KR102606887B1 - Electrochemically conductive polydopamine-Au composite material electrode by electrochemical method and their manufacturing method - Google Patents
Electrochemically conductive polydopamine-Au composite material electrode by electrochemical method and their manufacturing method Download PDFInfo
- Publication number
- KR102606887B1 KR102606887B1 KR1020210090223A KR20210090223A KR102606887B1 KR 102606887 B1 KR102606887 B1 KR 102606887B1 KR 1020210090223 A KR1020210090223 A KR 1020210090223A KR 20210090223 A KR20210090223 A KR 20210090223A KR 102606887 B1 KR102606887 B1 KR 102606887B1
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- Prior art keywords
- gold
- polydopamine
- dopamine
- electrode
- composite electrode
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 30
- 238000002848 electrochemical method Methods 0.000 title claims abstract description 17
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Classifications
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- A61B—DIAGNOSIS; SURGERY; IDENTIFICATION
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- A61B5/24—Detecting, measuring or recording bioelectric or biomagnetic signals of the body or parts thereof
- A61B5/25—Bioelectric electrodes therefor
- A61B5/263—Bioelectric electrodes therefor characterised by the electrode materials
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- A—HUMAN NECESSITIES
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- A61B5/25—Bioelectric electrodes therefor
- A61B5/263—Bioelectric electrodes therefor characterised by the electrode materials
- A61B5/268—Bioelectric electrodes therefor characterised by the electrode materials containing conductive polymers, e.g. PEDOT:PSS polymers
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- A—HUMAN NECESSITIES
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- A61B5/25—Bioelectric electrodes therefor
- A61B5/279—Bioelectric electrodes therefor specially adapted for particular uses
- A61B5/291—Bioelectric electrodes therefor specially adapted for particular uses for electroencephalography [EEG]
- A61B5/293—Invasive
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- A—HUMAN NECESSITIES
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- A61B5/24—Detecting, measuring or recording bioelectric or biomagnetic signals of the body or parts thereof
- A61B5/25—Bioelectric electrodes therefor
- A61B5/279—Bioelectric electrodes therefor specially adapted for particular uses
- A61B5/294—Bioelectric electrodes therefor specially adapted for particular uses for nerve conduction study [NCS]
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
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- A61N1/02—Details
- A61N1/04—Electrodes
- A61N1/05—Electrodes for implantation or insertion into the body, e.g. heart electrode
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- A—HUMAN NECESSITIES
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- A61N1/32—Applying electric currents by contact electrodes alternating or intermittent currents
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- H—ELECTRICITY
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- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
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- H—ELECTRICITY
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- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
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- Spectroscopy & Molecular Physics (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
본 발명은 전기화학적 방법을 이용한 전기전도성 폴리도파민-금 복합재 전극 및 이의 제조방법에 관한 것으로, 전기화학적 방법을 이용하여 높은 전기화학적 특성을 가지는 폴리도파민-금 복합재가 전극 표면에 증착된 형태를 가지는 폴리도파민-금 복합재 전극 및 이의 제조방법에 관한 것이다.The present invention relates to an electrically conductive polydopamine-gold composite electrode and a manufacturing method thereof using an electrochemical method, in which a polydopamine-gold composite with high electrochemical properties is deposited on the electrode surface using an electrochemical method. It relates to a polydopamine-gold composite electrode and its manufacturing method.
Description
본 발명의 전기화학적 방법을 이용한 전기전도성 폴리도파민-금 복합재 전극 및 이의 제조방법에 관한 것으로, 더욱 상세하게는, 일반적으로 낮은 전기전도성을 가진 폴리도파민을 전기화학적 방법을 이용하여 금과 복합재화하여 전극 표면에 증착시킴으로써, 전극의 전기화학적 임피던스를 낮추고, 전하충전용량, 전하주입한계 및 사용 안정성을 향상시킬 수 있는 전기화학적 방법을 이용한 전기전도성 폴리도파민-금 복합재 전극 및 이의 제조방법에 관한 것이다.The present invention relates to an electrically conductive polydopamine-gold composite electrode using an electrochemical method and a method of manufacturing the same. More specifically, polydopamine, which generally has low electrical conductivity, is composited with gold using an electrochemical method. It relates to an electrically conductive polydopamine-gold composite electrode and a method of manufacturing the same using an electrochemical method that can lower the electrochemical impedance of the electrode and improve the charge charging capacity, charge injection limit, and stability of use by depositing it on the electrode surface.
사람의 뇌-신경과 기계장치와의 신호전달 시스템인 신경인터페이스는 인공와우, 인공눈, 인공팔 그리고 전자약과 같이 환자의 불편함을 해소하고 질병을 완화시키기 위한 다양한 능동형 이식장치의 원활한 작동을 위해서 필수적인 기술이다. 이러한 신경인터페이스의 형성을 위해서 필수적인 구성요소 중 하나가 이식형 신경전극이다.Neural interface, a signal transmission system between the human brain and nerves and mechanical devices, is used to ensure smooth operation of various active implant devices such as cochlear implants, artificial eyes, artificial arms, and electronic medicine to relieve patient discomfort and alleviate diseases. It is an essential skill. One of the essential components for forming such a neural interface is an implantable nerve electrode.
사람의 뇌와 신경에 직접 접촉하여 생체신호를 수집하거나 반대로 신경을 자극하여 특정 효과를 유도하기 위해서는 이식가능한 신경전극이 필요하다. 하지만 현재까지 알려진 신경전극 소재는 낮은 생체적합성과 장기간 사용시 전극소재의 분해와 면역반응에 의해 신경과의 접합을 상실하여 기능을 잃는 문제점들이 있다. 이를 극복하기 위해서 신경전극에 사용되는 소재는 생체적합성 뿐만 아니라 장시간 사용에도 신경전극으로서의 성능을 유지할 수 있어야 한다.Implantable nerve electrodes are needed to directly contact a person's brain and nerves to collect biological signals or, conversely, to induce specific effects by stimulating nerves. However, the nerve electrode materials known to date have problems such as low biocompatibility and loss of function when used for a long time due to decomposition of the electrode material and loss of connection with the nerve due to immune reaction. To overcome this, the materials used in nerve electrodes must not only be biocompatible but also be able to maintain their performance as nerve electrodes even when used for long periods of time.
일반적으로 사용되는 신경전극용 소재는 체내에서 반응성이 없고 높은 전기전도성을 가진 귀금속류 (백금, 금, 티타늄 등)를 이용하지만, 높은 전기전도성에 비하여 전기화학적 특성은 낮은 것으로 알려져 있으며, 특정 조건에서 귀금속의 용해와 같은 부반응으로 인해 반응성 물질이 형성될 수 있다는 가능성이 있다. 전도성고분자인 폴리에틸렌디옥시티오펜(poly(3,4-ethylenedioxythiophene), PEDOT), 폴리피롤(polypyrrole, PPy), 폴리아닐린(polyaniline, PANI) 등은 전기화학적 특성이 뛰어나며, 생체적합성 물질로 알려져 있어 신경전극 대체소재로서 많은 연구가 진행되고 있지만, 여전히 낮은 생체내 안정성으로 인한 장시간 사용이 힘들다는 점으로 인해 한계가 뚜렷하다. 또한, 전도성고분자의 분해산물은 독성을 가질 수 있기 때문에 장기간 사용시 생체 내에서의 적합성도 문제점이다. 그 밖에도 탄소나노튜브와 그래핀 같은 탄소나노물질의 경우에도 높은 전기화학적 특성과 안정성을 가지고 있어 신경전극소재로 연구되고 있지만, 아직 탄소나노물질의 생체 내에서의 적합성에 대한 증명이 더 필요한 상황이다. Commonly used materials for nerve electrodes use precious metals (platinum, gold, titanium, etc.) that are non-reactive in the body and have high electrical conductivity, but are known to have low electrochemical properties compared to high electrical conductivity, and under certain conditions, precious metals are used. There is a possibility that reactive substances may be formed due to side reactions such as dissolution. Conductive polymers such as poly(3,4-ethylenedioxythiophene) (PEDOT), polypyrrole (PPy), and polyaniline (PANI) have excellent electrochemical properties and are known to be biocompatible materials, making them a substitute for nerve electrodes. Although much research is underway as a material, it still has clear limitations due to its low in vivo stability, making it difficult to use it for a long time. Additionally, since decomposition products of conductive polymers can be toxic, compatibility in the body is also a problem when used for long periods of time. In addition, carbon nanomaterials such as carbon nanotubes and graphene have high electrochemical properties and stability and are being studied as nerve electrode materials, but further proof of the suitability of carbon nanomaterials in vivo is still needed. .
본 발명에서는 상기와 같이 현재 사용되고 있거나 개발되고 있는 생체전극소재의 한계점을 극복하기 위하여 생체내에 존재하는 물질인 도파민(dopamine)을 이용하여 생체유래 전도성 물질인 유멜라닌(eumelanin)과 유사한 구조의 합성 폴리도파민(polydopamine, PDA)을 이용한다.In the present invention, in order to overcome the limitations of bioelectrode materials currently in use or being developed as described above, dopamine, a substance existing in the body, is used to create a synthetic polyester with a structure similar to eumelanin, a bio-derived conductive material. It uses dopamine (polydopamine, PDA).
생체유래전도성 물질로 알려져 있는 유멜라닌은 DHI(5,6-dihydroxyindole)와 DHICA(5,6-dihydroxyindole-2-carboxylic acid) 단량체의 중합체로서, 다른 전도성 고분자들과 유사하게 공액구조(pi-pi conjugation)를 가지고 있다. 유멜라닌은 일반적으로 100 내지 150 nm 크기의 구형입자형태로, 사람의 피부, 머리카락과 새의 깃털, 오징어의 먹물 등과 같이 다양한 생체 내에서 안정적으로 존재하는 물질이며, 자외선을 차단하거나 구조색을 구현하는 등의 역할을 한다. 일반적으로 낮은 전도성을 가진 것으로 알려져 있으며, 최대 10-3에서 10-9 S/cm까지 수화될수록 전기전도성이 향상되는 것으로 알려져 있다(비특허문헌 1,2,3,4). 하지만 최근 오징어먹물로부터 추출한 유멜라닌 입자를 이용하여 1.17 S/cm의 고전도성 복합재 연구결과가 보고되어 전도성소재로서의 유멜라닌 사용의 가능성을 열어주었다(비특허문헌 5).Eumelanin, known as a bio-derived conductive material, is a polymer of DHI (5,6-dihydroxyindole) and DHICA (5,6-dihydroxyindole-2-carboxylic acid) monomers, and has a conjugated structure (pi-pi) similar to other conductive polymers. It has conjugation. Eumelanin is generally in the form of spherical particles of 100 to 150 nm in size, and is a substance that exists stably in various living organisms such as human skin, hair, bird feathers, and squid ink. It blocks ultraviolet rays and provides structural color. It plays a role such as It is generally known to have low conductivity, and electrical conductivity is known to improve as it is hydrated from a maximum of 10 -3 to 10 -9 S/cm (Non-patent Documents 1, 2, 3, 4). However, research results on a highly conductive composite of 1.17 S/cm were recently reported using eumelanin particles extracted from squid ink, opening the possibility of using eumelanin as a conductive material (Non-patent Document 5).
본 발명에서 사용하는 폴리도파민은 생체 내에 존재하는 도파민이 중합된 유멜라닌 유사 고분자로 알려져 있다. 일반적으로 염기성용액, 활성산소종, 산화제 등의 조건에서 도파민의 산화에 의해 중합되는 물질이다. 유멜라닌과 유사한 단량체와 구조, 특성을 가지고 있는 것으로 알려져 있으며, 마찬가지로 낮은 전기전도성으로 전도성소재로 사용하는데 한계가 있다. 하지만 최근 산화 화학 기상 증착법 (oxidative chemical vapor deposition)을 이용하여 0.43 S/cm의 높은 전기전도성을 가지는 폴리도파민을 합성하여 폴리도파민의 전도성 소재 활용 가능성을 보여주었다(비특허문헌 6).Polydopamine used in the present invention is known to be a eumelanin-like polymer obtained by polymerizing dopamine present in the body. In general, it is a substance polymerized by oxidation of dopamine under conditions such as basic solutions, active oxygen species, and oxidizing agents. It is known to have similar monomers, structure, and properties to eumelanin, and its use as a conductive material is limited due to its low electrical conductivity. However, polydopamine with high electrical conductivity of 0.43 S/cm was recently synthesized using oxidative chemical vapor deposition, showing the possibility of using polydopamine as a conductive material (Non-patent Document 6).
폴리도파민의 전기화학적 합성은 ‘ECECEE’ 메커니즘으로 알려져 있으며, ‘E’는 전기화학적 반응(electrochemical reaction)을 의미하고 ‘C’는 화학적 반응(chemical reaction)을 의미한다(비특허문헌 7). 이 때문에 일반적으로 자기중합(self-polymerization)이 일어나는 용매 조건에서 전기화학적 합성을 하며, 인산염 완충용액(phosphate buffer saline, PBS)과 트리스 완충용액(Tris buffer, tris(hydroxymethyl)aminomethane)이 대표적인 용액조건이다. 이 조건에 합성된 폴리도파민은 합성과정에서 전극에 흐르는 전류의 양을 감소시키며, 전기화학적 임피던스를 감소시키는 등 절연체에 가까운 전기전도성으로 인하여 전극의 성능을 떨어트린다(비특허문헌 8,9). 이를 해결하기 위하여 폴리에틸렌디옥시티오펜, 폴리피롤 등과 같은 다른 전도성 물질과의 복합재화를 시도하고 있다(비특허문헌 10,11). The electrochemical synthesis of polydopamine is known as the ‘ECECEE’ mechanism, where ‘E’ means electrochemical reaction and ‘C’ means chemical reaction (Non-patent Document 7). For this reason, electrochemical synthesis is generally performed under solvent conditions where self-polymerization occurs, and representative solution conditions include phosphate buffer saline (PBS) and Tris buffer (tris(hydroxymethyl)aminomethane). am. Polydopamine synthesized under these conditions reduces the amount of current flowing through the electrode during the synthesis process and reduces the performance of the electrode due to electrical conductivity close to that of an insulator, such as reducing electrochemical impedance (Non-patent Documents 8, 9). . To solve this problem, attempts are being made to composite it with other conductive materials such as polyethylenedioxythiophene and polypyrrole (Non-patent Documents 10 and 11).
그러나 여전히 폴리도파민의 낮은 전기전도성으로 인하여 응용성이 떨어지므로, 폴리도파민의 낮은 전기전도성을 개선할 필요가 있다.However, the applicability of polydopamine is still low due to its low electrical conductivity, so there is a need to improve the low electrical conductivity of polydopamine.
본 발명은 폴리도파민이 가지고 있는 친수성, 생체적합성, 생분해성, 금속이온킬레이션 등과 같은 다기능성을 생체인터페이스용 생체전극 등의 분야에 적용하는 데 있어서 걸림돌이 되는 폴리도파민의 낮은 전기전도성 문제를 해결하기 위한 것으로, 폴리도파민을 금과 복합재화 하여 폴리도파민의 전기전도성을 향상시킬 수 있도록 하는 폴리도파민-금 복합재 전극 및 이의 제조방법을 제공하고자 하는 데 그 목적이 있다.The present invention solves the problem of polydopamine's low electrical conductivity, which is an obstacle in applying polydopamine's multifunctionality, such as hydrophilicity, biocompatibility, biodegradability, and metal ion chelation, to fields such as bioelectrodes for biointerfaces. The purpose is to provide a polydopamine-gold composite electrode and a method of manufacturing the same that can improve the electrical conductivity of polydopamine by complexing polydopamine with gold.
또한, 본 발명은 상기와 같이 폴리도파민을 금과 복합재화 하는데 있어서, 자기중합이 일어나지 않는 조건에서 순환전압전류법을 통하여 도파민의 산화와 금의 용해반응을 유도하고, 도파민 산화체와 금이온의 산화/환원 반응을 이용하여 금나노입자가 포함된 폴리도파민이 코팅된 전극을 제조하는 폴리도파민-금 복합재 전극 제조방법을 제공하고자 하는 데 그 목적이 있다.In addition, in the present invention, in complexing polydopamine with gold as described above, the oxidation of dopamine and the dissolution reaction of gold are induced through cyclic voltammetry under conditions in which self-polymerization does not occur, and the oxidation of dopamine and gold ions are induced. The purpose is to provide a method for manufacturing a polydopamine-gold composite electrode using an oxidation/reduction reaction to produce an electrode coated with polydopamine containing gold nanoparticles.
상기 과제를 해결하기 위하여, 본 발명은 a) 도파민 혹은 도파민 유도체 중 하나가 용액 내에 용해되어 있거나 준고체상에 포함되어 있는 도파민 용액을 준비하는 단계; b) 전기화학시스템을 도파민 용액에 작동 할 수 있도록 준비하되, 전기화학시스템의 전극이 금을 포함하도록 구성하거나, 또는 상기 도파민 용액에 금을 첨가하는 단계; c) 전기화학적 방법으로 상기 용액 내 도파민을 도파민 산화체로 산화시키고 상기 용액 내에 금을 금 이온으로 이온화 시키는 단계; 및 d) 상기 c) 단계에서 생성되는 도파민 산화체와 금 이온이 산화/환원 반응되면서 폴리도파민과 금나노입자가 생성되고, 상기 작동전극의 표면에 폴리도파민과 금나노입자의 복합체가 증착되는 단계;를 포함하는 것을 특징으로 하는, 폴리도파민-금 복합재 전극의 제조방법을 제공한다.In order to solve the above problem, the present invention includes the steps of a) preparing a dopamine solution in which either dopamine or a dopamine derivative is dissolved in the solution or contained in a semi-solid phase; b) preparing an electrochemical system to operate in a dopamine solution, but configuring the electrodes of the electrochemical system to include gold, or adding gold to the dopamine solution; c) oxidizing dopamine in the solution to dopamine oxide and ionizing gold in the solution into gold ions using an electrochemical method; and d) a step of producing polydopamine and gold nanoparticles through an oxidation/reduction reaction between the dopamine oxide and gold ions produced in step c), and depositing a complex of polydopamine and gold nanoparticles on the surface of the working electrode. It provides a method for manufacturing a polydopamine-gold composite electrode, characterized in that it includes;
본 발명의 일 실시예에 있어서, 상기 폴리도파민-금 복합재 전극은, 금 전극 대비 104 내지 1 Hz 주파수 영역에서의 전기화학적 임피던스가 1 내지 105 배 감소된 것일 수 있다.In one embodiment of the present invention, the polydopamine-gold composite electrode may have electrochemical impedance reduced by 1 to 10 5 times in the 10 4 to 1 Hz frequency range compared to the gold electrode.
본 발명의 일실시예에 있어서, 상기 도파민 혹은 도파민 유도체는, 유사 멜라닌 물질로서, 도파민(dopamine), L-DOPA(L-3,4-dihydroxyphenylalanine), D-DOPA(D-3,4-dihydroxyphenylalanine), D,L-DOPA(D,L-3,4-dihydroxyphenylalanine), DHI(5,6-dihydroxyindole), DHICA(5,6-dihydroxyindole-2-carboxylic acid)와 이들 물질의 유도체 중 하나 이상의 혼합물이 포함되어 중합된 고분자일 수 있다.In one embodiment of the present invention, the dopamine or dopamine derivative is a similar melanin substance, such as dopamine, L-DOPA (L-3,4-dihydroxyphenylalanine), D-DOPA (D-3,4-dihydroxyphenylalanine) ), D,L-DOPA (D,L-3,4-dihydroxyphenylalanine), DHI (5,6-dihydroxyindole), DHICA (5,6-dihydroxyindole-2-carboxylic acid) and mixtures of one or more of these substances. It may be a polymerized polymer containing this.
본 발명의 일실시예에 있어서, 상기 용액은, 도파민의 용해가 가능한 극성 양자성 용매, 또는 상기 극성 양자성 용매와 극성 비양자성 용매의 혼합물을 포함할 수 있다.In one embodiment of the present invention, the solution may include a polar protic solvent capable of dissolving dopamine, or a mixture of the polar protic solvent and a polar aprotic solvent.
본 발명의 일실시예에 있어서, 상기 극성 양자성 용매는, 증류수, 메탄올, 에탄올, 아이소프로판올, 나이트로메테인, n-뷰탄올 중 하나 이상을 포함하고, 상기 극성 비양자성 용매는, 용매의 반응성에 대하여 -3V ~ 3V(vs Ag/AgCl) 범위의 전위창을 가지는 것을 특징으로 한다.In one embodiment of the present invention, the polar protic solvent includes one or more of distilled water, methanol, ethanol, isopropanol, nitromethane, and n-butanol, and the polar aprotic solvent is a solvent of It is characterized by having a potential window in the range of -3V to 3V (vs Ag/AgCl) for reactivity.
본 발명의 일실시예에 있어서, 상기 용매는, pH 가 4.5 ~ 7.0의 약산성 혹은 중성 이고, 용매 내 용존산소가 10 ppm 이하인 것을 특징으로 한다.In one embodiment of the present invention, the solvent is slightly acidic or neutral with a pH of 4.5 to 7.0, and the dissolved oxygen in the solvent is 10 ppm or less.
본 발명의 일실시예에 있어서, 상기 b) 단계는, 상기 작동전극이 금 이온, 금, 합금된 금, 금 입자, 금 코팅, 금박, 금 화합물, 금 복합재 등의 형태로 금을 포함하거나, 도파민 용액 내에 금 이온, 금, 합금된 금, 금 입자, 금 코팅, 금박, 금 화합물, 금 복합재 등의 형태로 금을 포함할 수 있다.In one embodiment of the present invention, in step b), the working electrode includes gold in the form of gold ions, gold, alloyed gold, gold particles, gold coating, gold foil, gold compounds, gold composites, etc., The dopamine solution may contain gold in the form of gold ions, gold, alloyed gold, gold particles, gold coating, gold foil, gold compounds, gold composites, etc.
본 발명의 일실시예에 있어서, 상기 전극은, 금을 포함하는 각종 금속, 합금, 스테인리스 스틸, 전도성고분자, 탄소재료, 그래핀, 탄소나노섬유, 활성산소, 반도체, 세라믹 및 금속산화물 중 하나 이상을 포함하는 도파민의 전기화학적 산화를 유도할 수 있는 전기 혹은 전기화학적 전도성을 가지는 소재를 포함할 수 있다.In one embodiment of the present invention, the electrode is one or more of various metals including gold, alloys, stainless steel, conductive polymers, carbon materials, graphene, carbon nanofibers, active oxygen, semiconductors, ceramics, and metal oxides. It may include a material having electrical or electrochemical conductivity that can induce electrochemical oxidation of dopamine.
본 발명의 일실시예에 있어서, 상기 c) 단계는, 상기 전기화학적 방법으로서, 순환전압전류법, 정전압법, 정전류법 및 플라즈마 처리법 중 하나 이상을 응용하거나 혼합사용하며, 작동전극에 인가되는 전압은 Ag/AgCl 기준전극 또는 상대전극 대비 -3.0 ~ 3.0 V, 바람직하게는 -0.5 ~ 2 V의 전압범위일 수 있다.In one embodiment of the present invention, in step c), as the electrochemical method, one or more of cyclic voltammetry, constant voltage method, constant current method, and plasma treatment method is applied or mixed, and the voltage applied to the working electrode is used. It may be in the voltage range of -3.0 to 3.0 V, preferably -0.5 to 2 V, compared to the Ag/AgCl reference electrode or counter electrode.
또한 본 발명은 상기 폴리도파민-금 복합재 전극의 제조방법에 의해 제조되는 폴리도파민-금 복합재 전극을 제공한다.Additionally, the present invention provides a polydopamine-gold composite electrode manufactured by the method for producing the polydopamine-gold composite electrode.
또한 본 발명은 전극 표면에 폴리도파민-금 복합재가 증착된 것을 특징으로 하는, 폴리도파민-금 복합재 전극을 제공한다.The present invention also provides a polydopamine-gold composite electrode, characterized in that the polydopamine-gold composite is deposited on the electrode surface.
상기 폴리도파민-금 복합재는, 금나노입자 표면에 폴리도파민이 고르게 코팅되어 있는 코어쉘 구조를 가지는 폴리도파민-금 입자 또는 폴리도파민 덩어리에 금나노입자가 박혀있는 구조를 가지는 폴리도파민-금 입자를 포함할 수 있으며, 상기 코어쉘 구조를 가지는 폴리도파민-금 입자의 크기는 10 ~ 100 nm이고, 상기 폴리도파민 덩어리에 금나노입자가 박혀있는 구조를 가지는 폴리도파민-금 입자의 크기는 1 ~ 50 μm 인 것을 특징으로 할 수 있다.The polydopamine-gold composite consists of polydopamine-gold particles having a core-shell structure in which polydopamine is evenly coated on the surface of the gold nanoparticles, or polydopamine-gold particles having a structure in which gold nanoparticles are embedded in a polydopamine lump. It may include, the size of the polydopamine-gold particles having the core-shell structure is 10 to 100 nm, and the size of the polydopamine-gold particles having a structure in which gold nanoparticles are embedded in the polydopamine lump is 1 to 50 nm. It can be characterized as μm.
본 발명의 전기화학적 방법을 이용한 전기전도성 폴리도파민-금 복합재 전극 및 이의 제조방법에 따르면, 자기중합이 일어나지 않는 조건에서 순환전압전류법을 통하여 도파민을 산화시키고 금을 금이온으로 용해시키며, 이에 따라 생성되는 도파민 산화체와 금이온의 산화/환원 반응을 이용하여 폴리도파민과 금나노입자를 생성하고, 이와 같이 생성된 폴리도파민은 금나노입자 표면에 고르게 코팅되거나 금나노입자가 포함된 폴리도파민 입자가 되어 전극 표면에 코팅됨으로써, 폴리도파민-금 복합재 전극을 형성할 수 있다.According to the electrically conductive polydopamine-gold composite electrode using the electrochemical method of the present invention and its manufacturing method, dopamine is oxidized and gold is dissolved into gold ions through cyclic voltammetry under conditions in which self-polymerization does not occur, thereby dissolving gold into gold ions. Polydopamine and gold nanoparticles are produced using the oxidation/reduction reaction of the dopamine oxidation product and gold ions, and the polydopamine produced in this way is evenly coated on the surface of the gold nanoparticles or polydopamine particles containing gold nanoparticles. By coating the surface of the electrode, a polydopamine-gold composite electrode can be formed.
또한, 본 발명은 동시에 폴리도파민의 킬레이션 효과에 의하여 카테콜의 수산화기가 금나노입자 표면에 정렬되면서 폴리도파민의 공액구조가 형성됨으로써, 전극의 전기화학적 임피던스를 낮추고, 전하충전용량과 전하주입한계는 향상시키는 효과가 있다.In addition, the present invention simultaneously forms a conjugated structure of polydopamine by aligning the hydroxyl groups of catechol on the surface of gold nanoparticles due to the chelation effect of polydopamine, thereby lowering the electrochemical impedance of the electrode and reducing the charge charging capacity and charge injection limit. has an improving effect.
또한, 본 발명은 높은 전기화학적전도성, 생체적합성 및 생체안정성을 가지는 폴리도파민을 이용하여 전기전도성이 향상된 폴리도파민-금 복합재 전극를 제조함으로써, 이와 같이 제조된 폴리도파민-금 복합재 전극는 생체바이오센서, 생체배터리, 신경전극, 이식형전극 등의 각종 신경인터페이스와 생체인터페이스의 전극, 인공근육 및 약물전달 시스템을 포함하는 미래의 생체전자공학을 위한 전도성 재료에 적용할 수 있는 효과가 있다.In addition, the present invention manufactures a polydopamine-gold composite electrode with improved electrical conductivity using polydopamine, which has high electrochemical conductivity, biocompatibility, and biostability, so that the polydopamine-gold composite electrode manufactured in this way can be used as a biological biosensor, biological material, etc. It can be applied to conductive materials for future bioelectronics, including various neural interfaces such as batteries, nerve electrodes, and implantable electrodes, biointerface electrodes, artificial muscles, and drug delivery systems.
또한, 본 발명에 따른 폴리도파민-금 복합재 전극는 특정 분자들을 검출하기 위한 친환경센서, 친환경기능성 전극 등의 친환경 소자로의 다양한 응용이 가능한 효과가 있다.In addition, the polydopamine-gold composite electrode according to the present invention has the effect of enabling various applications as eco-friendly devices such as eco-friendly sensors and eco-friendly functional electrodes for detecting specific molecules.
도 1은 본 발명의 실시예 및 비교예에서 제조된 폴리도파민-금 복합재 전극과과 금 전극의 주사전자현미경 사진이다.
도 2는 본본 발명의 실시예 및 비교예에서 제조된 폴리도파민-금 복합재 전극과과 금 전극에 대한 임피던스 성능 평가 결과이다.Figure 1 is a scanning electron microscope photograph of a polydopamine-gold composite electrode and a gold electrode prepared in Examples and Comparative Examples of the present invention.
Figure 2 shows the impedance performance evaluation results for the polydopamine-gold composite electrode and the gold electrode prepared in the Examples and Comparative Examples of the present invention.
이하, 첨부된 도면을 참조하여 본 발명이 속하는 기술분야에서 통상의 지식을 가진 자가 본 발명을 용이하게 실시할 수 있도록 전기화학적 방법을 이용한 전기전도성 폴리도파민-금 복합재 전극 및 이의 제조방법을 상세히 설명하도록 한다. Hereinafter, with reference to the attached drawings, an electrically conductive polydopamine-gold composite electrode and its manufacturing method using an electrochemical method will be described in detail so that those skilled in the art can easily practice the present invention. Let's do it.
본 발명의 바람직한 실시예에 대한 원리를 상세하게 설명함에 있어 관련된 공지 기능 또는 구성에 대한 구체적인 설명이 본 발명의 요지를 불필요하게 흐릴 수 있다고 판단되는 경우에는 그 상세한 설명을 생략한다.In explaining in detail the principles of a preferred embodiment of the present invention, if it is determined that a detailed description of a related known function or configuration may unnecessarily obscure the gist of the present invention, the detailed description will be omitted.
또한, 본 명세서에 기재된 실시예와 도면에 도시된 구성은 본 발명의 가장 바람직한 일 실시예에 불과할 뿐이고 본 발명의 기술적 사상을 모두 대변하는 것은 아니므로, 본 출원 시점에 있어서 이들을 대체할 수 있는 다양한 균등물과 변형 예들이 있을 수 있음을 이해하여야 한다.In addition, the embodiments described in this specification and the configurations shown in the drawings are only one of the most preferred embodiments of the present invention and do not represent the entire technical idea of the present invention, so at the time of filing the present application, various methods that can replace them are available. It should be understood that equivalents and variations may exist.
본 발명을 설명하는 데 있어서, 어떤 부분이 어떤 구성요소를 "포함" 한다고 할 때, 이는 특별히 반대되는 기재가 없는 한 다른 구성요소를 제외하는 것이 아니라 다른 구성요소를 더 포함할 수 있는 것을 의미한다.In describing the present invention, when it is said that a part "includes" a certain component, this means that it does not exclude other components but may further include other components unless specifically stated to the contrary. .
폴리도파민의 전기화학적 중합과 전기화학적 특성에 관하여 많은 선행연구가 진행되어 왔다. 하지만 현재까지 보고된 전기화학적 중합조건은 자가중합이 일어나는 인산염 완충용액나 트리스 완충용액 조건에서 진행되는 경우가 대부분이며, 그 결과 중합 후 전극의 전기화학적 성능을 저하시킨다. Many previous studies have been conducted on the electrochemical polymerization and electrochemical properties of polydopamine. However, electrochemical polymerization conditions reported to date are mostly carried out in phosphate buffer or Tris buffer conditions where self-polymerization occurs, and as a result, the electrochemical performance of the electrode deteriorates after polymerization.
여기서, 상기 자가중합이란 용매 내에서 화학적 산화반응에 의하여 도파민의 산화가 일어나 산화된 도파민이 서서히 폴리도파민으로 중합되는 것을 의미하며, 일반적으로 pH 7.0 이상의 약염기 조건, 활성산소종이 생성되는 조건 등이 용매조건에 해당한다. Here, the self-polymerization means that the oxidation of dopamine occurs through a chemical oxidation reaction in a solvent and the oxidized dopamine is gradually polymerized into polydopamine. Generally, the solvent is under weak base conditions of pH 7.0 or higher and conditions where reactive oxygen species are generated. It corresponds to the condition.
또한, 상기 전기화학적 특성이란 임피던스, 전하충전용량, 전하전달저항, 전하주입한계를 포함하는 전자-이온 전도도와 관련된 특성을 의미한다. Additionally, the electrochemical properties refer to properties related to electron-ion conductivity including impedance, charge charging capacity, charge transfer resistance, and charge injection limit.
본 발명에서는 이러한 전기화학적으로 합성된 낮은 전기화학적 특성의 폴리도파민의 문제점을 해결하여, 보다 높은 전기화학적 특성을 가지며 높은 수준의 안정성을 가지는 복합재를 제조하는 것을 목적으로 지니고 있다.The purpose of the present invention is to solve the problems of electrochemically synthesized polydopamine with low electrochemical properties and to produce a composite material with higher electrochemical properties and a high level of stability.
참고로, 본 발명의 폴리도파민은 도파민을 중합 시킨 고분자를 기본으로 하며, 상기 도파민은 유사 유멜라닌 물질로서, 도파민(dopamine), L-DOPA(L-3,4-dihydroxyphenylalanine), D-DOPA(D-3,4-dihydroxyphenylalanine), D,L-DOPA(D,L-3,4-dihydroxyphenylalanine), DHI(5,6-dihydroxyindole), DHICA(5,6-dihydroxyindole-2-carboxylic acid)와 이들 물질의 유도체 중 하나 이상의 혼합물이 포함되어 중합된 고분자이다.For reference, the polydopamine of the present invention is based on a polymer polymerized with dopamine, and the dopamine is a similar eumelanin substance, including dopamine, L-DOPA (L-3,4-dihydroxyphenylalanine), and D-DOPA ( D-3,4-dihydroxyphenylalanine), D,L-DOPA (D,L-3,4-dihydroxyphenylalanine), DHI (5,6-dihydroxyindole), DHICA (5,6-dihydroxyindole-2-carboxylic acid) and these It is a polymer polymerized by containing a mixture of one or more derivatives of a substance.
본 발명에 따른 높은 전기화학적 특성을 가지는 폴리도파민-금 복합재 전극은 전극 표면에 전기전도성이 뛰어난 폴리도파민-금 복합재가 증착된 것으로, 더욱 상세하게는, 금나노입자 표면에 폴리도파민이 고르게 코팅되어 있는 코어쉘 구조를 가지는 폴리도파민-금 입자와 폴리도파민 덩어리에 금나노입자가 박혀있는 구조를 가지는 폴리도파민-금 입자가 전극 표면에 증착되어 있는 구조를 가진다.The polydopamine-gold composite electrode with high electrochemical properties according to the present invention is a polydopamine-gold composite electrode with excellent electrical conductivity deposited on the electrode surface. More specifically, polydopamine is evenly coated on the surface of the gold nanoparticles. It has a structure in which polydopamine-gold particles, which have a core-shell structure, and polydopamine-gold particles, which have a structure where gold nanoparticles are embedded in polydopamine lumps, are deposited on the electrode surface.
상기 코어쉘 구조를 가지는 폴리도파민-금 입자의 크기는 10 ~ 100 nm이고, 상기 폴리도파민 덩어리에 금나노입자가 박혀있는 구조를 가지는 폴리도파민-금 입자의 크기는 1 ~ 50 μm 이다.The size of the polydopamine-gold particles having the core-shell structure is 10 to 100 nm, and the size of the polydopamine-gold particles having a structure in which gold nanoparticles are embedded in the polydopamine lump is 1 to 50 μm.
이와 같은 구조를 통하여, 기존의 금 전극 표면에 폴리도파민이 코팅된 전극에 비하여 향상된 폴리도파민의 공액구조를 형성함으로써, 기존의 금 전극에 비해 극적으로 개선된 전기화학적 특성을 가지며, 금 전극 표면에 안정적으로 코팅되어 전기화학적으로 높은 안정성을 가진다. Through this structure, a conjugated structure of polydopamine is formed, which is improved compared to the electrode coated with polydopamine on the surface of the existing gold electrode, resulting in dramatically improved electrochemical properties compared to the existing gold electrode. It is stably coated and has high electrochemical stability.
보다 구체적으로는, 본 발명에 따른 폴리도파민-금 복합재 전극은 금 전극에 비하여 임피던스(ElectrochemicalImpedance Spectroscopy, EIS)는 104 내지 1 Hz의 주파수 영역에서의 전기화학적 임피던스를 1 내지 105 배 감소시키며, 전하저장용량(charge storage capacity, CSC) 및 전하주입한계(charge injection limit, CIL)가 각각 수 배에서 수십 배 증가한 특성을 가진다.More specifically, the polydopamine-gold composite electrode according to the present invention reduces the electrochemical impedance (ElectrochemicalImpedance Spectroscopy, EIS) in the frequency range of 10 4 to 1 Hz by 1 to 10 5 times compared to the gold electrode, The charge storage capacity (CSC) and charge injection limit (CIL) are each increased several to dozens of times.
또한, 본 발명에 따른 폴리도파민-금 복합재 전극은 1000회의 CV(cyclic voltammetry) 테스트 후에도 안정적인 임피던스 및 전하주입한계 성능을 유지하여 높은 전기화학적 안정성을 가지는 것으로 나타났다.In addition, the polydopamine-gold composite electrode according to the present invention was found to have high electrochemical stability by maintaining stable impedance and charge injection limit performance even after 1000 CV (cyclic voltammetry) tests.
이하, 본 발명의 전기화학적 방법을 이용한 전기전도성 폴리도파민-금 복합재 전극의 제조방법을 상세히 설명하도록 한다. Hereinafter, the method for manufacturing an electrically conductive polydopamine-gold composite electrode using the electrochemical method of the present invention will be described in detail.
본 발명에 따른 폴리도파민-금 복합재 전극의 제조방법은 다음과 같다. The manufacturing method of the polydopamine-gold composite electrode according to the present invention is as follows.
a) 도파민 혹은 도파민 유도체 중 하나가 용액 내에 용해되어 있거나 준고체상에 포함되어 있는 도파민 용액을 준비하는 단계;a) preparing a dopamine solution in which dopamine or one of the dopamine derivatives is dissolved in the solution or contained in a semi-solid phase;
b) 기화학시스템을 도파민 용액에 작동 할 수 있도록 준비하되, 전기화학시스템의 전극이 금을 포함하도록 구성하거나, 또는 상기 도파민 용액에 금을 첨가하는 단계;b) preparing an electrochemical system to operate in a dopamine solution, but configuring the electrodes of the electrochemical system to include gold, or adding gold to the dopamine solution;
c) 전기화학적 방법으로 상기 용액 내 도파민을 도파민 산화체로 산화시키고 상기 용액 내에 금을 금 이온으로 이온화 시키는 단계; 및c) oxidizing dopamine in the solution to dopamine oxide and ionizing gold in the solution into gold ions using an electrochemical method; and
d) 상기 c) 단계에서 생성되는 도파민 산화체와 금 이온이 산화/환원 반응되면서 폴리도파민과 금나노입자가 생성되고, 상기 작동전극의 표면에 폴리도파민과 금나노입자의 복합체가 증착되는 단계;를 포함한다.d) a step of oxidation/reduction reaction between the dopamine oxide and gold ions produced in step c) to produce polydopamine and gold nanoparticles, and depositing a complex of polydopamine and gold nanoparticles on the surface of the working electrode; Includes.
이와 같이, 전기화학적으로 용해된 금 이온은 전기화학적으로 산화된 도파민 산화체와 산화/환원 반응하여, 산화된 도파민을 고리화시켜 폴리도파민을 형성시키고, 금 이온은 다시 환원되어 금나노입자가 되며, 상기 금나노입자와 폴리도파민은 함께 작동전극 표면에 증착된다.In this way, the electrochemically dissolved gold ions undergo an oxidation/reduction reaction with the electrochemically oxidized dopamine oxide, cyclizing the oxidized dopamine to form polydopamine, and the gold ions are reduced again to become gold nanoparticles. , the gold nanoparticles and polydopamine are deposited together on the surface of the working electrode.
이때, 산화된 도파민은 도파민 퀴논(dopamine quinone)이며, 산화에 의하여 고리화되어 류코도파민크롬(leucodopaminechrome)으로 변하는 물질이다.At this time, the oxidized dopamine is dopamine quinone, which is a substance that is cyclized by oxidation and changes into leucodopaminechrome.
상기와 같이, 본 발명에 따른 폴리도파민-금 복합재 전극의 제조방법은 전기화학적 방법을 폴리도파민의 합성을 유도하고, 작동전극 표면에 폴리도파민과 금의 복합체 입자를 증착시켜 작동전극 표면에 폴리도파민-금 복합재가 코팅되도록 하며, 이와 같이 제조되는 폴리도파민-금 복합재 전극은 금 전극 대비 104 내지 1 Hz 주파수 영역에서의 전기화학적 임피던스가 1 내지 105 배 감소된 것을 특징으로 한다.As described above, the method for producing a polydopamine-gold composite electrode according to the present invention induces the synthesis of polydopamine using an electrochemical method, and deposits composite particles of polydopamine and gold on the surface of the working electrode to deposit polydopamine on the surface of the working electrode. -The gold composite is coated, and the polydopamine-gold composite electrode produced in this way is characterized in that the electrochemical impedance in the frequency range of 10 4 to 1 Hz is reduced by 1 to 10 5 times compared to the gold electrode.
이하, 상기 a) 단계 내지 d) 단계에 대하여 더욱 상세히 설명하도록 한다.Hereinafter, steps a) to d) will be described in more detail.
상기 a) 단계에서, 상기 용매는 도파민의 화학적 자기중합이 일어나지는 않는 용매가 바람직하다. 도파민은 pH 7.0 이상의 약염기성 조건, 활성산소종의 존재하, 산화제 등이 존재하는 조건에서 산화에 의해 화학적 자기중합이 일어난다. 화학적 반응에 의해 일어나는 자기중합은 일반적으로 낮은 전기전도성을 가지고 있는 것으로 알려져 있으며, 특히 전기화학적으로 절연체에 가까운 특성을 보이는 것으로 알려져 있다. In step a), the solvent is preferably a solvent in which chemical self-polymerization of dopamine does not occur. Dopamine undergoes chemical self-polymerization by oxidation under weakly basic conditions above pH 7.0, in the presence of reactive oxygen species, and in the presence of oxidizing agents. Self-polymerization that occurs through a chemical reaction is generally known to have low electrical conductivity, and is especially known to exhibit electrochemical characteristics close to that of an insulator.
즉, 상기와 같은 자기중합 조건에서 전기화학중합을 시도할 경우, 화학적 중합이 동시에 발생하기 때문에 증착된 폴리도파민은 낮은 전기화학적 특성을 보이게 된다. That is, when electrochemical polymerization is attempted under the above self-polymerization conditions, the deposited polydopamine shows low electrochemical properties because chemical polymerization occurs simultaneously.
따라서, 상기 a) 단계에서 도파민이 용해되는 용매는 pH 4.5 ~ 7.0의 약산성 혹은 중성 조건 및 용매 내 용존산소가 10 ppm 이하인 용매조건을 만족하도록 함으로써, 화학적 자기중합에 의해 폴리도파민이 합성되는 것을 방지한다.Therefore, in step a), the solvent in which dopamine is dissolved satisfies the solvent conditions of slightly acidic or neutral pH of 4.5 to 7.0 and dissolved oxygen in the solvent of 10 ppm or less, thereby preventing polydopamine from being synthesized by chemical self-polymerization. do.
이때, 본 발명에서 도파민의 전기화학중합 시 사용가능한 용매는 도파민의 용해가 가능한 극성 양자성 용매를 단독으로 사용하거나, 상기 극성 양자성 용매와 극성 비양자성 용매의 혼합물을 사용할 수 있다.At this time, the solvent that can be used in the electrochemical polymerization of dopamine in the present invention may be a polar protic solvent capable of dissolving dopamine alone, or a mixture of the polar protic solvent and the polar aprotic solvent.
여기서 상기 도파민의 용해가 가능한 극성 양자성 용매는, 증류수, 메탄올, 에탄올, 아이소프로판올, 나이트로메테인, n-뷰탄올 등과 같은 극성 양자성 용매 단일 혹은 1종 이상의 혼합액을 의미한다. 약산성 조건은 염산, 황산, 질산, 아세트산, 포름산, 시안산, 트리클로로아세트산 등의 산을 첨가하여 pH 4.5 ~ 7.0의 조건을 맞춘 것을 의미한다.Here, the polar protic solvent capable of dissolving dopamine refers to a single polar protic solvent or a mixture of one or more polar protic solvents such as distilled water, methanol, ethanol, isopropanol, nitromethane, n-butanol, etc. Weakly acidic conditions mean that conditions of pH 4.5 to 7.0 are adjusted by adding acids such as hydrochloric acid, sulfuric acid, nitric acid, acetic acid, formic acid, cyanic acid, and trichloroacetic acid.
또한, 상기 극성 비양자성 용매는 상기 극성 양자성 용매와 혼합이 가능한 것으로서, 프로필렌 카보네이트(propylene carbonate), 아세토니트릴(acetonitrile), 에틸아세테이트(ethyl acetate), 디메틸설폭사이드(dimethyl sulfoxide), 아세톤 (acetone), 디메틸포름아마이드(dimethylformamide) 등과 같이 넓은 전위창을 가지고 있으며, 바람직하게는 -3V ~ 3V (vs Ag/AgCl)의 범위를 가지는 극성 비양자성 용매를 의미한다.In addition, the polar aprotic solvent can be mixed with the polar protic solvent, such as propylene carbonate, acetonitrile, ethyl acetate, dimethyl sulfoxide, and acetone. ), dimethylformamide, etc., and has a wide potential window, preferably a polar aprotic solvent in the range of -3V to 3V (vs Ag/AgCl).
또한, 상기 준고체상은 액체, 고체, 기체, 고분자겔 등 도파민이 포함될 수 있는 모든 매체를 포함한다. In addition, the semi-solid phase includes all media that can contain dopamine, such as liquid, solid, gas, and polymer gel.
한편, 본 발명은 상기 a) 단계 이후에는 비전도성 고분자 물질을 상기 도파민 용액에 추가하여 용해시키거나, 비전도성 고분자용액을 상기 도파민 용액에 혼합하는 단계를 더 포함할 수 있다. 이러한 비전도성 고분자와의 혼합을 통해 폴리도파민-금 복합재 전극의 형상과 전기화학적 특성, 즉, 임피던스, 전하충전용량, 전하주입한계, 물질반응성 등이 조절할 수 있으며, 목적에 따라 생체적합성, 약물담지, 이온펌핑 등의 다양한 기능성을 부여할 수 있다.Meanwhile, after step a), the present invention may further include adding a non-conductive polymer material to the dopamine solution and dissolving it, or mixing the non-conductive polymer solution with the dopamine solution. Through mixing with these non-conductive polymers, the shape and electrochemical properties of the polydopamine-gold composite electrode, i.e., impedance, charge charging capacity, charge injection limit, and material reactivity, can be adjusted, and biocompatibility and drug carrying properties can be adjusted depending on the purpose. It can provide various functionalities such as ion pumping, etc.
즉, 본 발명은 상기 a) 단계의 도파민 용액에 비전도성 고분자를 혼합하여, 전기화학적으로 작동전극 표면에 증착되는 폴리도파민의 전기전도성을 개선할 수 있다.That is, the present invention can improve the electrical conductivity of polydopamine electrochemically deposited on the surface of the working electrode by mixing a non-conductive polymer with the dopamine solution in step a).
상기 비전도성 고분자는 폴리도파민과 함께 전극에 증착되거나, 폴리도파민의 구조에 영향을 줄 수 있는 고분자로서, 코팅된 폴리도파민의 전기화학적 특성에 영향을 줄 수 있는 것을 의미하며, 이로 제한되지는 않으나, 예시적으로 폴리스틸렌설포네이트, 폴리바이닐알코올, 폴리디아릴디메틸암모늄 클로라이드, 폴리에틸렌옥사이드, 폴리에틸렌글라이콜, 폴리비닐알콜 등을 포함한다.The non-conductive polymer is a polymer that is deposited on an electrode together with polydopamine or can affect the structure of polydopamine, meaning that it can affect the electrochemical properties of coated polydopamine, but is not limited to this. , examples include polystyrene sulfonate, polyvinyl alcohol, polydiaryldimethylammonium chloride, polyethylene oxide, polyethylene glycol, polyvinyl alcohol, etc.
상기 혼합용 고분자나 혼합물을 전도성이 있는 물질로 사용할 경우, 향상된 전극의 전기화학적 특성이 폴리도파민에 의한 것으로 보기 어려우므로, 비전도성 물질로 한정한다.When the mixing polymer or mixture is used as a conductive material, it is difficult to attribute the improved electrochemical properties of the electrode to polydopamine, so it is limited to a non-conductive material.
또한, 상기 b) 단계에서 전기화학시스템을 도파민 용액에 작동할 수 있도록 준비하기 위해서는 전극시스템을 구성하여야 하는데, 1개이상의 전극으로 구성되어있으며, 바람직하게는 작동전극, 상대전극, 기준전극으로 구성된 3 전극시스템이어야 한다. 이 때의 작동전극은 금을 포함하는 각종 금속, 합금, 스테인리스 스틸, 전도성고분자, 탄소재료, 그래핀, 탄소나노섬유, 활성산소, 반도체, 세라믹, 금속산화물 등 도파민의 전기화학적 산화를 유도할 수 있는 전기 혹은 전기화학적 전도성을 가진 소재를 포함하는 전극으로 구성된다. 본 발명의 일 실시예에서, 상기 전극 시스템을 3 전극 시스템으로 구성할 수 있으며, 이 때의 상대전극 및 기준전극은 각각 백금 및 Ag/AgCl 전극을 사용할 수 있으나, 이에 한정되지는 않으며 상대전극은 금, 스테인리스스틸, ITO, FTO 등 반응성이 적고 전도성이 좋은 소재, 기준전극은 SCE, SHE, NHE, RHE 등의 전극이 사용될 수 있다. In addition, in order to prepare the electrochemical system to operate in the dopamine solution in step b), an electrode system must be constructed, which consists of one or more electrodes, preferably consisting of a working electrode, a counter electrode, and a reference electrode. It must be a three electrode system. At this time, the working electrode can induce electrochemical oxidation of dopamine, such as various metals including gold, alloys, stainless steel, conductive polymers, carbon materials, graphene, carbon nanofibers, active oxygen, semiconductors, ceramics, and metal oxides. It consists of an electrode containing a material with electrical or electrochemical conductivity. In one embodiment of the present invention, the electrode system may be configured as a three-electrode system, and in this case, the counter electrode and the reference electrode may use platinum and Ag/AgCl electrodes, respectively, but are not limited thereto, and the counter electrode may be Materials with low reactivity and good conductivity, such as gold, stainless steel, ITO, and FTO, and reference electrodes such as SCE, SHE, NHE, and RHE can be used.
또한, 본 발명에서 전기화학적 폴리도파민의 중합을 위해서는 금 이온이 사용되며, 상기 금 이온은 상기 작동전극 또는 용매 내에 포함될 수 있다. Additionally, in the present invention, gold ions are used for electrochemical polymerization of polydopamine, and the gold ions may be included in the working electrode or solvent.
즉, 본 발명은 금 이온원으로서, 상기 작동전극 내에 금 이온, 금, 합금된 금, 금 입자, 금 코팅, 금박, 금 화합물, 금 복합재 등의 형태로 금을 포함하거나, 또는 도파민 용액 내에 금 이온, 금, 합금된 금, 금 입자, 금 코팅, 금박, 금 화합물, 금 복합재 등의 형태로 금을 포함한다.That is, the present invention is a gold ion source that contains gold in the form of gold ions, gold, alloyed gold, gold particles, gold coating, gold foil, gold compounds, gold composites, etc. in the working electrode, or gold in the dopamine solution. It contains gold in the form of ions, gold, alloyed gold, gold particles, gold coatings, gold foil, gold compounds, gold composites, etc.
상기와 같이, 작동전극 또는 용액 내에 존재하는 금은 염소이온(Cl-)이 존재하는 용액에서 전기화학적으로 금 이온(Au3+)으로의 용해가 가능하다. As described above, gold present in the working electrode or solution can be electrochemically dissolved into gold ions (Au 3+ ) in a solution containing chlorine ions (Cl - ).
또한, 상기(c) 단계에서 상기 전기화학적 방법은, 순환전압전류법, 정전압법, 정전류법 및 플라즈마 처리법 중 적어도 하나 이상을 응용하거나 혼합사용하며, 작동전극에 인가되는 전압은 -3.0 ~ 3.0 V, 바람직하게는 -0.5 ~ 2.0 V (vs. Ag/AgCl)의 전압범위를 포함한다. 참고로, 0.5 ~ 1.0 V (vs. Ag/AgCl)의 전압범위에서는 도파민의 산화가 일어나며, 0.8 ~ 1.3 V (vs. Ag/AgCl)의 전압범위에서는 금의 이온화가 일어난다. In addition, in step (c), the electrochemical method applies or mixes at least one of cyclic voltammetry, constant voltage, constant current, and plasma processing methods, and the voltage applied to the working electrode is -3.0 to 3.0 V. , preferably including a voltage range of -0.5 to 2.0 V (vs. Ag/AgCl). For reference, oxidation of dopamine occurs in the voltage range of 0.5 to 1.0 V (vs. Ag/AgCl), and ionization of gold occurs in the voltage range of 0.8 to 1.3 V (vs. Ag/AgCl).
이때, 상기 순환전압전류법은 -0.5 ~1.5 V (vs. Ag/AgCl)의 전압 범위를 포함하는 전압 범위에서 전압을 일정 속도 (0.1 ~ 1000 mV/s), 일정 횟수 동안 (1 ~ 1000회) 수차례 반복하여 인가하는 방법을 의미한다. 정전압법은 0.8 ~ 1.3V (vs. Ag/AgCl) 이상의 전압을 일정 시간 (1s ~ 24hr) 동안 인가하는 방법을 의미하며, 정전류법은 일정 전류 (1μA ~ 10mA)를 일정 시간 (1s ~ 24hr) 동안 인가하는 방법을 의미하며, 플라즈마 처리법은 전극에 고전압(1~1000V) 혹은 고전류(1mA ~ 1000A)를 인가하여 발생하는 플라즈마를 이용하는 방법을 의미한다.At this time, the cyclic voltammetry method measures the voltage in a voltage range including the voltage range of -0.5 to 1.5 V (vs. Ag/AgCl) at a constant rate (0.1 to 1000 mV/s) for a certain number of times (1 to 1000 times). ) This refers to a method of repeated authorization several times. The constant voltage method refers to a method of applying a voltage of 0.8 ~ 1.3V (vs. Ag/AgCl) or more for a certain period of time (1s ~ 24hr), while the constant current method applies a constant current (1μA ~ 10mA) for a certain period of time (1s ~ 24hr). Plasma treatment refers to a method of using plasma generated by applying high voltage (1 to 1000 V) or high current (1 mA to 1000 A) to an electrode.
이러한 단계를 거쳐 d)단계에서 파민 산화체와 금 이온이 산화/환원 반응되면서 폴리도파민과 금나노입자가 생성되고, 상기 작동전극의 표면에 폴리도파민과 금나노입자의 복합체가 증착되게 된다.Through these steps, in step d), polydopamine and gold nanoparticles are produced through an oxidation/reduction reaction between pamine oxide and gold ions, and a complex of polydopamine and gold nanoparticles is deposited on the surface of the working electrode.
이하, 본 발명에 따른 높은 전기화학적 성능의 폴리도파민-금 복합재 전극의 실시예를 포함하여 상세히 설명한다. 본 발명은 이하에 설명되는 실시예에 한정되는 것이 아니라 더 다양한 방법 및 형태로 구현될 수 있으며, 본 실시예는 본 발명이 실질적으로 적용 가능함을 보이기 위한 수단으로 제공되는 것이다.Hereinafter, the polydopamine-gold composite electrode with high electrochemical performance according to the present invention will be described in detail, including examples. The present invention is not limited to the embodiments described below, but can be implemented in more diverse methods and forms, and this embodiment is provided as a means to show that the present invention is practically applicable.
<실시예 1><Example 1>
본 발명에 따른 높은 전기화학적 성능을 가지는 폴리도파민-금 복합재 전극을 제조하기 위하여 다음과 같이 실험을 구성하였다.In order to manufacture a polydopamine-gold composite electrode with high electrochemical performance according to the present invention, an experiment was conducted as follows.
(a) 도파민 용액의 준비(a) Preparation of dopamine solution
도파민은 일반적으로 구매가능한 도파민 하이드로클로라이드(dopamine hydrochloride)를 구매하여 사용하며, 증류수에 20 mM 농도가 되도록 용해시킨다. 이때, 도파민 용액은 자외선 등에 의한 자기중합이 일어날 수 있기 때문에 4시간 이내에 사용하였다.Dopamine is commonly used as commercially available dopamine hydrochloride, and is dissolved in distilled water to a concentration of 20mM. At this time, the dopamine solution was used within 4 hours because self-polymerization may occur due to ultraviolet rays, etc.
(b) 합성용 금 전극 준비(b) Preparation of gold electrode for synthesis
순도 99.99 % 이상의 100 μm의 금와이어를 20 mm 길이로 절단한 후, 한쪽 끝을 5 mm 남기고 10 mm 폭의 폴리이미드 테이프를 이용하여 절연층을 형성해준다.Cut a 100 μm gold wire with a purity of 99.99% or higher to a length of 20 mm, leave 5 mm at one end, and form an insulating layer using a 10 mm wide polyimide tape.
(c) 3전극 시스템 구성(c) Three-electrode system configuration
전위차발생기에 작동전극으로 상기 (b)의 금와이어를 연결하고, 기준전극은 Ag/AgCl 전극, 상대전극은 백금판을 이용하여 구성하였다.The gold wire in (b) above was connected to the potential generator as a working electrode, the reference electrode was an Ag/AgCl electrode, and the counter electrode was a platinum plate.
(d) 폴리도파민-금 복합재 전극 제조(d) Fabrication of polydopamine-gold composite electrode
상기 (c) 3전극 시스템을 상기 (a) 도파민 용액에 담근 후 -0.5 내지 1.3 V의 전압을 작동전극에 100mV/s의 속도로 100회 반복하여 인가하였다.The three-electrode system (c) was immersed in the dopamine solution (a), and then a voltage of -0.5 to 1.3 V was applied to the working electrode repeatedly 100 times at a rate of 100 mV/s.
<비교예 1> <Comparative Example 1>
폴리도파민-금 복합재 전극 제조에 있어서, 작동전극에 인가하는 전압범위를 -0.5 내지 0.9 V 로 한 것을 제외하고는 상기 실시예 1과 동일한 방법으로 폴리도파민-금 복합재 전극 제조하였다.In manufacturing the polydopamine-gold composite electrode, the polydopamine-gold composite electrode was manufactured in the same manner as Example 1, except that the voltage range applied to the working electrode was -0.5 to 0.9 V.
<비교예 2> <Comparative Example 2>
도파민 용액을 준비하는데 있어서, 증류수 대신 20mM Tris-HCl 완충용액(pH 8.5)을 사용하는 것을 제외하고는 상기 실시예 1과 동일한 방법으로 폴리도파민-금 복합재 전극 제조하였다.In preparing the dopamine solution, a polydopamine-gold composite electrode was prepared in the same manner as Example 1, except that 20mM Tris-HCl buffer solution (pH 8.5) was used instead of distilled water.
<시험예 1><Test Example 1>
상기 실시예 및 비교예에서 제조된 복합재 전극은 1X PBS, 20mM Fe(CN6)3-/4- 및 Ru(NH3)6 2+/3+ 의 전해질 용액에서 전기화학적 특성을 측정하여 비교하였다. 측정된 결과는 도 2에 나타내었다.The composite electrodes prepared in the above examples and comparative examples were compared by measuring electrochemical properties in an electrolyte solution of 1X PBS, 20mM Fe(CN 6 ) 3-/4-, and Ru(NH 3 ) 6 2+/3+. . The measured results are shown in Figure 2.
도 1은 본 발명의 실시예 및 비교예에서 제조된 폴리도파민-금 복합재 전극과과 금 전극의 주사전자현미경 사진이다. Figure 1 is a scanning electron microscope photograph of a polydopamine-gold composite electrode and a gold electrode prepared in Examples and Comparative Examples of the present invention.
도 1에 나타난 바와 같이, 실시예 1에 대한 사진을 확인해보면 폴리도파민-금 복합재가 전극 표면에 형성된 것을 확인할 수 있었다.As shown in Figure 1, when checking the photo for Example 1, it was confirmed that the polydopamine-gold composite was formed on the electrode surface.
또한, 비교예 1의 경우는 기존 금 전극과 큰 차이가 없어, 폴리도파민의 합성이 원할하게 이루어지지 않은 것을 확인할 수 있으며, 비교예 2의 경우는 실시예 1과 비슷한 형태로 폴리도파민-금 복합재가 형성된 것을 확인할 수 있다.In addition, in the case of Comparative Example 1, there was no significant difference from the existing gold electrode, confirming that the synthesis of polydopamine was not performed smoothly, and in the case of Comparative Example 2, a polydopamine-gold composite was used in a similar form to Example 1. It can be confirmed that was formed.
도 2는 본본 발명의 실시예 및 비교예에서 제조된 폴리도파민-금 복합재 전극과과 금 전극에 대한 임피던스 성능 평가 결과이다.Figure 2 shows the impedance performance evaluation results for the polydopamine-gold composite electrode and the gold electrode prepared in the Examples and Comparative Examples of the present invention.
도 2에 나타난 바와 같이, 1X PBS의 전해질 용액에서 폴리도파민-금 복합재 전극의 임피던스를 측정한 경우, 기존 금 전극에 비하여 실시예 1은 약 100배 가량 전기화학적 임피던스가 감소한 것을 확인할 수 있으며, 비교예 1 및 2는 각각 증가 혹은 소량의 감소만 보였다. As shown in Figure 2, when the impedance of the polydopamine-gold composite electrode was measured in an electrolyte solution of 1X PBS, it was confirmed that the electrochemical impedance of Example 1 was reduced by about 100 times compared to the existing gold electrode, Examples 1 and 2 showed only an increase or a small decrease, respectively.
또한, Fe(CN)6 3-/4-의 전해질 용액에서 폴리도파민-금 복합재 전극의 임피던스를 측정한 경우, 실시예 1은 감소하였지만 비교예 2는 증가하였다.In addition, when the impedance of the polydopamine-gold composite electrode was measured in an electrolyte solution of Fe(CN) 6 3-/4- , it decreased in Example 1 but increased in Comparative Example 2.
또한, Ru(NH3)6 2+/3+의 전해질 용액에서 폴리도파민-금 복합재 전극의 임피던스를 측정한 경우, 실시예 1은 기존 금 전극과 유사한 임피던스를 나타냈지만, 비교예 2는 크게 증가하였다.In addition, when the impedance of the polydopamine-gold composite electrode was measured in an electrolyte solution of Ru(NH 3 ) 6 2+/3+ , Example 1 showed an impedance similar to that of the existing gold electrode, but Comparative Example 2 significantly increased. did.
즉, 금 전극 표면에 폴리도파민-금 입자를 증착시켜는 폴리도파민-금 복합재 전극을 제조하는 데 있어서, 전기화학적 제조방법을 이용하여 폴리도파민-금 복합재 전극 제조 시 -0.5 내지 0.8 V의 전압범위에서는 폴리도파민-금 입자가 금 전극 표면에 제대로 증착되지 않았고, -0.5 내지 1.3 V의 전압범위에서 폴리도파민-금 입자가 생성되어 금 전극 표면에 제대로 증착되는 것으로 나타났다.That is, in manufacturing a polydopamine-gold composite electrode by depositing polydopamine-gold particles on the surface of the gold electrode, when manufacturing a polydopamine-gold composite electrode using an electrochemical manufacturing method, the voltage range is -0.5 to 0.8 V. It was found that polydopamine-gold particles were not properly deposited on the gold electrode surface, and polydopamine-gold particles were generated in the voltage range of -0.5 to 1.3 V and were properly deposited on the gold electrode surface.
또한, 상기와 같은 전기화학적 방법을 이용하여 폴리도파민-금 복합재 전극을 제조하는 데 있어서, 도파민이 용해되는 용매가 pH 8.5와 같은 약염기 조건에서는 폴리도파민-금 복합재 전극의 전기전도도가 크게 감소하는 것으로 나타났다.In addition, when manufacturing a polydopamine-gold composite electrode using the above electrochemical method, the electrical conductivity of the polydopamine-gold composite electrode is significantly reduced when the solvent in which dopamine is dissolved is a weak base such as pH 8.5. appear.
이상으로 본 발명은 첨부된 도면에 도시된 실시예를 참조하여 설명되었으나, 이는 예시적인 것에 불과하며, 당해 기술에 속하는 분야에서 통상의 지식을 가진 자라면 이로부터 다양한 변형 및 균등한 타 실시예가 가능하다는 것을 이해할 것이다. 따라서 본 발명의 기술적 보호범위는 아래의 특허청구범위에 의해서 정하여져야 할 것이다.The present invention has been described above with reference to the embodiments shown in the attached drawings, but these are merely illustrative, and various modifications and other equivalent embodiments can be made by those skilled in the art. You will understand that Therefore, the scope of technical protection of the present invention should be determined by the scope of the patent claims below.
Claims (12)
a) 도파민 혹은 도파민 유도체 중 하나가 용액 내에 용해되어 있거나 준고체상에 포함되어 있는 도파민 용액을 준비하는 단계;
b) 전기화학시스템을 도파민 용액에 작동 할 수 있도록 준비하되, 전기화학시스템의 전극이 금을 포함하도록 구성하거나, 또는 상기 도파민 용액에 금을 첨가하는 단계;
c) 전기화학적 방법으로 상기 용액 내 도파민을 도파민 산화체로 산화시키고 상기 용액 내에 금을 금 이온으로 이온화 시키는 단계; 및
d) 상기 c) 단계에서 생성되는 도파민 산화체와 금 이온이 산화/환원 반응되면서 폴리도파민과 금나노입자가 생성되고, 상기 전극의 표면에 폴리도파민과 금나노입자의 복합체가 증착되는 단계;를 포함하며,
상기 용매는 pH 가 4.5 ~ 7.0 이고, 용매 내 용존산소가 10 ppm 이하인 것을 특징으로 하는 것을 특징으로 하는, 폴리도파민-금 복합재 전극의 제조방법.
In the method of manufacturing a polydopamine-gold composite electrode,
a) preparing a dopamine solution in which dopamine or one of the dopamine derivatives is dissolved in the solution or contained in a semi-solid phase;
b) preparing an electrochemical system to operate in a dopamine solution, but configuring the electrodes of the electrochemical system to include gold, or adding gold to the dopamine solution;
c) oxidizing dopamine in the solution to dopamine oxide and ionizing gold in the solution into gold ions using an electrochemical method; and
d) a step of oxidation/reduction reaction between the dopamine oxide and gold ions produced in step c) to produce polydopamine and gold nanoparticles, and depositing a complex of polydopamine and gold nanoparticles on the surface of the electrode; Includes,
A method for producing a polydopamine-gold composite electrode, characterized in that the solvent has a pH of 4.5 to 7.0 and dissolved oxygen in the solvent is 10 ppm or less.
상기 폴리도파민-금 복합재 전극은,
금 전극 대비 104 내지 1 Hz 주파수 영역에서의 전기화학적 임피던스가 1 내지 105 배 감소된 것을 특징으로 하는, 폴리도파민-금 복합재 전극의 제조방법.
According to paragraph 1,
The polydopamine-gold composite electrode is,
A method for producing a polydopamine-gold composite electrode, characterized in that the electrochemical impedance in the 10 4 to 1 Hz frequency range is reduced by 1 to 10 5 times compared to the gold electrode.
상기 도파민 혹은 도파민 유도체는,
유사 유멜라닌 물질로서, 도파민(dopamine), L-DOPA(L-3,4-dihydroxyphenylalanine), D-DOPA(D-3,4-dihydroxyphenylalanine), D,L-DOPA(D,L-3,4-dihydroxyphenylalanine), DHI(5,6-dihydroxyindole), DHICA(5,6-dihydroxyindole-2-carboxylic acid)와 이들 물질의 유도체 중 하나 이상의 혼합물이 포함되어 중합된 고분자인 것을 특징으로 하는, 폴리도파민-금 복합재 전극의 제조방법.
According to paragraph 1,
The dopamine or dopamine derivative,
Similar eumelanin substances include dopamine, L-DOPA (L-3,4-dihydroxyphenylalanine), D-DOPA (D-3,4-dihydroxyphenylalanine), D,L-DOPA (D,L-3,4) Polydopamine, characterized in that it is a polymerized polymer containing a mixture of one or more of -dihydroxyphenylalanine), DHI (5,6-dihydroxyindole), DHICA (5,6-dihydroxyindole-2-carboxylic acid) and derivatives of these substances - Method for manufacturing gold composite electrode.
상기 용액은,
도파민의 용해가 가능한 극성 양자성 용매, 또는 상기 극성 양자성 용매와 극성 비양자성 용매의 혼합물을 포함하는 것을 특징으로 하는, 폴리도파민-금 복합재 전극의 제조방법.
According to paragraph 1,
The solution is,
A method for producing a polydopamine-gold composite electrode, comprising a polar protic solvent capable of dissolving dopamine, or a mixture of the polar protic solvent and the polar aprotic solvent.
상기 극성 양자성 용매는,
증류수, 메탄올, 에탄올, 아이소프로판올, 나이트로메테인, n-뷰탄올 중 하나 이상을 포함하고,
상기 극성 비양자성 용매는, 상기 극성 양자성 용매와 혼합이 가능한 것으로서, -3V ~ 3V(vs. Ag/AgCl)의 전위창을 가지는 것을 특징으로 하는, 폴리도파민-금 복합재 전극의 제조방법.
According to clause 4,
The polar protic solvent is,
Contains one or more of distilled water, methanol, ethanol, isopropanol, nitromethane, and n-butanol,
The polar aprotic solvent is capable of mixing with the polar protic solvent and has a potential window of -3V to 3V (vs. Ag/AgCl). Method for producing a polydopamine-gold composite electrode.
상기 b) 단계에서,
전극이 금 이온, 금, 합금된 금, 금 입자, 금 코팅, 금박, 금 화합물, 금 복합재 등의 형태로 금을 포함하거나,
도파민 용액 내에 금 이온, 금, 합금된 금, 금 입자, 금 코팅, 금박, 금 화합물, 금 복합재 등의 형태로 금을 포함하는 것을 특징으로 하는, 폴리도파민-금 복합재 전극의 제조방법.
According to paragraph 1,
In step b) above,
The electrode contains gold in the form of gold ions, gold, alloyed gold, gold particles, gold coatings, gold foil, gold compounds, gold composites, etc.;
A method for producing a polydopamine-gold composite electrode, characterized in that it contains gold in the form of gold ions, gold, alloyed gold, gold particles, gold coating, gold foil, gold compounds, gold composites, etc. in the dopamine solution.
상기 c) 단계는,
상기 전기화학적 방법으로서, 순환전압전류법, 정전압법, 정전류법 및 플라즈마 처리법 중 하나 이상을 응용하거나 혼합사용하며, 작동전극에 인가되는 전압은 기준전극 또는 상대전극 대비 -3.0 ~ 3.0 V(vs. Ag/AgCl)를 포함하는 것을 특징으로 하는, 폴리도파민-금 복합재 전극의 제조방법.
According to paragraph 1,
In step c),
As the electrochemical method, one or more of the cyclic voltammetry method, constant voltage method, galvanostatic method, and plasma treatment method are applied or mixed, and the voltage applied to the working electrode is -3.0 to 3.0 V (vs. A method for producing a polydopamine-gold composite electrode, characterized in that it contains Ag/AgCl).
A polydopamine-gold composite electrode manufactured by the method for producing a polydopamine-gold composite electrode according to any one of claims 1 to 5, 7, and 8.
상기 폴리도파민-금 복합재는,
금나노입자 표면에 폴리도파민이 고르게 코팅되어 있는 코어쉘 구조를 가지는 폴리도파민-금 입자 또는 폴리도파민 덩어리에 금나노입자가 박혀있는 구조를 가지는 폴리도파민-금 입자를 포함하는 것을 특징으로 하는, 폴리도파민-금 복합재 전극.
Polydopamine-gold composite is deposited on the electrode surface,
The polydopamine-gold composite,
Poly, characterized in that it contains polydopamine-gold particles having a core-shell structure in which polydopamine is evenly coated on the surface of the gold nanoparticles, or polydopamine-gold particles having a structure in which gold nanoparticles are embedded in a polydopamine lump. Dopamine-gold composite electrode.
상기 코어쉘 구조를 가지는 폴리도파민-금 입자의 크기는 10 ~ 100 nm이고, 상기 폴리도파민 덩어리에 금나노입자가 박혀있는 구조를 가지는 폴리도파민-금 입자의 크기는 1 ~ 50 μm 인 것을 특징으로 하는, 폴리도파민-금 복합재 전극.According to clause 10,
The size of the polydopamine-gold particles having the core-shell structure is 10 to 100 nm, and the size of the polydopamine-gold particles having a structure in which gold nanoparticles are embedded in the polydopamine lump is 1 to 50 μm. Polydopamine-gold composite electrode.
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