WO2018090329A1 - 一种具有功能化的柔性电极及其制备方法 - Google Patents
一种具有功能化的柔性电极及其制备方法 Download PDFInfo
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- WO2018090329A1 WO2018090329A1 PCT/CN2016/106428 CN2016106428W WO2018090329A1 WO 2018090329 A1 WO2018090329 A1 WO 2018090329A1 CN 2016106428 W CN2016106428 W CN 2016106428W WO 2018090329 A1 WO2018090329 A1 WO 2018090329A1
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- flexible electrode
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
- H01B5/14—Non-insulated conductors or conductive bodies characterised by their form comprising conductive layers or films on insulating-supports
Definitions
- the invention relates to a flexible electrode, in particular to a flexible electrode with functionalization and a preparation method thereof.
- implantable devices such as implantable medical devices
- flexible electrodes because most of the human tissues are rugged or even have a certain curvature, such as the retina, cochlea, brain, etc.
- Good adhesion to the stimulation site directly affects the effectiveness of the implanted device (Survey of Ophthalmology, 2002, 47, 335-356).
- implantable devices in the event of malfunction and danger, they can only be removed by surgery, which can cause greater trauma to the patient. What's more, some implanted devices, such as artificial retinas, combine with human tissue after implantation, so they are not easily replaceable.
- the shape change of the flexible electrode was achieved by pressure-induced deformation in an annealed manner, but it was easy to damage expensive electrodes (Survey of Ophthalmology, 2002, 47, 335-356).
- Recently, Harvard University's Charles M. Lieber team developed an injectable metal mesh electrode that automatically unfolds when injected into a living body.
- the electrode deployment is based solely on the release of stress in the metal mesh electrode, which may result in Tissue damage (Nature Nanotechnology, 2015, 10, 629-636), and the entire metal network can only be used as a single stimulus or information acquisition unit, unable to achieve multi-channel stimulation or information collection.
- the present invention is directed to a functionalized flexible electrode and a method of making the same.
- the functionalized flexible electrode can be realized by stimulation of temperature, humidity, light, etc., has good practicability and wide adaptability, and can be widely applied in the fields of aviation, aerospace, medicine and bioengineering.
- a flexible electrode having a flexible substrate, the flexible substrate comprising a flexible material, one side of the flexible substrate is provided with an electrode material, and the other side of the flexible substrate is functionalized material.
- the functionalized material has a thickness of from 0.01 ⁇ m to 2 cm. Further preferably, the functionalized material has a thickness of from 0.1 ⁇ m to 800 ⁇ m. The thickness selection of the functionalized material allows for adjustment of the functionalized flexible electrode response time.
- the functionalized material has a molecular weight of from 100 to 70 million. Further preferably, the functionalized material has a molecular weight of from 100 to 10 million. The molecular weight of the functionalized material is selected to achieve mechanical properties adjustment of the functionalized flexible electrode responsive material.
- the functionalized material comprises at least one of a temperature sensitive material, a humidity sensitive material, and a light sensitive material.
- the temperature sensitive material comprises ethylene oxide, polyvinyl methyl ether, polyhydroxypropyl acrylate, polyethylene glycol, derivatives of polyethylene glycol, poly-N substituted acrylamide, and elastic-like Protein polypeptide, styrene-butadiene copolymer, trans-polyisoprene, ethylene-vinyl acetate copolymer, polynorbornene, polyurethane (PU), epoxy resin (EP), ethylene-vinyl acetate copolymerization (EVA), polyimide (PI), cellulose, polycaprolactone (PCL), polylactic acid (PLA), polyglycolic acid (PGA), polylactic acid-glycolic acid copolymer (PLGA), polyethylene At least one of alcohol (PVA) polymers;
- the moisture sensitive material comprises at least one of silk protein, spider silk, hydrogel;
- the light sensitive material comprises cinnamyl, azo, triphenylmethane, two At least one of the st
- the functionalized material further comprises a functional conversion material.
- the weight of the functionalized conversion material is from 0.001% to 50% by weight of the functionalized material. , further preferably 0.01% to 30%.
- the functional conversion material includes at least one of an inorganic photothermal conversion material, an organic photothermal conversion material, an organic electrothermal conversion material, and a magnetothermal conversion material.
- the inorganic photothermal conversion material comprises one or more of nano gold, nano silver, nano copper, nano platinum, nano palladium, nano bismuth, carbon nanotube, black phosphorus and graphene, or surface functionalization One or more of nano gold, nano silver, nano copper, nano platinum, nano palladium, nano bismuth, carbon nanotube, carbon black, black phosphorus and graphene, or nano gold, nano silver, nano copper, nano One or more of a composite material of platinum, nanopalladium, nano cerium, carbon nanotube, carbon black, black phosphorus, graphene; the organic photothermal conversion material comprises polypyrrole, polyaniline, polyethylene dioxythiophene One or more of polystyrene sulfonate, phthalocyanine green, porphyrin liposome, and modified materials thereof; magnetocaloric conversion materials include Fe 2 O 3 , Fe 3 O 4 , FeCo, One or more of NiFe, CoFeO, NiFeO, MnFeO,
- the flexible substrate is at least one of a plastic, a rubber, a hydrogel, and a composite thereof.
- the plastic comprises one or more of polyimide (PI), parylene, polylactic acid, polyglycolic acid, polylactic acid-glycolic acid copolymer, and composite materials thereof;
- the rubber includes one or more of polydimethylsiloxane (PDMS), silica gel, and a composite thereof;
- the hydrogel includes polyethylene glycol, polyvinyl alcohol, chitosan, alginic acid One or more of sodium, agarose, cellulose, silk fibroin, nucleic acids, polypeptides, and composites thereof.
- the present invention provides a method for preparing a functionalized flexible electrode as described above, comprising the steps of:
- the manner of curing in the step (2) comprises photocuring, heat curing, radiation curing or chemical crosslinking.
- the functionalized material is grafted to the surface of the flexible substrate by chemical crosslinking.
- the functional material is grafted to the surface of the flexible substrate by chemical crosslinking, and the surface of the flexible substrate needs to be chemically modified to be attached to at least one of a carbon-carbon double bond, an amino group, a carboxyl group, a hydroxyl group and a thiol group.
- the functional material is then grafted to the surface of the flexible substrate by chemical crosslinking by irradiation polymerization, thermal polymerization, photoinitiated polymerization.
- the functional material is applied to the surface of the flexible substrate by casting, spin coating, knife coating, spraying, etc., and then cured on the surface of the flexible substrate.
- the invention designs a plurality of functionalized polymer materials to the surface of the flexible electrode substrate, and by compounding with the functional micro-nano material, the flexible electrode shape adaptive change function can be realized under the stimulation of temperature, humidity and light.
- the method for preparing the functionalized flexible electrode is diversified, and the composite material can also be applied to the substrate of the flexible electrode to realize the functionalization of the flexible electrode.
- the functional adaptability of the functionalized flexible electrode can be remotely adjusted, and the functionalized flexible electrode can be extended in the fields of medical and bioengineering such as wearing and implanting.
- the invention realizes the functionalization of the wearable and implantable electrodes, has various preparation methods, high reliability and good safety, and expands the application field of the intelligent polymer materials.
- the functionalized flexible electrode can realize shape change by temperature, humidity, light and other stimuli, and the method is diversified, and the control is convenient, which lays a solid foundation for the application of the functionalized flexible electrode in the field of wearable and implantable medical treatment.
- the functionalized flexible electrode of the invention can adapt the shape to match the living tissue, and solves the problems that the existing flexible electrode can not effectively match the living tissue and affect the electrophysiological stimulation and signal acquisition. Improve the reliability and effectiveness of functionalized flexible electrodes in the field of wearable and implantable medical applications.
- Embodiment 1 is a shape-adjustable flexible electrode according to Embodiment 1 of the present invention.
- FIG. 2 is a functional diagram of a shape-adjustable flexible electrode of the real-time example 2 of the present invention.
- the flexible electrode comprises a flexible substrate, the flexible substrate is made of polydimethylsiloxane, and one side of the flexible substrate is provided with an electrode material. The other side of the flexible substrate is provided with a functionalized material.
- the preparation method of the functionalized flexible electrode comprises the following steps:
- the poly-N-isopropylacrylamide hydrogel with temperature-sensitive properties grafted onto the flexible substrate surface of the PI flexible electrode by grafting method can realize the shape change of the PI substrate flexible electrode under human body temperature, as shown in Fig. 1. It is shown that the left side of Fig. 1 is before the deformation of the flexible electrode, and the right side is after the deformation of the flexible electrode.
- the flexible electrode comprises a flexible substrate, the flexible substrate is made of parylene, and one side of the flexible substrate is provided with an electrode material, the flexibility The other side of the substrate is provided with a functionalized material.
- the preparation method of the functionalized flexible electrode comprises the following steps:
- the flexible electrode based on parylene was used as a spinning voltage of 20KV between the receiving devices, the spinning distance between the spinning needle and the receiving aluminum foil was controlled to be 13 cm, and the flow rate of the electrospinning solution was adjusted to 0.01 mL/min.
- the wire needle has an inner diameter of 0.9 mm, a spinning temperature of 25 ° C, and an air humidity of 53%.
- a functionalized flexible electrode having a shape memory effect is produced by an electrospinning technique.
- the flexible electrode coated with polycaprolactone (PCL) on the surface of the flexible substrate can be shaped and curled in vitro, and the body temperature is triggered to realize the self-expanding function after the implant, as shown in FIG. 2, the shape is fixed on the left side in FIG.
- the middle is the electrode when unfolded
- the right is the front view of the flexible electrode after unfolding.
- the flexible electrode comprises a flexible substrate, the material of the flexible substrate is polyimide, and one side of the flexible substrate is provided with an electrode material, the flexibility The other side of the substrate is provided with a functionalized material.
- the preparation method of the functionalized flexible electrode comprises the following steps:
- the shape memory function of the flexible electrode is realized, and the flexible electrode is specifically shaped, and the shape recovery of the flexible electrode can be realized by near-infrared illumination. .
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Abstract
Description
Claims (14)
- 一种具有功能化的柔性电极,其特征在于,所述柔性电极包括柔性基底,所述柔性基底的一面设有电极材料,所述柔性基底的另一面设有功能化材料。
- 根据权利要求1所述的具有功能化的柔性电极,其特征在于,所述功能化材料的厚度为0.1μm~1cm。
- 根据权利要求1所述的具有功能化的柔性电极,其特征在于,所述功能化材料的厚度为0.1μm~8 00μm。
- 根据权利要求1所述的具有功能化的柔性电极,其特征在于,所述功能化材料的分子量为100~7000万。
- 根据权利要求1所述的具有功能化的柔性电极,其特征在于,所述功能化材料的分子量为100~1000万。
- 根据权利要求1所述的具有功能化的柔性电极,其特征在于,所述功能化材料包括温敏材料、湿度敏感材料、光敏感材料中的至少一种。
- 根据权利要求6所述的具有功能化的柔性电极,其特征在于,所述的温敏材料包括环氧乙烷、聚乙烯基甲醚、聚羟丙基丙烯酸酯、聚乙二醇、聚乙二醇的衍生物、聚-N取代丙烯酰胺、类弹性蛋白多肽、苯乙烯-丁二烯共聚物、反式聚异戊二烯、乙烯-醋酸乙烯共聚物、聚降冰片烯、聚氨酯、环氧树脂、乙烯-醋酸乙烯酯共聚物、聚酰亚胺、纤维素、聚己内酯、聚乳酸、聚乙醇酸、聚乳酸-羟基乙酸共聚物、聚乙烯醇聚合物中的至少一种;所述湿度敏感材料包括蚕丝蛋白、蜘蛛丝、水凝胶中的至少一种;所述光敏感材料包括肉桂基、偶氮、三苯甲烷、二苯乙烯基团中的至少一种。
- 根据权利要求6所述的具有功能化的柔性电极,其特征在于,所述功能化材料还包括功能转换材料。
- 根据权利要求8所述的具有功能化的柔性电极,其特征在于,所述功能转换材料包括无机光热转换材料、有机光热转换材料、有机电热转换材料和磁致热转换材料中的至少一种。
- 根据权利要求9所述的具有功能化的柔性电极,其特征在于,所述无 机光热转换材料包括纳米金、纳米银、纳米铜、纳米铂、纳米钯、纳米锗、碳纳米管、黑磷和石墨烯中的一种或多种,或表面功能化的纳米金、纳米银、纳米铜、纳米铂、纳米钯、纳米锗、碳纳米管、炭黑、黑磷和石墨烯中的一种或多种,或纳米金、纳米银、纳米铜、纳米铂、纳米钯、纳米锗、碳纳米管、炭黑、黑磷、石墨烯的复合材料中的一种或多种;所述有机光热转换材料包括聚吡咯、聚苯胺、聚乙烯二氧噻吩、聚苯乙烯磺酸盐、吲哚菁绿、卟啉脂质体以及它们的改性材料中的一种或多种;磁致热转换材料包括Fe2O3、Fe3O4、FeCo、NiFe、CoFeO、NiFeO、MnFeO以及它们的复合材料中的一种或多种。
- 根据权利要求1所述的具有功能化的柔性电极,其特征在于,所述柔性基底为塑料、橡胶、水凝胶以及它们的复合材料中的至少一种。
- 根据权利要求11所述的具有功能化的柔性电极,其特征在于,所述塑料包括聚酰亚胺、聚对二甲苯、聚乳酸、聚乙醇酸、聚乳酸-羟基乙酸共聚物以及它们的复合材料中的一种或多种;所述橡胶包括聚二甲基硅氧烷、硅胶以及它们的复合材料中的一种或多种;所述水凝胶包括聚乙二醇、聚乙烯醇、壳聚糖、海藻酸钠、琼脂糖、纤维素、蚕丝蛋白、核酸、多肽以及它们的复合材料中的一种或多种。
- 一种如权利要求1-12任一所述的具有功能化的柔性电极的制备方法,其特征在于,包括以下步骤:(1)提供具有柔性基底的柔性电极;(2)将功能化材料固化到所述柔性电极的柔性基底表面。
- 根据权利要求13所述的制备方法,其特征在于,所述步骤(2)中固化的方式包括光固化、热固化、辐照固化或化学交联。
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