形刺激响应材料具有局部杨氏模量差异，所述局部杨氏模量差异由碳纳米管的定向排列带来，所述可变形刺激响应材料为一厚度为20μm湿度响应薄膜。
该可变形刺激响应材料的制备方法，包括以下步骤：
(1)取1g琼脂糖加入10mL的二甲基甲酰胺溶剂中于100度热台上加热溶剂，另取1g聚甲基丙烯酸甲酯(平均分子量为15000)溶于二甲基甲酰胺溶剂中，取4.5g溶解好的琼脂糖溶液，加入900μL上述溶解完全的聚甲基丙烯酸酯溶液，搅拌混合均匀。
(2)将上述混合均匀的溶液注入模具中，所述模具由一片含有定向排列碳纳米管(与玻片长轴平行)的玻璃片，夹在玻片上具有一定厚度的聚四氟乙烯框组成，随后将样品置于80度烘箱中干燥24h去溶剂即得所述湿度响应薄膜。
将所述薄膜置于湿度为50％、温度为25℃的恒温恒湿箱中，琼脂糖溶胀薄膜弯曲形成空心管状结构，将薄膜转移于湿度为20％、温度为25℃的恒温恒湿箱中，薄膜水分挥发回复至初始平整结构，通过调节测试湿度含量能够有效调节薄膜的响应速率，由此可见本实施例所得湿度响应薄膜可以实现自身形状的可控调节。
实施例6
一种可变形刺激响应材料，其由pH响应材料构成，所述pH响应材料为聚甲基丙烯酸，所述可变形刺激响应材料具有局部杨氏模量差异，所述局部杨氏模量差异由区域交联度的差异带来，所述可变形刺激响应材料为一厚度为5mm的pH响应水凝胶。
该可变形刺激响应材料的制备方法，包括以下步骤：
(1)将0.9156g甲基丙烯酸，97mg甲叉双丙烯酰胺溶于10mL的水中混合均匀，随后加 入光引发剂二乙氧基苯乙酮125μL，待溶液混合均匀后即得到预聚液；
(2)将预聚液注入模具中，所述模具由两片玻璃片以及夹在中间的具有一定厚度的聚四氟乙烯框组成，然后将具有特定结构的光掩模版(掩模版的线条角度为45°)置于所述模具上表面，将样品置于冰浴中紫外辐照10min，待遮挡部分与辐照部分的预聚液均聚合成型后，将样品浸泡在去离子水中24h去除未反应完的预聚液，即得到所述可变形的刺激响应材料，实质为pH响应水凝胶，所述可变形的刺激响应材料整体具有相同的组分构成，且分区域具有不同的交联度，其中辐照部分的交联度高于遮挡部分，所述局部杨氏模量的差异由不同区域的交联度差异形成。
将本发明实施例1所得光热响应水凝胶置于pH＝3的水溶液中，水凝胶由透明状逐步变为不透明的乳白色，并开始收缩，逐渐弯曲形成三维螺旋状结构，将水凝胶放置于pH＝12的水溶液中，螺旋状的水凝胶逐步恢复至初始的平面结构，由此可见本实施例所得pH响应水凝胶可以实现自身形状的可控调节。
实施例7
一种刺激响应柔性微电极阵列，包括聚酰亚胺基底，设置在所述基底一侧的电极结构，以及接枝在所述基底另一侧的具有局部杨氏模量差异的刺激响应层，聚酰亚胺基底的厚度为10μm，刺激响应层的厚度为500μm，所述刺激响应层的材料为可变形的刺激响应材料，所述可变性的刺激响应材料为温敏聚合物(聚异丙基丙烯酰胺)所述局部杨氏模量差异由区域交联度的差异带来。
该刺激响应柔性微电极阵列的制备方法，包括以下步骤：
(1)基底表面的清洗
采用氮气吹扫除去聚酰亚胺基底表面的灰尘；
(2)基底表面氨基化
将柔性微电极阵列浸没于1.65mol/L的乙二胺水溶液中反应2h，经过胺类物质处理后，其链段当中的亚胺环断裂，生成酰胺，使得基底表面会出现大量的氨基，反应结束后用去离子水反复洗涤4-5次，自然干燥，得到氨基化的柔性微电极阵列；
(3)功能化丙烯酸酯类单体的自组装
待氨基化的柔性微电极阵列干燥后，将电极置于正己烷与四氯化碳的混合溶液中(正己烷与四氯化碳v:v＝1:4)，通N2 30min排除容器内的空气，随后将12mM(mmol/L)的三氯硅烷基丙基丙烯酸酯注入体系内，在N2氛围内反应1h，待反应结束后用正己烷与去离子水各洗涤3次，得到化学修饰后的柔性微电极阵列。
(4)热响应水凝胶的表面接枝
将0.9156g异丙基丙烯酰胺，97mg甲叉双丙烯酰胺溶于10mL的水溶液中，混合均匀，加入光引发剂二乙氧基苯乙酮125μL，待溶液混合均匀后的得到预聚液，将预聚液注入模具中，所述模具由两片玻璃片、化学修饰后的柔性微电极阵列以及夹在中间的具有一定厚度的聚四氟乙烯框组成，然后将具有特定结构的光掩模版(掩模版的线条角度为0°)置于所述模具上表面，将样品置于冰浴中紫外辐照10min，待遮挡部分与辐照部分的预聚液均聚合成型后，将样品浸泡在去离子水中24h去除未反应完的预聚液，得到形成在电极背面的刺激响应层，即得到刺激响应柔性微电极阵列。
图2是本发明实施例7中的刺激响应柔性微电极阵列的结构示意图(拆解图)；其中，10 为基底，201为刺激响应层，202为局部杨氏模量的差异。电极结构在基底10另一侧表面(图中未示出)。
将本实施例所得刺激响应柔性微电极阵列变置于45℃水溶液中，水凝胶层由透明状逐步变为不透明的乳白色，水凝胶层开始收缩，带动平面状的柔性微电极弯曲形成三维圆柱体结构(如图3所示)，将刺激响应柔性电极至于25℃水溶液中，圆柱体状的柔性电极逐步恢复至初始的平面结构，由此可见本实施例所得刺激响应柔性微电极阵列可以实现自身形状的可控调节。
实施例8
一种刺激响应柔性微电极阵列，包括聚酰亚胺基底，设置在所述基底一侧的电极结构，以及接枝在所述基底另一侧的具有局部杨氏模量差异的刺激响应层，聚酰亚胺基底的厚度为500μm，刺激响应层的厚度为5mm，所述刺激响应层的材料为可变形的刺激响应材料，其由A、B两组不同组分构成的光热响应材料构成，即可变形刺激响应材料部分区域由A组构成的光热响应材料构成，部分区域由B组构成的光热响应材料构成，具体地，A组构成包括温敏聚合物(具体为聚异丙基丙烯酰胺和聚(N-乙基丙烯酰胺))和光热纳米粒子(具体为金纳米棒)，B组构成为包括温敏聚合物(具体为聚(N-乙基丙烯酰胺))和光热纳米粒子(具体为金纳米棒)，A、B两组构成中，所述光热纳米粒子的重量百分比含量均为5％，所述可变形刺激响应材料具有局部杨氏模量差异，所述局部杨氏模量差异由A、B两组不同组分构成的材料本身的力学性质的差异带来。
该刺激响应柔性微电极阵列的制备方法，包括以下步骤：
(1)基底表面的清洗
采用氮气吹扫除去聚酰亚胺基底表面的灰尘；
(2)基底表面氨基化
将柔性微电极阵列浸没于1.65mol/L的乙二胺水溶液中反应2h，经过胺类物质处理后，其链段当中的亚胺环断裂，生成酰胺，使得基底表面会出现大量的氨基，反应结束后用去离子水反复洗涤4-5次，自然干燥，得到氨基化的柔性微电极阵列；
(3)功能化丙烯酸酯类单体的自组装
待氨基化的柔性微电极阵列干燥后，将电极置于正己烷与四氯化碳的混合溶液中(正己烷与四氯化碳v:v＝1:4)，通N2 30min排除容器内的空气，随后将12mmol/L的三氯硅烷基丙基丙烯酸酯注入体系内，在N2氛围内反应1h，待反应结束后用正己烷与去离子水各洗涤3次，得到化学修饰后的柔性微电极阵列。
(4)光热响应水凝胶的表面接枝
将0.9156g异丙基丙烯酰胺，97mg甲叉双丙烯酰胺溶于5mL的水中，随后加入5mL金纳米棒(4mmol/L)溶液，混合均匀，加入光引发剂二乙氧基苯乙酮125μL，待溶液混合均匀后得到预聚液A；将0.9156g N-乙基丙烯酰胺,97mg甲叉双丙烯酰胺溶于5mL的水中，加入光引发剂二乙氧基苯乙酮125μL，及加入一定量的金纳米棒(5wt％)，混合均匀得到预聚液B；将预聚液A注入模具中，所述模具由两片玻璃片、化学修饰后的柔性微电极阵列以及夹在中间的具有一定厚度的聚四氟乙烯框组成，然后将具有特定结构的光掩模版(掩模版的线条角度为45°)置于所述模具上表面，然后将样品置于冰浴中紫外曝光辐照5min，反应结束后用去离子水冲洗掉未曝光辐照区域的预聚液A；再向模具中加入预聚液B，然后将样品 置于冰浴中紫外曝光辐照5min，反应结束后，将样品浸泡在去离子水中24h去除未反应完的预聚液B，得到形成在电极背面的刺激响应层，即得到刺激响应柔性微电极阵列。
将本实施例所得刺激响应柔性微电极阵列置于25℃水溶液中，采用功率为5W的近红外光激光器去照射光热响应水凝胶层，水凝胶层由透明状逐步变为不透明的乳白色，平面状的柔性微电极阵列逐步变为三维螺旋形结构(如图4所示)，停止光照后，螺旋状的柔性电极逐步恢复至初始的平面结构。
实施例9
一种刺激响应柔性微电极阵列，包括聚酰亚胺基底，设置在所述基底一侧的电极结构，以及接枝在所述基底另一侧的具有局部杨氏模量差异的刺激响应层，聚酰亚胺基底的厚度为5μm，刺激响应层的厚度为100μm，所述刺激响应层的材料为可变形的刺激响应材料，包括温敏聚合物(聚异丙基丙烯酰胺)和电热纳米粒子(碳黑)，其中，所述光热纳米粒子的重量百分比含量为10％，所述局部杨氏模量差异由由微结构(微凸起)的定向排列带来。
该刺激响应柔性微电极阵列的制备方法，包括以下步骤：
(1)基底表面的清洗
采用氮气吹扫除去聚酰亚胺基底表面的灰尘；
(2)基底表面氨基化
将柔性微电极阵列浸没于1.65mol/L的乙二胺水溶液中反应2h，经过胺类物质处理后，其链段当中的亚胺环断裂，生成酰胺，使得基底表面会出现大量的氨基，反应结束后用去离子水反复洗涤4-5次，自然干燥，得到氨基化的柔性微电极阵列；
(3)功能化丙烯酸酯类单体的自组装
待氨基化的柔性微电极阵列干燥后，将电极置于正己烷与四氯化碳的混合溶液中(正己烷与四氯化碳v:v＝1:4)，通N2 30min排除容器内的空气，随后将12mmol/L的三氯硅烷基丙基丙烯酸酯注入体系内，在N2氛围内反应1h，待反应结束后用正己烷与去离子水各洗涤3次，得到化学修饰后的柔性微电极阵列。
(4)电热响应水凝胶的表面接枝
将0.9156g低聚(乙二醇)单甲醚甲基丙烯酸酯，97mg甲叉双丙烯酰胺溶于5mL的水溶液中，随后加入5mL炭黑(8mmol/L)溶液，混合均匀，加入光引发剂二乙氧基苯乙酮125μL，待溶液混合均匀后得到预聚液；将预聚液注入模具中，模具由两片玻璃片、化学修饰后的柔性微电极阵列以及夹在中间的具有一定厚度的聚四氟乙烯框组成，将样品置于冰浴中紫外辐照5min，聚合成型后在原先聚四氟乙烯框上加一层同等尺寸厚度为5微米的聚四氟乙烯框，并在上玻片表面放置具有特定结构的光掩模版(掩模版的线条角度为90°)，将预聚液注入模具中，将样品置于冰浴中紫外辐照5min，辐照区域聚合，遮挡部分未聚合，表面形成定向排列的凸起微结构，得到形成在电极背面的刺激响应层，即得到刺激响应柔性微电极阵列。将本实施例所得刺激响应柔性微电极阵列置于25℃水溶液中，将容器置于5V的外加电场中，电极间距为50mm，炭黑将部分电能转化为热能使自身温度升高，当温度超过聚[低聚(乙二醇)单甲醚甲基丙烯酸酯])的最低临界溶解温度时，水凝胶层开始收缩，平面状的柔性微电极阵列逐步变为空心管状结构(如图5所示)，撤出电场后，空心管状的柔性电极逐步恢复至初始的平面结构，由此可见本实施例所得刺激响应柔性微电极阵列可以实现自身形状的可控调节。
实施例10
一种刺激响应柔性微电极阵列，包括聚二甲基硅氧烷基底，设置在所述基底一侧的电极结构，以及接枝在所述基底另一侧的具有局部杨氏模量差异的刺激响应层，聚二甲基硅氧烷基底的厚度为5μm，刺激响应层的厚度为100μm，所述刺激响应层的材料为可变形的刺激响应材料，包括温敏聚合物(聚(三聚(乙二醇)单甲醚甲基丙烯酸酯))和光热纳米粒子(还原氧化石墨烯)，其中，所述光热纳米粒子的重量百分比含量为0.01％，所述局部杨氏模量差异由区域交联度的差异带来。
该刺激响应柔性微电极阵列的制备方法，包括以下步骤：
(1)基底表面的清洗
采用氮气吹扫除去聚二甲基硅氧烷基底表面的灰尘；
(2)基底表面活化
将柔性微电极阵列置于等离子体表面清洗机中，用氧气plasma轰击基底2min，使得聚二甲基硅氧烷基底表面形成大量羟基，得到羟基化的柔性微电极阵列；
(3)功能化丙烯酸酯类单体的自组装
将羟基化的柔性微电极阵列置于正己烷与四氯化碳的混合溶液中(v:v＝1:4)，通N2 30min排除容器内的空气，随后将12mmol/L的三氯硅烷基丙基丙烯酸酯注入体系内，在N2氛围内反应1h，待反应结束后用正己烷与去离子水各洗涤3次，得到化学修饰后的柔性微电极阵列。
(4)光热响应水凝胶的表面接枝
将0.9156g三聚(乙二醇)单甲醚甲基丙烯酸酯，97mg甲叉双丙烯酰胺溶液5mL的水溶液中，随后加入5mL还原氧化石墨烯(0.008mmol/L)溶液，混合均匀，加入光引发剂二乙氧基苯乙酮125μL，待溶液混合均匀后，将预聚液注入模具中，模具由两片玻璃片、化学修饰后的柔性微电极阵列以及夹在中间的具有一定厚度的聚四氟乙烯框组成，然后将具有特定结构的光掩模版(掩模版的线条角度为90°)置于所述模具上表面，将样品置于冰浴中紫外辐照10min，待遮挡部分与辐照部分的预聚液均聚合成型后，将样品浸泡在去离子水中24h去除未反应完的预聚液，得到形成在电极背面的刺激响应层，即得到刺激响应柔性微电极阵列。
将本实施例所得刺激响应柔性微电极阵列置于25℃水溶液中，采用功率为5W的近红外光激光器去照射光热响应水凝胶层，平面状的柔性微电极阵列逐步变为空心管状结构，停止光照后，空心管状的柔性电极逐步恢复至初始的平面结构。
实施例11
一种刺激响应柔性微电极阵列，包括聚对二甲苯基底，设置在所述基底一侧的电极结构，以及接枝在所述基底另一侧的具有局部杨氏模量差异的刺激响应层，聚对二甲苯基底的厚度为5μm，刺激响应层的厚度为100μm，所述刺激响应层的材料为可变形的刺激响应材料，包括温敏聚合物(聚(三聚(乙二醇)单甲醚甲基丙烯酸酯))和光热纳米粒子(还原氧化石墨烯)，其中，所述光热纳米粒子的重量百分比含量为0.5％，所述局部杨氏模量差异由区域交联度的差异带来。
该刺激响应柔性微电极阵列的制备方法，包括以下步骤：
(1)基底表面的清洗
采用氮气吹扫除去聚对二甲苯基底表面的灰尘；
(2)基底表面活化
将柔性微电极阵列置于等离子体表面清洗机中，用氧气plasma轰击基底2min，使得聚二甲基硅氧烷基底表面形成大量羟基，得到羟基化的柔性微电极阵列；
(3)功能化丙烯酸酯类单体的自组装
将羟基化的柔性微电极阵列置于正己烷与四氯化碳的混合溶液中(v:v＝1:4)，通N2 30min排除容器内的空气，随后将12mmol/L的三氯硅烷基丙基丙烯酸酯注入体系内，在N2氛围内反应1h，待反应结束后用正己烷与去离子水各洗涤3次，得到化学修饰后的柔性微电极阵列。
(4)光热响应水凝胶的表面接枝
将0.9156g三聚(乙二醇)单甲醚甲基丙烯酸酯，97mg甲叉双丙烯酰胺溶液5mL的水溶液中，随后加入5mL还原氧化石墨烯(0.4mmol/L)溶液，混合均匀，加入光引发剂二乙氧基苯乙酮125μL，待溶液混合均匀后，将预聚液注入模具中，模具由两片玻璃片、化学修饰后的柔性微电极阵列以及夹在中间的具有一定厚度的聚四氟乙烯框组成，然后将具有特定结构的光掩模版(掩模版的线条角度为45°)置于所述模具上表面，将样品置于冰浴中紫外辐照10min，待遮挡部分与辐照部分的预聚液均聚合成型后，将样品浸泡在去离子水中24h去除未反应完的预聚液，得到形成在电极背面的刺激响应层，即得到刺激响应柔性微电极阵列。
将本实施例所得刺激响应三维柔性微电极阵列置于25℃水溶液中，采用功率为5W的近红外光激光器去照射光热响应水凝胶层，平面状的柔性微电极阵列逐步变为螺旋状结构，停止光照后，螺旋状的柔性电极逐步恢复至初始的平面结构。
实施例12
一种刺激响应柔性微电极阵列，包括聚对二甲苯基底，设置在所述基底一侧的电极结构，以及接枝在所述基底另一侧的具有局部杨氏模量差异的刺激响应层，聚对二甲苯基底的厚度为5μm，刺激响应层的厚度为100μm，所述刺激响应层的材料为可变形的刺激响应材料，包括温敏聚合物(聚异丙基丙烯酰胺)和光热纳米粒子(碳纳米管)，其中，所述光热纳米粒子的重量百分比含量为0.5％，所述局部杨氏模量差异由区域交联度的差异带来。
该刺激响应柔性微电极阵列的制备方法，包括以下步骤：
(1)基底表面的清洗
采用氮气吹扫除去聚对二甲苯基底表面的灰尘；
(2)基底表面活化
将柔性微电极阵列置于等离子体表面清洗机中，用氧气plasma轰击基底2min，使得聚对二甲苯基底表面形成大量羟基，得到羟基化的柔性微电极阵列；
(3)功能化丙烯酸酯类单体的自组装
将羟基化的柔性微电极置于正己烷与四氯化碳的混合溶液中(v:v＝1:4)，通N2 30min排除容器内的空气，随后将12mmol/L的三氯硅烷基丙基丙烯酸酯注入体系内，在N2氛围内反应1h，待反应结束后用正己烷与去离子水各洗涤3次，得到化学修饰后的柔性微电极阵列。
(4)光热响应水凝胶的表面接枝
将0.9156g异丙基丙烯酰胺，97mg甲叉双丙烯酰胺溶液5mL的水溶液中，随后加入5mL碳纳米管(0.4mmol/L)溶液，混合均匀，加入光引发剂二乙氧基苯乙酮125μL，待溶液混合均匀后得到预聚液，将预聚液注入模具中，模具由两片玻璃片、化学修饰后的柔性微电极阵列以及夹在中间的具有一定厚度的聚四氟乙烯框组成，然后将具有特定结构的光掩模版(掩模版的线条角度为90°)置于所述模具上表面，将样品置于冰浴中紫外辐照10min，待遮挡部 分与辐照部分的预聚液均聚合成型后，将样品浸泡在去离子水中24h去除未反应完的预聚液，得到形成在电极背面的刺激响应层，即得到刺激响应柔性微电极阵列。
将本实施例所得刺激响应柔性微电极阵列置于25℃水溶液中，采用功率为5W的日光灯去照射光热响应水凝胶层，水凝胶层开始逐步收缩，带动平面状的柔性微电极阵列逐步弯曲形成空心管状结构，通过调节光照强度能够有效调节柔性微电极阵列的曲率，停止光照后，空心管状的柔性电极逐步恢复至初始的平面结构。
实施例13
一种刺激响应柔性微电极阵列，包括聚对二甲苯基底，设置在所述基底一侧的电极结构，以及接枝在所述基底另一侧的具有局部杨氏模量差异的刺激响应层，聚对二甲苯基底的厚度为5μm，刺激响应层的厚度为100μm，所述刺激响应层的材料为可变形的刺激响应材料，包括温敏聚合物(聚异丙基丙烯酰胺)和光热纳米粒子(碳纳米管)，其中，所述光热纳米粒子的重量百分比含量为0.5％，所述局部杨氏模量差异由区域交联度的差异带来。
该刺激响应柔性微电极阵列的制备方法，包括以下步骤：
(1)基底表面的清洗
采用氮气吹扫除去聚对二甲苯基底表面的灰尘；
(2)基底表面活化
将柔性微电极阵列置于等离子体表面清洗机中，用氧气plasma轰击基底2min，使得聚对二甲苯基底表面形成大量羟基，得到羟基化的柔性微电极阵列；
(3)功能化丙烯酸酯类单体的自组装
将羟基化的柔性微电极置于正己烷与四氯化碳的混合溶液中(v:v＝1:4)，通N2 30min排除容器内的空气，随后将12mmol/L的三氯硅烷基丙基丙烯酸酯注入体系内，在N2氛围内反应1h，待反应结束后用正己烷与去离子水各洗涤3次，得到化学修饰后的柔性微电极阵列。
(4)光热响应水凝胶的表面接枝
将0.9156g异丙基丙烯酰胺，97mg甲叉双丙烯酰胺溶液5mL的水溶液中，随后加入5mL碳纳米管(0.4mmol/L)溶液，混合均匀，加入光引发剂二乙氧基苯乙酮125μL，待溶液混合均匀后得到预聚液，将预聚液注入模具中，模具由两片玻璃片、化学修饰后的柔性微电极阵列以及夹在中间的具有一定厚度的聚四氟乙烯框组成，然后将具有特定结构的光掩模版(掩模版的线条角度为0°)置于所述模具上表面，将样品置于冰浴中紫外辐照10min，待遮挡部分与辐照部分的预聚液均聚合成型后，将样品浸泡在去离子水中24h去除未反应完的预聚液，得到形成在电极背面的刺激响应层，即得到刺激响应柔性微电极阵列。
将本实施例所得刺激响应柔性微电极阵列置于25℃水溶液中，采用功率为5W的日光灯去照射光热响应水凝胶层，水凝胶层开始逐步收缩，带动平面状的柔性微电极阵列逐步弯曲形成三维圆柱体结构，通过调节光照强度能够有效调节柔性微电极阵列的曲率，停止光照后，圆柱体状的柔性电极逐步恢复至初始的平面结构。
实施例14
一种刺激响应柔性微电极阵列，包括聚酰亚胺基底，设置在所述基底一侧的电极结构，以及接枝在所述基底另一侧的具有局部杨氏模量差异的刺激响应层，聚酰亚胺基底的厚度为5μm，刺激响应层的厚度为10μm，所述刺激响应层的材料为可变形的刺激响应材料，包括湿 度响应材料(琼脂糖和聚甲基丙烯酸甲酯的复合物)和光热纳米粒子(定向排列的碳纳米管)，其中，所述光热纳米粒子的重量百分比含量为0.5％，所述局部杨氏模量差异由碳纳米管的定向排列带来。
该刺激响应柔性微电极阵列的制备方法，包括以下步骤：
(1)基底表面的清洗
采用氮气吹扫除去聚酰亚胺基底表面的灰尘；
(2)基底表面氨基化
将柔性微电极阵列浸没于1.65mol/L的乙二胺水溶液中反应2h，经过胺类物质处理后，其链段当中的亚胺环断裂，生成酰胺，使得基底表面会出现大量的氨基，反应结束后用去离子水反复洗涤4-5次，自然干燥，得到氨基化的柔性微电极阵列；
(3)功能化丙烯酸酯类单体的自组装
待氨基化的柔性微电极阵列干燥后，将电极置于正己烷与四氯化碳的混合溶液中(正己烷与四氯化碳v:v＝1:4)，通N2 30min排除容器内的空气，随后将12mmol/L的三氯硅烷基丙基丙烯酸酯注入体系内，在N2氛围内反应1h，待反应结束后用正己烷与去离子水各洗涤3次，得到化学修饰后的柔性微电极阵列。
(4)湿度响应薄膜的流延成膜
称取1g琼脂糖溶于10mL二甲基甲酰胺中，另取1g聚甲基丙烯酸甲酯(MW＝4000)，溶于10mL二甲基甲酰胺中。取9g溶解好的琼脂糖溶液，加入450μL聚甲基丙烯酸甲酯溶液混合均匀。取一个洁净的载玻片，表面放置柔性微电极阵列，在电极背面平铺一层定向排列的碳纳米管(90°)，放置一定尺寸的聚四氟乙烯垫片，并用夹子固定，把混合均匀的琼脂糖与甲基丙烯酸甲酯的溶液平铺到垫片中流延成膜，置于70℃烘箱中烘烤48小时去除溶剂，得到形成在电极背面的刺激响应层，即得到刺激响应柔性微电极阵列。
取一片润湿的滤纸置于45℃热台上5分钟，待大部分水分去除后将本实施例所得刺激响应柔性微电极阵列置于45℃的滤纸上，湿度响应层吸水溶胀，沿着垂直于碳纳米管定向排列的方向弯曲(长轴)，形成三维圆柱体结构。待水分完全挥发后，圆柱体状的柔性电极逐步恢复至初始的平面结构。
实施例15
一种刺激响应柔性微电极阵列，包括聚酰亚胺基底，设置在所述基底一侧的电极结构，以及接枝在所述基底另一侧的具有局部杨氏模量差异的刺激响应层，聚酰亚胺基底的厚度为5μm，刺激响应层的厚度为500μm，所述刺激响应层的材料为可变形的刺激响应材料，包括pH响应材料(聚甲基丙烯酸二甲氨基乙酯水凝胶)，所述局部杨氏模量差异由区域交联度的差异带来。
该刺激响应柔性微电极阵列的制备方法，包括以下步骤：
(1)基底表面的清洗
采用氮气吹扫除去聚酰亚胺基底表面的灰尘；
(2)基底表面氨基化
将柔性微电极阵列浸没于1.65mol/L的乙二胺水溶液中反应2h，经过胺类物质处理后，其链段当中的亚胺环断裂，生成酰胺，使得基底表面会出现大量的氨基，反应结束后用去离子水反复洗涤4-5次，自然干燥，得到氨基化的柔性微电极阵列；
(3)功能化丙烯酸酯类单体的自组装
待氨基化的柔性微电极阵列干燥后，将电极置于正己烷与四氯化碳的混合溶液中(正己烷与四氯化碳v:v＝1:4)，通N2 30min排除容器内的空气，随后将12mmol/L的三氯硅烷基丙基丙烯酸酯注入体系内，在N2氛围内反应1h，待反应结束后用正己烷与去离子水各洗涤3次，得到化学修饰后的柔性微电极阵列。
(4)pH响应水凝胶的表面接枝
将0.9156g甲基丙烯酸二甲氨基乙酯，97mg甲叉双丙烯酰胺溶液10mL的水溶液中，超声溶解均匀，加入光引发剂二乙氧基苯乙酮125μL，待溶液混合均匀后得到预聚液，将预聚液注入模具中，模具由两片玻璃片、化学修饰后的柔性微电极阵列以及夹在中间的具有一定厚度的聚四氟乙烯框组成，然后将具有特定结构的光掩模版(掩模版的线条角度为90°)置于所述模具上表面，将样品置于冰浴中紫外辐照10min，待遮挡部分与辐照部分的预聚液均聚合成型后，将样品浸泡在去离子水中24h去除未反应完的预聚液，得到形成在电极背面的刺激响应层，即得到刺激响应柔性微电极阵列。
将本实施例所得刺激响应柔性微电极阵列置于pH＝10的氢氧化钠水溶液中，刺激响应层由透明状逐步变为不透明的乳白色，平面状的柔性微电极阵列逐步变为空心管状结构，随后将刺激响应柔性微电极阵列置于pH＝3的盐酸水溶液中，空心管状的柔性电极逐步恢复至初始的平面结构。
实施例16
一种刺激响应柔性微电极阵列，包括聚酰亚胺基底，设置在所述基底一侧的电极结构，以及接枝在所述基底另一侧的具有局部杨氏模量差异的刺激响应层，聚酰亚胺基底的厚度为5μm，刺激响应层的厚度为500μm，所述刺激响应层的材料为可变形的刺激响应材料，包括磁热响应材料(聚异丙基丙烯酰胺@Fe3O4水凝胶)，所述局部杨氏模量差异由微纳米材料的定向排列的定向排列带来。
该刺激响应柔性微电极阵列的制备方法，包括以下步骤：
(1)基底表面的清洗
采用氮气吹扫除去聚酰亚胺基底表面的灰尘；
(2)基底表面氨基化
将柔性微电极阵列浸没于1.65mol/L的乙二胺水溶液中反应2h，经过胺类物质处理后，其链段当中的亚胺环断裂，生成酰胺，使得基底表面会出现大量的氨基，反应结束后用去离子水反复洗涤4-5次，自然干燥，得到氨基化的柔性微电极阵列；
(3)功能化丙烯酸酯类单体的自组装
待氨基化的柔性微电极阵列干燥后，将电极置于正己烷与四氯化碳的混合溶液中(正己烷与四氯化碳v:v＝1:4)，通N2 30min排除容器内的空气，随后将12mmol/L的三氯硅烷基丙基丙烯酸酯注入体系内，在N2氛围内反应1h，待反应结束后用正己烷与去离子水各洗涤3次，得到化学修饰后的柔性微电极阵列。
(4)磁热响应水凝胶的表面接枝
将0.9156g异丙基丙烯酰胺，97mg甲叉双丙烯酰胺溶液5mL的水溶液中，加入5mLFe3O4的水溶液(2mmol/L)超声混合均匀，加入光引发剂二乙氧基苯乙酮125μL，待溶液混合均匀后得到预聚液，将预聚液注入如图2所示的模具中，模具由两片玻璃片、化学修饰后的柔 性微电极阵列以及夹在中间的具有一定厚度的聚四氟乙烯框组成，在模具附近施加一外加磁场，调节外加磁场的方向使得四氧化三铁沿与长轴成45°方向定向排列，随后将样品置于冰浴中紫外辐照10min，待遮挡部分与辐照部分的预聚液均聚合成型后，将样品浸泡在去离子水中24h去除未反应完的预聚液，得到形成在电极背面的刺激响应层，即得到刺激响应柔性微电极阵列。
将本实施例所得刺激响应柔性微电极阵列置于25℃水溶液中，并置于0.05-1.2MHz的交变磁场中，磁性纳米颗粒吸收大量电磁波能量，铁氧体发生能量损耗，将部分电磁能转化为热能使自身温度升高，当温度接近聚异丙基丙烯酰胺的相变温度时，水凝胶网络开始逐渐收缩，形成三维螺旋状结构，当撤去磁场后，体系温度降低，螺旋状的柔性电极逐步恢复至初始的平面结构。
需要说明的是，根据上述说明书的揭示和和阐述，本发明所属领域的技术人员还可以对上述实施方式进行变更和修改。因此，本发明并不局限于上面揭示和描述的具体实施方式，对本发明的一些等同修改和变更也应当在本发明的权利要求的保护范围之内。此外，尽管本说明书中使用了一些特定的术语，但这些术语只是为了方便说明，并不对本发明构成任何限制。

Claims (16)

  1. 一种可变形的刺激响应材料，其特征在于，所述可变形的刺激响应材料具有局部杨氏模量差异，所述可变形的刺激响应材料由热响应材料、光热响应材料、磁热响应材料、电热响应材料、湿度响应材料和pH响应材料中的至少一种刺激响应材料构成，所述可变形的刺激响应材料在温度、光、磁、电、湿度、pH中的一种或多种外界刺激条件下，可由平面二维结构转变成三维结构。
  2. 如权利要求1所述的可变形的刺激响应材料，其特征在于，所述局部杨氏模量差异的差异程度在0.0001Pa-2000Gpa范围内。
  3. 如权利要求1所述的可变形的刺激响应材料，其特征在于，所述可变形的刺激响应材料整体具有相同的组分构成，且分区域具有不同的交联度，所述局部杨氏模量差异由不同区域的交联度差异形成。
  4. 如权利要求1所述的可变形的刺激响应材料，其特征在于，所述可变形的刺激响应材料分区域具有不同的组分构成，所述局部杨氏模量差异由所述不同组分构成的不同力学性能差异形成。
  5. 如权利要求1所述的可变形的刺激响应材料，其特征在于，所述可变形的刺激响应材料整体具有相同的组分构成，且所述可变形的刺激响应材料中设置有定向排列的微结构，所述局部杨氏模量差异由所述微结构的定向排列形成，所述微结构包括凹坑、凸起或微纳米材料，所述微纳米材料包括石墨烯、碳纳米管、玻璃纤维、纳米颗粒中的至少一种。
  6. 如权利要求1所述的可变形的刺激响应材料，其特征在于，所述可变形的刺激响应材料分区域具有不同的组分构成，且所述可变形的刺激响应材料中设置有定向排列的微结构，所述局部杨氏模量差异由所述微结构的定向排列、以及所述不同组分构成的不同力学性能差异形成，所述微结构包括凹坑、凸起或微纳米材料，所述微纳米材料包括石墨烯、碳纳米管、玻璃纤维、纳米颗粒中的至少一种。
  7. 如权利要求5或6所述的可变形的刺激响应材料，其特征在于，所述凹坑的深度为10nm-5cm，所述凸起的高度为10nm-5cm。
  8. 如权利要求1所述的可变形的刺激响应材料，其特征在于，所述三维结构包括圆柱体、螺旋形、空心管状结构。
  9. 一种可变形的刺激响应材料的制备方法，其特征在于，包括以下步骤：
    取可变形的刺激响应材料的预聚液，所述预聚液包括热响应材料、光热响应材料、磁热响应材料、电热响应材料、pH响应材料中的至少一种的预聚体；
    将所述预聚液注入模具中，然后将具有特定结构的光掩模版置于所述模具上表面，采用辐照聚合的方式，待遮挡部分与曝露部分的预聚液均聚合成型后，得到可变形的刺激响应材料，所述可变形的刺激响应材料具有局部杨氏模量差异，所述可变形的刺激响应材料整体具有相同的组分构成，且分区域具有不同的交联度，所述曝露部分的交联度大于所述遮挡部分的交联度，所述局部杨氏模量差异由不同区域的交联度差异形成。
  10. 一种可变形的刺激响应材料的制备方法，其特征在于，包括以下步骤：
    取两份具有不同组分构成的可变形的刺激响应材料的预聚液，所述预聚液包括热响应材料、光热响应材料、磁热响应材料、电热响应材料和pH响应材料中的至少一种的预聚体；
    将其中一份所述预聚液注入模具中，然后将具有特定结构的掩模版置于所述模具上表面， 采用辐照聚合的方式，待曝露部分聚合成型，而遮挡部分未聚合成型时，除去所述遮挡部分未聚合的预聚液，然后将另一份所述预聚液注入上述模具中，经辐照聚合后，得到可变形的刺激响应材料，所述可变形的刺激响应材料具有局部杨氏模量差异，所述可变形的刺激响应材料分区域具有不同的组分构成，所述局部杨氏模量差异由所述不同组分构成的不同力学性能差异形成。
  11. 一种可变形的刺激响应材料的制备方法，其特征在于，包括以下步骤：
    取可变形的刺激响应材料的预聚液，所述预聚液包括热响应材料、光热响应材料、磁热响应材料、电热响应材料和pH响应材料中的至少一种的预聚体；
    取基底，在所述基底上形成定向排列的微结构，所述微结构包括凹坑、凸起或微纳米材料，然后将一框体置于所述基底上，形成模具，将所述预聚液注入所述模具中，经辐照聚合后，得到可变形的刺激响应材料，所述可变形的刺激响应材料具有局部杨氏模量差异，所述可变形的刺激响应材料整体具有相同的组分构成，且所述可变形的刺激响应材料中设有定向排列的微结构，所述局部杨氏模量差异由所述微结构的定向排列形成，所述微纳米材料包括石墨烯、碳纳米管、玻璃纤维、纳米颗粒中的至少一种。
  12. 一种可变形的刺激响应材料的制备方法，其特征在于，包括以下步骤：
    取两份具有不同组分构成的可变形的刺激响应材料的预聚液，所述预聚液包括热响应材料、光热响应材料、磁热响应材料、电热响应材料和pH响应材料中的至少一种的预聚体；
    取基底，在所述基底上形成定向排列的微结构，所述微结构包括凹坑、凸起或微纳米材料，然后将一框体置于所述基底上，形成模具，将其中一份所述预聚液注入模具中，然后将具有特定结构的掩模版置于所述模具上表面，采用辐照聚合的方式，待曝露部分聚合成型，而遮挡部分未聚合成型时，除去所述遮挡部分未聚合的预聚液，然后将另一份所述预聚液注入上述模具中，经辐照聚合后，得到可变形的刺激响应材料，所述可变形的刺激响应材料具有局部杨氏模量差异，所述可变形的刺激响应材料分区域具有不同的组分构成，所述局部杨氏模量差异由所述微结构的定向排列和所述不同组分构成的不同力学性能差异形成，所述微纳米材料包括石墨烯、碳纳米管、玻璃纤维、纳米颗粒中的至少一种。
  13. 一种可变形的刺激响应材料的制备方法，其特征在于，包括以下步骤：
    取含有大量亲水基团的高分子和含有大量羰基的聚酯类聚合物，将两者分别溶于溶剂中，然后以一定质量比混合均匀，得到湿度响应材料溶液；
    取基底，将微纳米材料在所述基底上定向排列，然后将一框体置于所述基底上，形成模具，将上述湿度响应材料溶液注入模具中，经流延成膜后得到可变形的刺激响应材料，所述可变形的刺激响应材料具有局部杨氏模量差异，所述局部杨氏模量差异由微纳米材料的定向排列形成，所述微纳米材料包括石墨烯、碳纳米管、玻璃纤维、纳米颗粒中的至少一种。
  14. 一种刺激响应柔性微电极阵列，其特征在于，包括柔性基底，设置在所述柔性基底一侧的电极结构，以及设置在所述柔性基底另一侧的刺激响应层，所述刺激响应层的材料包括权利要求1-8任一项所述的可变形的刺激响应材料。
  15. 如权利要求14所述的刺激响应柔性微电极阵列，所述柔性基底的厚度为1μm-5mm，所述刺激响应层的厚度为1μm-1cm。
  16. 如权利要求14所述的刺激响应柔性微电极阵列，所述刺激响应层通过表面化学接枝或物理涂覆的方式形成在所述柔性基底表面。
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CN118892983A (zh) * 2024-07-15 2024-11-05 哈尔滨工业大学 一种柔性致动器及其制备方法
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CN111013014A (zh) * 2019-12-17 2020-04-17 中国科学院深圳先进技术研究院 神经组织刺激复合材料、复合膜及神经组织假体
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CN115926072A (zh) * 2022-10-08 2023-04-07 南京师范大学 一种基于水相沉淀聚合法制备Fe3O4复合纳米粒子方法
CN116376084A (zh) * 2023-04-07 2023-07-04 哈尔滨工业大学 一种形状记忆结构与响应分子协同调控固体和液体粘附复合材料及其制备和粘附调控方法
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CN117226806A (zh) * 2023-09-26 2023-12-15 广东工业大学 一种集群磁控微纳机器人及其制备方法
CN118147820A (zh) * 2024-03-14 2024-06-07 山东大学 一种有机聚合物纳米复合纤维收缩膜及其制备方法与在制备伤口敷料中的应用
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