WO2024109854A1 - Flexible optical electrode and preparation method therefor - Google Patents

Flexible optical electrode and preparation method therefor Download PDF

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WO2024109854A1
WO2024109854A1 PCT/CN2023/133462 CN2023133462W WO2024109854A1 WO 2024109854 A1 WO2024109854 A1 WO 2024109854A1 CN 2023133462 W CN2023133462 W CN 2023133462W WO 2024109854 A1 WO2024109854 A1 WO 2024109854A1
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flexible optical
optical fiber
flexible
pedot
inner core
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PCT/CN2023/133462
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French (fr)
Chinese (zh)
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蒋路遥
钟成
鲁艺
曹燚
孙重阳
吴歌
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中国科学院深圳先进技术研究院
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Abstract

The present application discloses a flexible optical electrode and a preparation method therefor, belonging to the technical field of biomedical materials. Compared with the prior art wherein the shape of existing commercial optical electrodes does not adapt well to the peripheral nerve tissue after being implanted therein, the flexible optical electrode of the present application comprises a flexible optical fiber inner core and a flexible optical fiber coating layer coating the outer side of the flexible optical fiber inner core. The flexible optical electrode of the present application thus exhibits excellent optical transmission performance as well as excellent flexibility and a low modulus of elasticity. The flexible optical electrode further comprises PEDOT conductive fiber arranged on two sides of the flexible optical fiber inner core. The flexible optical electrode of the present application thus further exhibits excellent electrical performance, can exert optical stimulation on the peripheral nerve tissue, and can further record neural electrical signals. The flexible optical electrode further comprises a flexible packaging layer, giving the entirety of the flexible optical electrode excellent biocompatibility, and can effectively reduce damage during long-term implantation in the peripheral nerve tissue.

Description

一种柔性光电极及其制备方法A flexible photoelectrode and a method for preparing the same 技术领域Technical Field
本申请涉及生物医用材料技术领域,尤其涉及一种柔性光电极及其制备方法。The present application relates to the technical field of biomedical materials, and in particular to a flexible photoelectrode and a preparation method thereof.
背景技术Background technique
将现有的商用光电极植入外周神经组织后,由于外周神经周围的组织和现有的商用光电极之间存在弹性模量的失配问题,光电极不会随组织一起形变,因此,在组织弯曲、收缩的过程中,光电极与组织接触的界面上会发生应力集中效应,导致界面上的组织严重受损,从而诱发组织的发炎、坏死、积液等。After the existing commercial photoelectrodes are implanted into the peripheral nerve tissue, due to the mismatch in elastic modulus between the tissue surrounding the peripheral nerve and the existing commercial photoelectrodes, the photoelectrodes will not deform along with the tissue. Therefore, during the bending and contraction of the tissue, a stress concentration effect will occur at the interface where the photoelectrode contacts the tissue, causing serious damage to the tissue at the interface, thereby inducing inflammation, necrosis, and effusion of the tissue.
技术问题technical problem
现有技术中存在植入光电极对外周神经组织损伤较大的问题。The existing technology has the problem that implanted photoelectrodes cause significant damage to peripheral nerve tissue.
技术解决方案Technical Solutions
本申请的主要目的在于提供一种柔性光电极的制备方法,旨在解决现有技术中植入光电极对外周神经组织损伤较大的技术问题。The main purpose of the present application is to provide a method for preparing a flexible photoelectrode, aiming to solve the technical problem in the prior art that implanted photoelectrodes cause significant damage to peripheral nerve tissue.
为实现上述目的,本申请提供一种柔性光电极,所述柔性光电极包括柔性光纤内芯、包覆于所述柔性光纤内芯外侧的柔性光纤包覆层、排列在所述柔性光纤内芯两侧的PEDOT导电纤维丝,以及柔性封装层。To achieve the above objectives, the present application provides a flexible optical electrode, which includes a flexible optical fiber core, a flexible optical fiber coating layer coated on the outside of the flexible optical fiber core, PEDOT conductive fiber filaments arranged on both sides of the flexible optical fiber core, and a flexible packaging layer.
可选地,所述柔性光纤内芯以及所述柔性封装层的材料均为PDMS,所述柔性光纤包覆层的材料为聚甲基氢硅氧烷。Optionally, the materials of the flexible optical fiber inner core and the flexible packaging layer are both PDMS, and the material of the flexible optical fiber coating layer is polymethylhydrogensiloxane.
可选地,所述柔性光纤内芯的折射率为1.41-1.412。Optionally, the refractive index of the inner core of the flexible optical fiber is 1.41-1.412.
本申请还提供一种柔性光电极的制备方法,所述制备方法包括:The present application also provides a method for preparing a flexible photoelectrode, the preparation method comprising:
在柔性光纤内芯表面涂覆一层聚甲基氢硅氧烷,形成柔性光纤包覆层;A layer of polymethylhydrogensiloxane is coated on the surface of the inner core of the flexible optical fiber to form a flexible optical fiber coating layer;
将多根PEDOT导电纤维丝排列在涂覆有聚甲基氢硅氧烷的柔性光纤内芯两侧;Arrange multiple PEDOT conductive fibers on both sides of a flexible optical fiber core coated with polymethylhydrogensiloxane;
通过3D打印机使用PDMS,对排列好的柔性光纤内芯以及PEDOT导电纤维丝进行封装,形成柔性封装层,得到制备好的柔性光电极。The arranged flexible optical fiber cores and PEDOT conductive fiber filaments are encapsulated using PDMS through a 3D printer to form a flexible encapsulation layer to obtain a prepared flexible photoelectrode.
可选地,所述柔性光纤内芯的制备方法,包括:Optionally, the method for preparing the flexible optical fiber inner core comprises:
将PDMS和PDMS固化剂混合并搅拌均匀,得到PDMS和PDMS固化剂的混合液,其中,PDMS和PDMS固化剂的质量比为5:1;The PDMS and the PDMS curing agent are mixed and stirred evenly to obtain a mixed solution of the PDMS and the PDMS curing agent, wherein the mass ratio of the PDMS and the PDMS curing agent is 5:1;
除去所述混合液中的气泡,通过注射装置将所述混合液注入至特氟龙管中;removing bubbles in the mixed solution, and injecting the mixed solution into a Teflon tube through an injection device;
待所述混合液固化成型后,将所述特氟龙管剥离,得到柔性光纤内芯。After the mixed liquid is solidified and formed, the Teflon tube is peeled off to obtain a flexible optical fiber inner core.
可选地,所述PEDOT导电纤维丝的制备方法,包括:Optionally, the method for preparing the PEDOT conductive fiber comprises:
通过3D打印机将PEDOT:PSS注入至异丙醇溶液中,凝固形成PEDOT:PSS导电纤维丝;PEDOT:PSS is injected into an isopropanol solution through a 3D printer and solidified to form PEDOT:PSS conductive fiber filaments;
将PEDOT:PSS导电纤维丝放至浓硫酸中酸洗8-15分钟;Place the PEDOT:PSS conductive fiber in concentrated sulfuric acid for pickling for 8-15 minutes;
使用乙醇将酸洗处理后的PEDOT:PSS导电纤维丝多次洗涤,干燥后得到PEDOT导电纤维丝。The acid-washed PEDOT:PSS conductive fiber filaments were washed multiple times with ethanol and dried to obtain PEDOT conductive fiber filaments.
可选地,所述通过3D打印机将PEDOT:PSS注入至异丙醇溶液的过程中使用的3D打印机的针头大小为23G,打印半径为50-80毫米的圆形,注入速度为300-400微升/分钟。Optionally, the needle size of the 3D printer used in the process of injecting PEDOT:PSS into the isopropanol solution through the 3D printer is 23G, the printing radius is 50-80 mm, and the injection speed is 300-400 μl/min.
可选地,所述PEDOT导电纤维丝的直径为10-100微米。Optionally, the diameter of the PEDOT conductive fiber is 10-100 microns.
可选地,所述在柔性光纤内芯表面涂覆一层聚甲基氢硅氧烷,形成柔性光纤包覆层的步骤之后,所述方法还包括:Optionally, after the step of coating a layer of polymethylhydrogensiloxane on the surface of the inner core of the flexible optical fiber to form a flexible optical fiber coating layer, the method further comprises:
将涂覆有聚甲基氢硅氧烷的柔性光纤内芯放入烘箱,在真空120-130摄氏度下加热30-35分钟。The flexible optical fiber inner core coated with polymethylhydrogensiloxane is placed in an oven and heated at 120-130 degrees Celsius for 30-35 minutes under vacuum.
可选地,所述在柔性光纤内芯表面涂覆一层聚甲基氢硅氧烷,形成柔性光纤包覆层的步骤之前,所述方法还包括:Optionally, before the step of coating a layer of polymethylhydrogensiloxane on the surface of the inner core of the flexible optical fiber to form a flexible optical fiber coating layer, the method further comprises:
使用乙醇和超纯水对制备好的柔性光纤内芯进行清洗。The prepared flexible optical fiber core was cleaned using ethanol and ultrapure water.
有益效果Beneficial Effects
本申请提出一种柔性光电极的制备方法,相较于现有技术中将现有的商用光电极植入外周神经组织后,光电极不会随外周神经组织一起形变,本申请的柔性光电极包括柔性光纤内芯以及包覆于所述柔性光纤内芯外侧的柔性光纤包覆层,因此,本申请的柔性光电极不仅具有良好的拥有良好的光传输性能,还具有良好的柔性,弹性模量较低,能够与神经组织相匹配;柔性光电极还包括排列在所述柔性光纤内芯两侧的PEDOT导电纤维丝,因此,本申请的柔性光电极还拥有良好电学性能,能够对外周神经组织施加光刺激,还能够记录神经电信号,保有光电极的基本性能;柔性光电极还包括柔性封装层,使柔性光电极整体具有良好的生物相容性,能够有效降低长期植入外周神经组织过程中的损伤。The present application proposes a method for preparing a flexible photoelectrode. Compared with the prior art in which the existing commercial photoelectrode is implanted into peripheral nerve tissue, the photoelectrode will not deform along with the peripheral nerve tissue. The flexible photoelectrode of the present application includes a flexible optical fiber core and a flexible optical fiber coating layer coated on the outside of the flexible optical fiber core. Therefore, the flexible photoelectrode of the present application not only has good light transmission performance, but also has good flexibility and a low elastic modulus, which can match the nerve tissue; the flexible photoelectrode also includes PEDOT conductive fiber filaments arranged on both sides of the flexible optical fiber core. Therefore, the flexible photoelectrode of the present application also has good electrical properties, can apply light stimulation to the peripheral nerve tissue, and can also record neural electrical signals, maintaining the basic properties of the photoelectrode; the flexible photoelectrode also includes a flexible packaging layer, so that the flexible photoelectrode as a whole has good biocompatibility, which can effectively reduce damage during long-term implantation in peripheral nerve tissue.
附图说明BRIEF DESCRIPTION OF THE DRAWINGS
此处的附图被并入说明书中并构成本说明书的一部分,示出了符合本申请的实施例,并与说明书一起用于解释本申请的原理。The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate embodiments consistent with the present application and, together with the description, serve to explain the principles of the present application.
为了更清楚地说明本申请实施例或现有技术中的技术方案,下面将对实施例或现有技术描述中所需要使用的附图作简单地介绍,显而易见地,对于本领域普通技术人员而言,在不付出创造性劳动性的前提下,还可以根据这些附图获得其他的附图。In order to more clearly illustrate the technical solutions in the embodiments of the present application or the prior art, the drawings required for use in the embodiments or the description of the prior art will be briefly introduced below. Obviously, for ordinary technicians in this field, other drawings can be obtained based on these drawings without paying any creative labor.
图1为本申请一种柔性光电极的结构示意图;FIG1 is a schematic diagram of the structure of a flexible photoelectrode of the present application;
图2为本申请一种柔性光电极的制备方法第二实施例的流程示意图。FIG. 2 is a schematic flow chart of a second embodiment of a method for preparing a flexible photoelectrode according to the present application.
本申请目的的实现、功能特点及优点将结合实施例,参照附图做进一步说明。The realization of the purpose, functional features and advantages of this application will be further explained in conjunction with embodiments and with reference to the accompanying drawings.
本发明的实施方式Embodiments of the present invention
应当理解,此处所描述的具体实施例仅仅用以解释本申请,并不用于限定本申请。It should be understood that the specific embodiments described herein are only used to explain the present application and are not used to limit the present application.
本申请实施例提供了一种柔性光电极,参照图1,图1为一种柔性光电极的结构示意图。An embodiment of the present application provides a flexible photoelectrode, referring to FIG. 1 , which is a schematic diagram of the structure of a flexible photoelectrode.
作为一种示例,光电极是一种将给光刺激与电活动记录结合在一起的电生理器件,在脑神经领域,目前被各大神经实验室广泛应用的光电极器件,是通过将多条金属(铬、镍、铜、铂等)微丝粘贴到同一段光纤上制成的,由于脑神经组织为静态组织,因此对光电极的弹性模量,也就是柔性要求不高。As an example, a photoelectrode is an electrophysiological device that combines light stimulation with the recording of electrical activity. In the field of brain nerves, photoelectrode devices, which are currently widely used in major neurological laboratories, are made by gluing multiple metal (chromium, nickel, copper, platinum, etc.) microwires to the same section of optical fiber. Since brain nerve tissue is a static tissue, the elastic modulus, that is, the flexibility requirements of the photoelectrode are not high.
外周神经系统又称周围神经系统,是指除中枢神经系统包括的脑神经和一部分脊神经以外的神经。The peripheral nervous system, also known as the peripheral nervous system, refers to the nerves other than the cranial nerves and part of the spinal nerves included in the central nervous system.
而与脑部成熟的光电极技术相比,外周神经的组织和现有的光电极之间存在弹性模量的失配问题,以膈肌为例,人类膈肌的弹性模量在8—10Kpa(静息),17-20Kpa(激活),而一般商用化的光电极的弹性模量在1.3-16Gpa之间。因此,这种光电极被植入外周神经组织(动态组织)后,光电极不会随组织一起形变,因此,在组织弯曲、收缩的过程中,光电极与组织接触的界面上会发生应力集中效应,导致界面上的组织严重受损,从而诱发组织的发炎、坏死、积液等。Compared with the mature photoelectrode technology in the brain, there is a mismatch in elastic modulus between the tissue of peripheral nerves and the existing photoelectrodes. Taking the diaphragm as an example, the elastic modulus of the human diaphragm is 8-10Kpa (resting) and 17-20Kpa (activated), while the elastic modulus of general commercial photoelectrodes is between 1.3-16Gpa. Therefore, after this photoelectrode is implanted in the peripheral nerve tissue (dynamic tissue), the photoelectrode will not deform with the tissue. Therefore, during the process of tissue bending and contraction, a stress concentration effect will occur at the interface where the photoelectrode contacts the tissue, causing serious damage to the tissue on the interface, thereby inducing inflammation, necrosis, and effusion of the tissue.
因此,外周神经系统尚缺乏一种可靠的光电极工具。Therefore, there is still a lack of a reliable optoelectronic tool for the peripheral nervous system.
在本实施例中,提供一种柔性光电极,参照图1,所述柔性光电极包括柔性光纤内芯4、包覆于所述柔性光纤内芯外侧的柔性光纤包覆层3、排列在所述柔性光纤内芯两侧的PEDOT导电纤维丝2,以及柔性封装层1。In this embodiment, a flexible optical electrode is provided. Referring to FIG. 1 , the flexible optical electrode includes a flexible optical fiber core 4, a flexible optical fiber coating layer 3 coated on the outside of the flexible optical fiber core, PEDOT conductive fiber filaments 2 arranged on both sides of the flexible optical fiber core, and a flexible packaging layer 1.
具体地,该柔性光电极包括柔性光纤内芯4以及包覆于所述柔性光纤内芯外侧的柔性光纤包覆层3,因此,本申请的柔性光电极不仅具有良好的拥有良好的光传输性能,还具有良好的柔性,弹性模量较低,能够与外周神经组织相匹配。Specifically, the flexible optical electrode includes a flexible optical fiber core 4 and a flexible optical fiber coating layer 3 coated on the outside of the flexible optical fiber core. Therefore, the flexible optical electrode of the present application not only has good light transmission performance, but also has good flexibility and a low elastic modulus, and can match peripheral nerve tissue.
具体地,柔性光电极还包括排列在所述柔性光纤内芯4两侧的PEDOT导电纤维丝2,具体地,PEDOT材料具备可抗弯折的性能,并具有良好导电性能,因此,本申请的柔性光电极还拥有良好电学性能,能够对神经组织施加光刺激,还能够记录神经电信号,保有光电极的基本性能。Specifically, the flexible photoelectrode also includes PEDOT conductive fiber filaments 2 arranged on both sides of the flexible optical fiber core 4. Specifically, the PEDOT material has the property of being resistant to bending and has good conductivity. Therefore, the flexible photoelectrode of the present application also has good electrical properties, can apply light stimulation to neural tissue, and can also record neural electrical signals, maintaining the basic properties of the photoelectrode.
具体地,柔性光电极还包括柔性封装层1,使柔性光电极整体具有良好的生物相容性,能够有效降低长期植入人体过程中的损伤。Specifically, the flexible photoelectrode also includes a flexible packaging layer 1, which makes the flexible photoelectrode as a whole have good biocompatibility and can effectively reduce damage during long-term implantation in the human body.
作为一种示例,所述柔性光纤内芯4以及所述柔性封装层1的材料均为PDMS(Polydimethylsiloxane,聚二甲基硅氧烷),所述柔性光纤包覆层3的材料为聚甲基氢硅氧烷。As an example, the materials of the flexible optical fiber inner core 4 and the flexible packaging layer 1 are both PDMS (Polydimethylsiloxane), and the material of the flexible optical fiber coating layer 3 is polymethylhydrogensiloxane.
具体地,柔性光纤内芯4的材料为Sylgard 184 PDMS(道康宁DC 184),该材料具有透明度高,流动性强,弹性系数高等特性,增加了柔性光纤内芯4的韧性和柔性,且提高了光传输效率。Specifically, the material of the flexible optical fiber inner core 4 is Sylgard 184 PDMS (Dow Corning DC 184), which has the characteristics of high transparency, strong fluidity, high elastic coefficient, etc., increases the toughness and flexibility of the flexible optical fiber inner core 4, and improves the light transmission efficiency.
具体地,所述柔性光纤内芯4的折射率为1.41-1.412。柔性光纤包覆层3的聚甲基氢硅氧烷材料的折射率为1.39,由于光在柔性光纤内芯4内传输,在柔性光纤包覆层3全反射,柔性光纤包覆层3使用的聚甲基氢硅氧烷材料的折射率比柔性光纤内芯4低,是为了不影响光在柔性光纤内芯4的传输速率。Specifically, the refractive index of the flexible optical fiber core 4 is 1.41-1.412. The refractive index of the polymethylhydrogensiloxane material of the flexible optical fiber coating 3 is 1.39. Since light is transmitted in the flexible optical fiber core 4 and is totally reflected in the flexible optical fiber coating 3, the refractive index of the polymethylhydrogensiloxane material used in the flexible optical fiber coating 3 is lower than that of the flexible optical fiber core 4, so as not to affect the transmission rate of light in the flexible optical fiber core 4.
因此,由柔性光纤内芯4和柔性光纤包覆层3组成的柔性光纤的柔性和韧性较好,且光的传输速率较高。Therefore, the flexible optical fiber composed of the flexible optical fiber core 4 and the flexible optical fiber coating layer 3 has good flexibility and toughness, and a high light transmission rate.
作为一种示例,柔性封装层1的材料为SE1700 PDMS,该材料具有,透明度高,弹性系数高,与Sylgard 184 PDMS相比流动性较低,因此,适合作为柔性封装层1,不仅封装后不易变形,且柔性较好,与上述的柔性光纤内芯4、柔性光纤包覆层3、PEDOT导电纤维丝2构成了一体化的柔性光电极。As an example, the material of the flexible encapsulation layer 1 is SE1700 PDMS, which has high transparency, high elastic modulus, and lower fluidity than Sylgard 184 PDMS. Therefore, it is suitable as the flexible encapsulation layer 1. It is not easy to deform after encapsulation and has good flexibility. It constitutes an integrated flexible optical electrode with the above-mentioned flexible optical fiber core 4, flexible optical fiber coating layer 3, and PEDOT conductive fiber filament 2.
作为一种示例,由上述柔性光纤内芯4、包覆于所述柔性光纤内芯外侧的柔性光纤包覆层3、排列在所述柔性光纤内芯两侧的PEDOT导电纤维丝2,以及柔性封装层1构成的柔性光电极的弹性模量小于1000kpa,而一般商用化的光电极的弹性模量在1.3-16Gpa之间。因此,本实施例提供的柔性光电极的柔性和韧性更好,具有更好的生物相容性,能够有效降低外周神经植入过程中的损伤。As an example, the elastic modulus of the flexible photoelectrode composed of the above-mentioned flexible optical fiber core 4, the flexible optical fiber coating layer 3 coated on the outside of the flexible optical fiber core, the PEDOT conductive fiber filaments 2 arranged on both sides of the flexible optical fiber core, and the flexible packaging layer 1 is less than 1000kPa, while the elastic modulus of the general commercial photoelectrode is between 1.3-16GPa. Therefore, the flexible photoelectrode provided in this embodiment has better flexibility and toughness, better biocompatibility, and can effectively reduce the damage during the peripheral nerve implantation process.
在本实施例中,由于本实施例提供的柔性光电极的柔性和韧性更好,因此,该柔性光电极适用于外周神经调控领域,也适用于对柔性要求不那么高的脑神经、脊神经的光遗传调控。In this embodiment, since the flexible photoelectrode provided in this embodiment has better flexibility and toughness, the flexible photoelectrode is suitable for the field of peripheral nerve regulation, and is also suitable for optogenetic regulation of cranial nerves and spinal nerves that do not require so much flexibility.
在本实施例中,还提供了上述柔性光电极的制备方法,所述制备方法包括:In this embodiment, a method for preparing the above-mentioned flexible photoelectrode is also provided, and the preparation method comprises:
步骤S10:在柔性光纤内芯表面涂覆一层聚甲基氢硅氧烷,形成柔性光纤包覆层;Step S10: coating a layer of polymethylhydrogensiloxane on the surface of the inner core of the flexible optical fiber to form a flexible optical fiber coating layer;
作为一种示例,在柔性光纤内芯4表面涂覆一层聚甲基氢硅氧烷,形成柔性光纤包覆层3。As an example, a layer of polymethylhydrogensiloxane is coated on the surface of the flexible optical fiber inner core 4 to form the flexible optical fiber coating layer 3 .
在本实施例中,所述在柔性光纤内芯表面涂覆一层聚甲基氢硅氧烷,形成柔性光纤包覆层的步骤之前,所述方法还包括:In this embodiment, before the step of coating a layer of polymethylhydrogensiloxane on the surface of the inner core of the flexible optical fiber to form a flexible optical fiber coating layer, the method further includes:
步骤S40:使用乙醇和超纯水对制备好的柔性光纤内芯进行清洗。Step S40: using ethanol and ultrapure water to clean the prepared flexible optical fiber inner core.
作为一种示例,将制备好的柔性光纤内芯4使用乙醇和超纯水进行清洗,能够去除柔性光纤内芯4的杂质,使柔性光纤表面更光滑,减小对光传输速率的影响。As an example, the prepared flexible optical fiber inner core 4 is cleaned with ethanol and ultrapure water, which can remove impurities in the flexible optical fiber inner core 4, make the surface of the flexible optical fiber smoother, and reduce the impact on the light transmission rate.
在本实施例中,所述在柔性光纤内芯表面涂覆一层聚甲基氢硅氧烷,形成柔性光纤包覆层的步骤之后,所述方法还包括:In this embodiment, after the step of coating a layer of polymethylhydrogensiloxane on the surface of the inner core of the flexible optical fiber to form a flexible optical fiber coating layer, the method further includes:
步骤S50:将涂覆有聚甲基氢硅氧烷的柔性光纤内芯放入烘箱,在真空120-130摄氏度下加热30-35分钟。Step S50: placing the flexible optical fiber inner core coated with polymethylhydrogensiloxane into an oven and heating it at 120-130 degrees Celsius under vacuum for 30-35 minutes.
作为一种示例,可以是将涂覆有聚甲基氢硅氧烷的柔性光纤内芯4放入烘箱,在真空130摄氏度下加热30分钟,还可以是将涂覆有聚甲基氢硅氧烷的柔性光纤内芯4放入烘箱,在真空120摄氏度下加热35分钟等,具体不做限定。As an example, the flexible optical fiber core 4 coated with polymethyl hydrogen siloxane can be placed in an oven and heated at 130 degrees Celsius in a vacuum for 30 minutes. Alternatively, the flexible optical fiber core 4 coated with polymethyl hydrogen siloxane can be placed in an oven and heated at 120 degrees Celsius in a vacuum for 35 minutes, etc., without specific limitation.
具体地,通过加热,可以使柔性光纤包覆层3与柔性光纤内芯4紧密结合,减小柔性光纤的体积,且避免了柔性光纤包覆层3与柔性光纤内芯4之间存在缝隙,不会对光的传输速率产生影响。Specifically, by heating, the flexible optical fiber coating 3 and the flexible optical fiber core 4 can be tightly combined, reducing the volume of the flexible optical fiber and avoiding the existence of a gap between the flexible optical fiber coating 3 and the flexible optical fiber core 4, without affecting the transmission rate of light.
步骤S20:将多根PEDOT导电纤维丝排列在涂覆有聚甲基氢硅氧烷的柔性光纤内芯两侧;Step S20: arranging a plurality of PEDOT conductive fiber filaments on both sides of the inner core of the flexible optical fiber coated with polymethylhydrogensiloxane;
作为一种示例,多根PEDOT导电纤维丝2可以是一根、两根、三根等,具体不做限定。As an example, the plurality of PEDOT conductive fiber filaments 2 may be one, two, three, etc., without specific limitation.
具体地,可以根据需求,通过增减PEDOT导电纤维丝2的数量,调整电生理记录的所需要的信号通道数量,操作简单便捷。Specifically, the number of signal channels required for electrophysiological recording can be adjusted by increasing or decreasing the number of PEDOT conductive fibers 2 according to demand, and the operation is simple and convenient.
作为一种示例,可以将两根PEDOT导电纤维丝2对称排列在涂覆有聚甲基氢硅氧烷的柔性光纤内芯4两侧,也可以是将三根PEDOT导电纤维丝2随意排列在涂覆有聚甲基氢硅氧烷的柔性光纤内芯4两侧等,具体不做限定。As an example, two PEDOT conductive fiber filaments 2 can be symmetrically arranged on both sides of the flexible optical fiber core 4 coated with polymethylhydrogensiloxane, or three PEDOT conductive fiber filaments 2 can be randomly arranged on both sides of the flexible optical fiber core 4 coated with polymethylhydrogensiloxane, etc., without specific limitation.
此时,参照图1,由于PEDOT导电纤维丝2和柔性光纤都很小,排列好后,可以看作在一个平面上。At this time, referring to FIG. 1 , since the PEDOT conductive fiber filaments 2 and the flexible optical fiber are very small, they can be regarded as being on the same plane after being arranged.
步骤S30:通过3D打印机使用PDMS,对排列好的柔性光纤内芯以及PEDOT导电纤维丝进行封装,形成柔性封装层,得到制备好的柔性光电极。Step S30: using PDMS through a 3D printer to encapsulate the arranged flexible optical fiber cores and PEDOT conductive fiber filaments to form a flexible encapsulation layer to obtain a prepared flexible photoelectrode.
作为一种示例,通过3D打印机使用的PDMS为SE1700 PDMS。As an example, the PDMS used by the 3D printer is SE1700 PDMS.
作为一种示例,参照图1,通过3D打印机使用PDMS,对排列好的柔性光纤内芯以及PEDOT导电纤维丝进行封装,可以是在排列好后的PEDOT导电纤维丝2和柔性光纤所在平面的上层通过3D打印机涂覆一层SE1700 PDMS,再在在排列好后的PEDOT导电纤维丝2和柔性光纤所在平面的下层通过3D打印机涂覆一层SE1700 PDMS,完成封装,形成柔性封装层,得到制备好的柔性光电极。As an example, referring to Figure 1, PDMS is used by a 3D printer to encapsulate the arranged flexible optical fiber core and PEDOT conductive fiber filaments. A layer of SE1700 PDMS can be coated on the upper layer of the plane where the arranged PEDOT conductive fiber filaments 2 and the flexible optical fiber are located by a 3D printer, and then a layer of SE1700 PDMS is coated on the lower layer of the plane where the arranged PEDOT conductive fiber filaments 2 and the flexible optical fiber are located by a 3D printer to complete the encapsulation, form a flexible encapsulation layer, and obtain a prepared flexible photoelectrode.
相比于商用化的光电极需要精密手工来完成制备,本实施例提供的柔性光电极的制备步骤更少,制作过程更加简便,因此,制备成本更低。Compared with commercial photoelectrodes that require precise manual preparation, the flexible photoelectrode provided in this embodiment has fewer preparation steps and a simpler production process, and therefore has a lower preparation cost.
其中,所述柔性光纤内芯的制备方法,包括:Wherein, the method for preparing the flexible optical fiber inner core comprises:
步骤A1:将PDMS和PDMS固化剂混合并搅拌均匀,得到PDMS和PDMS固化剂的混合液,其中,PDMS和PDMS固化剂的质量比为5:1;Step A1: PDMS and PDMS curing agent are mixed and stirred evenly to obtain a mixed solution of PDMS and PDMS curing agent, wherein the mass ratio of PDMS to PDMS curing agent is 5:1;
作为一种示例,将质量比为5:1的sylgard 184 PDMS和sylgard 184 PDMS固化剂混合并搅拌均匀,得sylgard 184 PDMS和sylgard 184 PDMS固化剂的混合液。As an example, sylgard 184 PDMS and sylgard 184 PDMS curing agent in a mass ratio of 5:1 are mixed and stirred evenly to obtain a mixed solution of sylgard 184 PDMS and sylgard 184 PDMS curing agent.
步骤A2:除去所述混合液中的气泡,通过注射装置将所述混合液注入至特氟龙管中;Step A2: removing bubbles in the mixed solution, and injecting the mixed solution into a Teflon tube through an injection device;
作为一种示例,除去所述混合液中的气泡,通过注射装置将所述混合液注入至特氟龙管中,由于特氟龙管具备抗粘性,且具有较低的摩擦系数,因此,通过注射装置将原材料注入至特氟龙管中,使用特氟龙管作为模具对原材料塑型,能够制备出光滑且均匀的柔性光纤内芯4。As an example, the bubbles in the mixed liquid are removed, and the mixed liquid is injected into a Teflon tube through an injection device. Since the Teflon tube is anti-sticky and has a low friction coefficient, the raw materials are injected into the Teflon tube through the injection device, and the Teflon tube is used as a mold to shape the raw materials, so that a smooth and uniform flexible optical fiber core 4 can be prepared.
步骤A3:待所述混合液固化成型后,将所述特氟龙管剥离,得到柔性光纤内芯。Step A3: After the mixed liquid is solidified and formed, the Teflon tube is peeled off to obtain a flexible optical fiber core.
作为一种示例,待所述原材料固化成型后,将所述特氟龙管剥离,得到柔性光纤内芯4,整个制备过程中使用的工具较为简单,且制备过程也很简单,制备的柔性光纤内芯4不仅表面光滑,且粗细均匀,且制备过程较为简单。As an example, after the raw materials are solidified and formed, the Teflon tube is peeled off to obtain the flexible optical fiber core 4. The tools used in the entire preparation process are relatively simple, and the preparation process is also very simple. The prepared flexible optical fiber core 4 not only has a smooth surface and uniform thickness, but also has a relatively simple preparation process.
其中,所述PEDOT导电纤维丝的制备方法,包括:Wherein, the preparation method of the PEDOT conductive fiber comprises:
步骤B1:通过3D打印机将PEDOT:PSS注入至异丙醇溶液中,凝固形成PEDOT:PSS导电纤维丝;Step B1: injecting PEDOT:PSS into an isopropanol solution through a 3D printer to solidify and form PEDOT:PSS conductive fiber filaments;
作为一种示例,PEDOT导电纤维丝是使用PEDOT:PSS材料制备得到的。As an example, PEDOT conductive fiber is prepared using PEDOT:PSS material.
具体地,PEDOT:PSS为导电聚合物,是由组分PEDOT和PSS组成的导电聚合物,PEDOT为溶液,PSS用于辅助PEDOT溶液塑性。Specifically, PEDOT:PSS is a conductive polymer, which is a conductive polymer composed of components PEDOT and PSS. PEDOT is a solution, and PSS is used to assist the plasticity of the PEDOT solution.
因此,需要通过3D打印机将PEDOT:PSS注入至异丙醇溶液中,凝固形成PEDOT:PSS导电纤维丝;其中,异丙醇溶液能够起到凝固PEDOT:PSS的作用。 Therefore, it is necessary to use a 3D printer to inject PEDOT:PSS into an isopropyl alcohol solution to solidify it into PEDOT:PSS conductive fiber filaments; wherein, the isopropyl alcohol solution can play a role in solidifying PEDOT:PSS.
在本实施例中,所述通过3D打印机将PEDOT:PSS注入至异丙醇溶液的过程中使用的3D打印机的针头大小为23G,打印半径为50-80毫米的圆形,注入速度为300-400微升/分钟。In this embodiment, the needle size of the 3D printer used in the process of injecting PEDOT:PSS into the isopropanol solution through the 3D printer is 23G, the printing radius is 50-80 mm, and the injection speed is 300-400 μl/min.
作为一种示例,在通过3D打印机将PEDOT:PSS注入至异丙醇溶液中的步骤之前,先更换3D打印机的针头,并设定打印半径以及注入速度(3D打印机挤出PEDOT:PSS的速度),注入速度若太慢,则会导致PEDOT:PSS导电纤维丝断断续续,不能成型,若注入速度太快,则会导致PEDOT:PSS材料堆积,导致制备得到的PEDOT:PSS导电纤维丝不均匀。As an example, before injecting PEDOT:PSS into an isopropyl alcohol solution through a 3D printer, first replace the needle of the 3D printer, and set the printing radius and injection speed (the speed at which the 3D printer extrude PEDOT:PSS). If the injection speed is too slow, the PEDOT:PSS conductive fiber filaments will be intermittent and unable to form. If the injection speed is too fast, the PEDOT:PSS material will accumulate, resulting in uneven prepared PEDOT:PSS conductive fiber filaments.
具体地,可以使用大小为23G的3D打印机的针头(其中,G为针头内径的大小,23G为340微米),3D打印机的打印半径(针头的运动半径)为50毫米的圆形,注入速度为300微升/分钟,制备得到PEDOT:PSS导电纤维丝。还可以使用大小为23G的3D打印机的针头,打印半径为75毫米的圆形,注入速度为400微升/分钟,制备得到PEDOT:PSS导电纤维丝。Specifically, a 23G needle of a 3D printer (where G is the inner diameter of the needle, 23G is 340 microns), a 50 mm printing radius (needle movement radius) of the 3D printer, and an injection speed of 300 microliters/minute can be used to prepare PEDOT:PSS conductive fiber filaments. A 23G needle of a 3D printer can also be used to print a 75 mm radius circle and an injection speed of 400 microliters/minute to prepare PEDOT:PSS conductive fiber filaments.
作为一种示例,PEDOT:PSS为重量百分比为1.1%的水溶液,在将PEDOT:PSS注入至异丙醇溶液中的过程中,能够将PEDOT:PSS进行脱水,根据PEDOT:PSS在异丙醇溶液中凝固时长的不同,制备得到的PEDOT:PSS导电纤维丝的直径发生改变(由原本的针头大小340微米,缩水后达到10-100微米)。As an example, PEDOT:PSS is an aqueous solution with a weight percentage of 1.1%. During the process of injecting PEDOT:PSS into an isopropanol solution, PEDOT:PSS can be dehydrated. Depending on the coagulation time of PEDOT:PSS in the isopropanol solution, the diameter of the prepared PEDOT:PSS conductive fiber changes (from the original needle size of 340 microns to 10-100 microns after shrinkage).
步骤B2:将PEDOT:PSS导电纤维丝放至浓硫酸中酸洗8-15分钟;Step B2: Place the PEDOT:PSS conductive fiber in concentrated sulfuric acid for pickling for 8-15 minutes;
作为一种示例,PSS对PEDOT的导电性能会产生副作用。因此,需要将PEDOT:PSS导电纤维丝放至浓硫酸中酸洗8-15分钟,以洗掉PEDOT:PSS导电纤维丝中的PSS组分。As an example, PSS has a negative effect on the conductive properties of PEDOT. Therefore, the PEDOT:PSS conductive fiber needs to be washed in concentrated sulfuric acid for 8-15 minutes to wash away the PSS component in the PEDOT:PSS conductive fiber.
具体地,可以是酸洗10分钟,12分钟或15分钟等,具体不做限定。Specifically, the pickling may be performed for 10 minutes, 12 minutes or 15 minutes, etc., without limitation.
作为一种示例,PEDOT:PSS导电纤维丝进行酸洗处理后,得到酸性的PEDOT导电纤维丝。As an example, after the PEDOT:PSS conductive fiber is subjected to acid washing, acidic PEDOT conductive fiber is obtained.
步骤B3:使用乙醇将酸洗处理后的PEDOT:PSS导电纤维丝多次洗涤,干燥后得到PEDOT导电纤维丝。Step B3: The acid-washed PEDOT:PSS conductive fiber filaments are washed multiple times with ethanol, and then dried to obtain PEDOT conductive fiber filaments.
作为一种示例,使用乙醇将酸洗处理后的PEDOT:PSS导电纤维丝(酸性的PEDOT导电纤维丝)多次洗涤,以中和掉多余的硫酸。As an example, the acid-washed PEDOT:PSS conductive fiber (acidic PEDOT conductive fiber) was washed several times with ethanol to neutralize the excess sulfuric acid.
作为一种示例,将PEDOT导电纤维丝干燥,得到可使用的PEDOT导电纤维丝。As an example, the PEDOT conductive fiber filaments are dried to obtain usable PEDOT conductive fiber filaments.
作为一种示例,最终制备得到的PEDOT导电纤维丝的直径为10-100微米。As an example, the diameter of the PEDOT conductive fiber filament finally prepared is 10-100 microns.
具体地,制备得到的PEDOT导电纤维丝的直径有20微米,85微米,100微米等。Specifically, the diameters of the prepared PEDOT conductive fibers are 20 microns, 85 microns, 100 microns, etc.
作为一种示例,将根据上述方法制备得到的柔性光纤内芯4、柔性光纤包覆层3、PEDOT导电纤维丝2,以及柔性封装层1按照上述方法制成柔性光电极,该柔性光电极的弹性模量小于1000kpa,而一般商用化的光电极的弹性模量在1.3-16Gpa之间。As an example, the flexible optical fiber core 4, the flexible optical fiber coating layer 3, the PEDOT conductive fiber filament 2, and the flexible packaging layer 1 prepared according to the above method are made into a flexible photoelectrode according to the above method. The elastic modulus of the flexible photoelectrode is less than 1000 kPa, while the elastic modulus of general commercial photoelectrodes is between 1.3-16 GPa.
因此,本实施例提供的柔性光电极的柔性和韧性更好,具有更好的生物相容性,能够有效降低外周神经植入过程中的损伤。Therefore, the flexible photoelectrode provided in this embodiment has better flexibility and toughness, better biocompatibility, and can effectively reduce damage to peripheral nerves during implantation.
本实施例提供的柔性光电极可通过转接头与现有的激光发生器和电生理记录设备相连,通过手术植入的方式固定到外周神经系统的特定区域,以实现该柔性光电极的应用。The flexible photoelectrode provided in this embodiment can be connected to an existing laser generator and an electrophysiological recording device through an adapter, and fixed to a specific area of the peripheral nervous system by surgical implantation to realize the application of the flexible photoelectrode.
需要说明的是,在本文中,术语“包括”、“包含”或者其任何其他变体意在涵盖非排他性的包含,从而使得包括一系列要素的过程、方法、物品或者系统不仅包括那些要素,而且还包括没有明确列出的其他要素,或者是还包括为这种过程、方法、物品或者系统所固有的要素。在没有更多限制的情况下,由语句“包括一个……”限定的要素,并不排除在包括该要素的过程、方法、物品或者系统中还存在另外的相同要素。It should be noted that, in this article, the terms "include", "comprises" or any other variations thereof are intended to cover non-exclusive inclusion, so that a process, method, article or system including a series of elements includes not only those elements, but also other elements not explicitly listed, or also includes elements inherent to such process, method, article or system. In the absence of further restrictions, an element defined by the sentence "comprises a ..." does not exclude the existence of other identical elements in the process, method, article or system including the element.
上述本申请实施例序号仅仅为了描述,不代表实施例的优劣。The serial numbers of the embodiments of the present application are for description only and do not represent the advantages or disadvantages of the embodiments.
通过以上的实施方式的描述,本领域的技术人员可以清楚地了解到上述实施例方法可借助软件加必需的通用硬件平台的方式来实现,当然也可以通过硬件,但很多情况下前者是更佳的实施方式。基于这样的理解,本申请的技术方案本质上或者说对现有技术做出贡献的部分可以以软件产品的形式体现出来,该计算机软件产品存储在如上所述的一个存储介质(如ROM/RAM、磁碟、光盘)中,包括若干指令用以使得一台终端设备(可以是手机,计算机,服务器,或者网络设备等)执行本申请各个实施例所述的方法。Through the description of the above implementation methods, those skilled in the art can clearly understand that the above-mentioned embodiment methods can be implemented by means of software plus a necessary general hardware platform, and of course by hardware, but in many cases the former is a better implementation method. Based on such an understanding, the technical solution of the present application is essentially or the part that contributes to the prior art can be embodied in the form of a software product, which is stored in a storage medium (such as ROM/RAM, magnetic disk, optical disk) as described above, and includes a number of instructions for a terminal device (which can be a mobile phone, computer, server, or network device, etc.) to execute the methods described in each embodiment of the present application.
以上仅为本申请的优选实施例,并非因此限制本申请的专利范围,凡是利用本申请说明书及附图内容所作的等效结构或等效流程变换,或直接或间接运用在其他相关的技术领域,均同理包括在本申请的专利保护范围内。The above are only preferred embodiments of the present application, and are not intended to limit the patent scope of the present application. Any equivalent structure or equivalent process transformation made using the contents of the present application specification and drawings, or directly or indirectly applied in other related technical fields, are also included in the patent protection scope of the present application.

Claims (10)

  1. 一种柔性光电极,其特征在于,所述柔性光电极包括柔性光纤内芯、包覆于所述柔性光纤内芯外侧的柔性光纤包覆层、排列在所述柔性光纤内芯两侧的PEDOT导电纤维丝,以及柔性封装层。A flexible optical electrode, characterized in that the flexible optical electrode comprises a flexible optical fiber core, a flexible optical fiber coating layer coated on the outside of the flexible optical fiber core, PEDOT conductive fiber filaments arranged on both sides of the flexible optical fiber core, and a flexible packaging layer.
  2. 如权利要求1所述的柔性光电极,其特征在于,所述柔性光纤内芯以及所述柔性封装层的材料均为PDMS,所述柔性光纤包覆层的材料为聚甲基氢硅氧烷。The flexible optical electrode according to claim 1 is characterized in that the materials of the flexible optical fiber inner core and the flexible packaging layer are both PDMS, and the material of the flexible optical fiber coating layer is polymethylhydrogensiloxane.
  3. 如权利要求2所述的柔性光电极,其特征在于,所述柔性光纤内芯的折射率为1.41-1.412。The flexible optical electrode as described in claim 2 is characterized in that the refractive index of the inner core of the flexible optical fiber is 1.41-1.412.
  4. 一种如权利要求1-3任一项所述的柔性光电极的制备方法,其特征在于,所述制备方法包括:A method for preparing a flexible photoelectrode according to any one of claims 1 to 3, characterized in that the preparation method comprises:
    在柔性光纤内芯表面涂覆一层聚甲基氢硅氧烷,形成柔性光纤包覆层;A layer of polymethylhydrogensiloxane is coated on the surface of the inner core of the flexible optical fiber to form a flexible optical fiber coating layer;
    将多根PEDOT导电纤维丝排列在涂覆有聚甲基氢硅氧烷的柔性光纤内芯两侧;Arrange multiple PEDOT conductive fibers on both sides of a flexible optical fiber core coated with polymethylhydrogensiloxane;
    通过3D打印机使用PDMS,对排列好的柔性光纤内芯以及PEDOT导电纤维丝进行封装,形成柔性封装层,得到制备好的柔性光电极。The arranged flexible optical fiber cores and PEDOT conductive fiber filaments are encapsulated using PDMS through a 3D printer to form a flexible encapsulation layer to obtain a prepared flexible photoelectrode.
  5. 在此处键入权利要求项5如权利要求4所述的柔性光电极的制备方法,其特征在于,所述柔性光纤内芯的制备方法,包括:Type claim 5 here The method for preparing a flexible optical electrode according to claim 4, characterized in that the method for preparing the flexible optical fiber inner core comprises:
    将PDMS和PDMS固化剂混合并搅拌均匀,得到PDMS和PDMS固化剂的混合液,其中,PDMS和PDMS固化剂的质量比为5:1;The PDMS and the PDMS curing agent are mixed and stirred evenly to obtain a mixed solution of the PDMS and the PDMS curing agent, wherein the mass ratio of the PDMS and the PDMS curing agent is 5:1;
    除去所述混合液中的气泡,通过注射装置将所述混合液注入至特氟龙管中;removing bubbles in the mixed solution, and injecting the mixed solution into a Teflon tube through an injection device;
    待所述混合液固化成型后,将所述特氟龙管剥离,得到柔性光纤内芯。After the mixed liquid is solidified and formed, the Teflon tube is peeled off to obtain a flexible optical fiber inner core.
  6. 如权利要求4所述的柔性光电极的制备方法,其特征在于,所述PEDOT导电纤维丝的制备方法,包括:The method for preparing a flexible photoelectrode according to claim 4, characterized in that the method for preparing the PEDOT conductive fiber comprises:
    通过3D打印机将PEDOT:PSS注入至异丙醇溶液中,凝固形成PEDOT:PSS导电纤维丝;PEDOT:PSS is injected into an isopropanol solution through a 3D printer and solidified to form PEDOT:PSS conductive fiber filaments;
    将PEDOT:PSS导电纤维丝放至浓硫酸中酸洗8-15分钟;Place the PEDOT:PSS conductive fiber in concentrated sulfuric acid for pickling for 8-15 minutes;
    使用乙醇将酸洗处理后的PEDOT:PSS导电纤维丝多次洗涤,干燥后得到PEDOT导电纤维丝。The acid-washed PEDOT:PSS conductive fiber filaments were washed multiple times with ethanol and dried to obtain PEDOT conductive fiber filaments.
  7. 如权利要求6所述的柔性光电极的制备方法,其特征在于,所述通过3D打印机将PEDOT:PSS注入至异丙醇溶液的过程中使用的3D打印机的针头大小为23G,打印半径为50-80毫米的圆形,注入速度为300-400微升/分钟。The method for preparing a flexible photoelectrode as described in claim 6 is characterized in that the needle size of the 3D printer used in the process of injecting PEDOT:PSS into the isopropanol solution through a 3D printer is 23G, the printing radius is 50-80 mm, and the injection speed is 300-400 μl/min.
  8. 如权利要求7所述的柔性光电极的制备方法,其特征在于,所述PEDOT导电纤维丝的直径为10-100微米。The method for preparing a flexible photoelectrode according to claim 7, characterized in that the diameter of the PEDOT conductive fiber filament is 10-100 microns.
  9. 如权利要求4所述的柔性光电极的制备方法,其特征在于,所述在柔性光纤内芯表面涂覆一层聚甲基氢硅氧烷,形成柔性光纤包覆层的步骤之后,所述方法还包括:The method for preparing a flexible optical electrode according to claim 4, characterized in that after the step of coating a layer of polymethylhydrogensiloxane on the surface of the inner core of the flexible optical fiber to form a flexible optical fiber coating layer, the method further comprises:
    将涂覆有聚甲基氢硅氧烷的柔性光纤内芯放入烘箱,在真空120-130摄氏度下加热30-35分钟。The flexible optical fiber inner core coated with polymethylhydrogensiloxane is placed in an oven and heated at 120-130 degrees Celsius for 30-35 minutes under vacuum.
  10. 如权利要求4所述的柔性光电极的制备方法,其特征在于,所述在柔性光纤内芯表面涂覆一层聚甲基氢硅氧烷,形成柔性光纤包覆层的步骤之前,所述方法还包括:The method for preparing a flexible optical electrode according to claim 4, characterized in that before the step of coating a layer of polymethylhydrogensiloxane on the surface of the inner core of the flexible optical fiber to form a flexible optical fiber coating layer, the method further comprises:
    使用乙醇和超纯水对制备好的柔性光纤内芯进行清洗。The prepared flexible optical fiber core was cleaned using ethanol and ultrapure water.
PCT/CN2023/133462 2022-11-23 2023-11-22 Flexible optical electrode and preparation method therefor WO2024109854A1 (en)

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