ITO 전극 위에 고정된 니켈 나노 입자를 이용한 무효소 혈당센서에 관한 전기화학적인 연구

오인돈,김사만다,최영봉,Oh, In-Don,Kim, Samantha,Choi, Young-Bong 한국전기화학회 2014 한국전기화학회지 Vol.17 No.3

무효소 혈당센서는 높은 선택성과 민감성을 가지고 저비용으로 체내 혈당(glucose)을 검출할 수차세대 기술이다. 현재 시판되고 있는 혈당센서는 당을 산화시켜주는 당산화효소와 전극과 효소사이에 전자 전달을 원활하게 해주는 산화/환원 매개체를 이용하여 효소센서로 제작된다. 그러나 이러한 효소센서는 pH, 온도, 습도, 화학적 독성물질 등에 영향을 많이 받아 안정성이 떨어지고, 제작에 비용이 많이 드는 단점을 가지고 있다. 본 논문은 위와 같은 단점을 해결하고자 환원제인 당에 의하여 환원되는 니켈 나노입자를 전기화학적 흡착방법을 이용하여 산화 인듐 주석 전극 (ITO)에 고정시켰다. 고정된 니켈 나노입자는 전극의 표면적을 넓혀 신호를 증폭시키는 효과를 가지고 있으며, 당에 의하여 계속적으로 니켈이 환원됨에 따라 전극 반응에서는 촉매산화전류 반응으로 나타낸다. 당의 농도에 따라서 선형적으로 감응 할 수 있는 최적 조건의 니켈 나노입자를 이용하여 혈당센서를 제작하였다. 또한 체내에 존재하는 방해 인자인 아스코브산의 간섭을 억제하기 위해 음이온 고분자의 표면처리를 통하여 상대적으로 당에 선택적으로 감응하도록 하였다. 제작된 전극을 통하여 당 농도 별 산화 촉매 전류를 순환 전압 전류 법으로 측정한 결과 650 mV (vs. Ag/AgCl)에서 최대 전기적 신호가 발생되었으며, 포도당 0~6.15 mM 의 농도범위에서 전기적 신호가 선형 증가함을 확인할 수 있었다. A highly sensitive and selective non-enzymatic glucose sensor has gained great attention because of simple signal transformation, low-cost, easily handling, and confirming the blood glucose as the representative technology. Until now, glucose sensor has been developed by the immobilization of glucose oxidase (GOx) on the surface of electrodes. However although GOx is quite stable compared with other enzymes, the enzyme-based biosensors are still impacted by various environment factors such as temperature, pH value, humidity, and toxic chemicals. Non-enzymatic sensor for direct detecting glucose is an attractive alternative device to overcome the above drawbacks of enzymatic sensor. Many efforts have been tried for the development of non-enzymatic sensors using various transition metals (Pt, Au, Cu, Ni, etc.), metal alloys (Pt-Pb, Pt-Au, Ni-Pd, etc.), metal oxides, carbon nanotubes and graphene. In this paper, we show that Ni-based nano-particles (NiNPs) exhibit remarkably catalyzing capability for glucose originating from the redox couple of $Ni(OH)_2/NiOOH$ on the surface of ITO electrode in alkaline medium. But, these non-enzymatic sensors are nonselective toward oxidizable species such as ascorbic acid the physiological fluid. So, the anionic polymer was coated on NiNPs electrode preventing the interferences. The oxidation of glucose was highly catalyzed by NiNPs. The catalytically anodic currents were linearly increased in proportion to the glucose concentration over the 0~6.15 mM range at 650 mV versus Ag/AgCl.

Recent advances in electrochemical non-enzymatic glucose sensors – A review

Hwang, Dae-Woong,Lee, Saram,Seo, Minjee,Chung, Taek Dong Elsevier 2018 Analytica chimica acta Vol.1033 No.-

<P><B>Abstract</B></P> <P>This review encompasses the mechanisms of electrochemical glucose detection and recent advances in non-enzymatic glucose sensors based on a variety of materials ranging from platinum, gold, metal alloys/adatom, non-precious transition metal/metal oxides to glucose-specific organic materials. It shows that the discovery of new materials based on unique nanostructures have not only provided the detailed insight into non-enzymatic glucose oxidation, but also demonstrated the possibility of direct detection in whole blood or interstitial fluids. We critically evaluate various aspects of non-enzymatic electrochemical glucose sensors in terms of significance as well as performance. Beyond laboratory tests, the prospect of commercialization of non-enzymatic glucose sensors is discussed.</P> <P><B>Highlights</B></P> <P> <UL> <LI> This review summarizes the latest progress in non-enzymatic electrochemical sensors. </LI> <LI> The review encompasses fundamental principles of electrochemical glucose detection. </LI> <LI> The merits and demerits of various electrode materials are discussed. </LI> <LI> The authors critically evaluate numerous aspects concerning current research. </LI> <LI> The prospect of clinical application of non-enzymatic glucose monitoring is described. </LI> </UL> </P> <P><B>Graphical abstract</B></P> <P>[DISPLAY OMISSION]</P>

Electrochemical Non-Enzymatic Glucose Sensor based on Hexagonal Boron Nitride with Metal-Organic Framework Composite

( Suresh Ranganethan ),( Sang-mae Lee ),( Jaewon Lee ),( Seung-cheol Chang ) 한국센서학회 2017 센서학회지 Vol.26 No.6

In this study, an amperometric non-enzymatic glucose sensor was developed on the surface of a glassy carbon electrode by simply drop-casting the synthesized homogeneous suspension of hexagonal boron nitride (h-BN) nanosheets with a copper metal-organic framework (Cu-MOF) composite. Comprehensive analytical methods, including field-emission scanning electron microscopy (FE-SEM), Fourier-transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD), cyclic voltammetry, electrochemical impedance spectroscopy, and amperometry, were used to investigate the surface and electrochemical characteristics of the h-BN-Cu-MOF composite. The FE-SEM, FT-IR, and XRD results showed that the h-BN-Cu-MOF composite was formed successfully and exhibited a good porous structure. The electrochemical results showed a sensor sensitivity of 18.1 μAμM^-1cm^-2 with a dynamic linearity range of 10-900 μM glucose and a detection limit of 5.5 μM glucose with a rapid turnaround time (less than 2 min). Additionally, the developed sensor exhibited satisfactory anti-interference ability against dopamine, ascorbic acid, uric acid, urea, and nitrate, and thus, can be applied to the design and development of non-enzymatic glucose sensors.

표면 개질된 샤프심 전극의 전기화학적 특성 고찰 및 비효소적 글루코스 센서 활용

송민정 한국화학공학회 2024 Korean Chemical Engineering Research(HWAHAK KONGHA Vol.62 No.2

의료용 센서들은 대부분 일회용 제품으로, 검사·진단 비용을 줄이기 위해서는 저가의 전극 소재 개발이 무엇보다 중요하다. 본 연구에서는 일회용 전기화학센서의 전극 소재로 pencil graphite를 도입하여 전처리 효과와 전도성 고분자 폴리아닐린(polyaniline; PANI) 및 금속 산화물 CuO NPs를 이용한 표면 개질(modification)을 통한 전기화학적 특성을 조사하고, 이를 글루코스 검출용 비효소 전기화학센서에 적용하였다. Pencil graphite electrode (PGE)의 표면 활성화를 위한 전처리는 화학적과 전기화학적으로 각각 진행되었으며, 전처리된 샘플들은 시간대전류법(CA)과 순환전압 전류법(CV), 전기화학 임피던스(EIS) 분석법을 이용한 전기화학적 특성 조사를 통해 최종적으로 전기화학적 전처리 방법을 채택하여 CuO NPs/PANI/E-PGE를 제작하였다. 이를 적용한 비효소적 글루코스 검출용 전기화학 센서는 0.282 ~2.112mM과 3.75423~50 mM의 선형 구간에서 각각 239.18 mA/mM×cm2과 36.99 mA/mM×cm2 정도의 감도(sensitivity)와 17.6μM의 검출 한계(detection limit), 글루코스에 대한 좋은 선택도(selectivity)를 보였다. 본 연구의 결과를 토대로 PGEs를 활용한 다양한 일회용 센서 응용과 저가의 고성능 전극 소재 개발 가능성을 확인하고, 더 많은 분야에 활용할 수 있을 것으로 기대된다. Most medical sensors are disposable products. In order to reduce inspection and diagnosis costs, it is more important to develop the inexpensive electrode materials. We fabricated the CuO NPs/PANI/E-PGE as an electrode material for disposable electrochemical sensors and applied it to a non-enzymatic glucose sensor. For surface activation of PGE, pretreatment was performed using chemical and electrochemical methods, respectively. Electrochemical properties according to the pretreatment method were analyzed through chronoamperometry (CA),cyclic voltammetry (CV) and electrochemical impedance (EIS). From these analytical results, the electrochemically pretreated PGE (E-PGE) was finally adopted. The non-enzymatic glucose sensor based on CuO NPs/PANI/E-PGE shows sensitivity of 239.18 mA/mM×cm2 (in a linear range of 0.282~2.112 mM) and 36.99 mA/mM×cm2 (3.75423~50mM), detection limit of 17.6 μM and good selectivity. Based on the results of this study, it was confirmed that the modified PGE is a high-performance electrode material. Therefore, these electrodes can be applied to a variety of disposable sensors.

A Metal-Free, Non-Enzymatic Electrochemical Glucose Sensor with a de-Bundled Single-Walled Carbon Nanotube-Modified Electrode

Dinakaran Thirumalai,Devaraju Subramani,신보성,백현종,장승철 대한화학회 2018 Bulletin of the Korean Chemical Society Vol.39 No.2

A new metal-free, non-enzymatic electrochemical sensor system for the detection of glucose was developed in this study. The developed sensor uses a de-bundled single-walled carbon nanotube (SWCNT)-modified glassy carbon electrode (GCE). SWCNTs were de-bundled in aqueous solution by adding a synthesized polymer dispersant, sulfonated poly(ether sulfone). The de-bundled SWCNTs showed two significant characteristics: (1) improvement of the aspect ratio and dispersibility in aqueous solution and (2) suitability for use as a selective and sensitive sensing element in non-enzymatic glucose sensors. The experimental results clearly demonstrated that the SWCNTs/GCE possesses high electro-catalytic activity and efficient sensitivity with a stable and faster amperometric response production. Furthermore, interference by ascorbic acid, acetaminophen, uric acid, and dopamine is effectively avoided. Therefore, the proposed approach is favorable for the design and development of non-enzymatic glucose sensors.

MOF-based Sensing Materials for Non-enzymatic Glucose Sensors

Jingjing Liu,Xiaoting Zha,Yajie Yang The Korean Electrochemical Society 2024 Journal of electrochemical science and technology Vol.15 No.1

Diabetes mellitus is one of the common chronic diseases, seriously threating to human health. The continuous monitoring of blood glucose concentration can effectively prevent diabetic diseases. The sensing performance of glucose non-enzymatic sensors is mainly determined by working electrode materials. Metal-organic frameworks (MOFs) are recognized as promising candidate for glucose sensor application, due to its large surface areas, ordered porous structure and nearly infinite designability. In this review, the sensing performance, research progress and future challenge of non-enzymatic glucose sensors based on MOF-based materials in recent years are presented. We hope that this review would provide valuable technology guidance for high performance non-enzymatic glucose sensors based on MOFs.

Fabrication of sensitive non-enzymatic nitrite sensor using silver-reduced graphene oxide nanocomposite

Ahmad, Rafiq,Mahmoudi, Tahmineh,Ahn, Min-Sang,Yoo, Jin-Young,Hahn, Yoon-Bong Elsevier 2018 JOURNAL OF COLLOID AND INTERFACE SCIENCE - Vol.516 No.-

<P><B>Abstract</B></P> <P>There are increasing demands of more sensitive sensors for monitoring potential hazards in real water that may cause serious problems to human health. Herein, we report the development of a non-enzymatic nitrite sensor using nanocomposite of reduced graphene oxide decorated with silver nanoparticle (Ag-rGO). First, Ag-rGO nanocomposite was synthesized using a facile and cost-effective microwave-assisted approach. Then, as-synthesized Ag-rGO nanocomposite was used to modify glassy carbon electrode (GCE) and applied for the sensitive and selective detection of nitrite in the aqueous medium with increasing concentration of nitrite. Under optimized conditions, sensor achieved high sensitive response (18.4 μA/μM·cm<SUP>2</SUP>) in a wide linear range (0.1–120 μM), low limit of detection (∼0.012 μM), and good selectivity using differential pulse voltammograms (DPV). The applicability of fabricated non-enzymatic nitrite sensor was checked in real sample with satisfactory results.</P> <P><B>Graphical abstract</B></P> <P>[DISPLAY OMISSION]</P>

탄소섬유 토우의 전처리 효과와 비효소적 포도당 센싱 성능 평가

송민정 한국화학공학회 2024 Korean Chemical Engineering Research(HWAHAK KONGHA Vol.62 No.1

웨어러블 디바이스용 유연 전극 소재 개발을 위해 탄소섬유 토우(carbon fibers tow)의 전처리에 따른 전기화학적 특성을 조사하고, 이를 활용하여 포도당을 타겟으로 전기화학적 비효소 센서를 제작하였다. 탄소섬유 토우는 탈사이징(desizing)과 활성화(activation) 공정을 통해 전처리 되었으며, 활성화는 화학적 산화와 전기화학적 산화의 두 가지 방법으로 이루어졌다. 전처리된 샘플은 주사전자 현미경(SEM)을 이용하여 표면 분석되었으며, 전기화학적 특성 및 센싱성능 분석은 시간대전류법와 순환전압 전류법, 전기화학 임피던스 분석법을 이용하여 수행되었다. 탄소섬유 토우는 전처리를 통해 감소된 Ret 와 ΔEp, 증가된 Ip 등 향상된 전기화학적 특성을 보였으며, 두 활성화 방법에서는 유사한 전기화학적 특성이 얻어졌다. 본 연구에서는 전기화학센서 적용을 위해 전기화학적으로 활성화된 탄소섬유 토우를 최종 전극 물질로 선정하였다. 이 전극을 기반으로 제작된 비효소적 포도당 검출 센서는 0.09899~3.754mM과 3.754~50 mM의선형 구간에서 각각 0.744 mA/mM과 0.330 mA/mM 정도의 향상된 감도를 보였다. 본 연구를 통해 탄소섬유 토우의전극 소재로서 사용 가능성을 확인했으며, 고성능 유연 전극 소재 개발에 기초 연구로 활용 가능할 것으로 기대된다. To develop flexible electrode materials for wearable devices, we investigated the electrochemical characteristics of carbon fibers tow according to pretreatment. And an electrochemical non-enzymatic sensor was fabricated using glucose as a target. The carbon fibers tow was pretreated through desizing and activation processes, and activation was performed in two ways: chemical oxidation and electrochemical oxidation. Surface morphology of carbon fibers tow samples was observed by SEM and their electrochemical characteristics and sensing performance were investigated by cyclic voltammetry, electrochemical impedance spectroscopy and chronoamperometry. Carbon fibers tow samples showed improved electrochemical properties such as reduced Ret, ΔEp, and increased Ip through pretreatment. And similar electrochemical properties were obtained with both activation methods. We selected electrochemically activated carbon fibers tow as the final electrode material for application of electrochemical sensor. The non-enzymatic glucose sensor based on this electrode has an enhanced sensitivity of 0.744 A/mM (in a linear range of 0.09899~3.75423 mM) and 0.330 mA/mM (3.75423~50 mM), respectively. Through this study, the possibility of using carbon fibers tow was confirmed as an electrode material. It is expected to be used as basic research for development of high-performance flexible electrode materials.

Debundling of Carbon Nanotube by Sulfonated Poly(ether sulfone) and Silver Nanowire for Hydrogen Peroxide Sensor

Thirumalai Dinakaran,Subramani Devaraju,Bosung Shin(신보성),Hyun-jong Paik(백현종),Seung-Cheol Chang(장승철) 한국고분자학회 2017 폴리머 Vol.41 No.6

탄소섬유전극을 기반으로 효소가 불필요한 과산화수소(H₂O₂) 센서를 분산된 은 나노와이어와 단일벽 탄소나노튜브를 탄소섬유전극 표면에 드롭캐스팅법으로 고정화하여 제작하였다. 센서 제작에 사용된 탄소나노튜브는 고분자 분산제인 술폰화 폴리(에테르 술폰)에 의하여 효과적인 길이/직경의 종횡비를 나타낼 수 있도록 개별 분산되었으며 센서의 성능 향상을 위하여 은 나노와이어와 더불어 컴포지트 형태로 제작되어 새로운 센서 제작법에 활용되었다. 제작된 센서는 H₂O₂에 대하여 높은 전기촉매활성과 재현성, 빠른 분석 시간 및 우수한 감도를 나타냄을 확인하였다(센서 감도: 1.3 μA·mM<SUP>-1</SUP>, 검출 한계: 0.69 μM (S/N=3) 및 검출 시간: 3초 미만). 따라서 본 연구에서 개발된 고분자 분산제를 사용한 단일벽 탄소나노튜브의 수용액 내에서의 분산도 향상은 효소가 불필요한 H₂O₂ 센서의 설계 및 제작에 활용될 것으로 기대된다. A new non-enzymatic hydrogen peroxide (H₂O₂) sensor based on carbon fiber microelectrodes (CFMEs) has been developed. The CFMEs were modified using a simple drop casting procedure with effectively dispersed silver nanowires (AgNWs) and debundled single-walled carbon nanotubes (SWCNTs). In aqueous solution, the SWCNTs were debundled with a high length/diameter aspect ratio using a synthesized polymer dispersant, sulfonated poly(ether sulfone) (SPES). Enhanced electrocatalytic activity of the sensor for the reduction of H₂O₂ was obtained with the sensor sensitivity of 1.3 μA·mM<SUP>-1</SUP> and the detection limit of 0.69 μM (S/N=3) with a quick turnaround time (less than 3 s). The results clearly reveal that the AgNW-SWCNTs/CFMEs possess high electro-catalytic activity and efficient sensitivity with high reproducibility and fast amperometric response production. Therefore, the proposed debundling approach can be expanded to design and develop nonenzymatic hydrogen peroxide sensors.

N-doped graphene-carbon nanotube hybrid networks attaching with gold nanoparticles for glucose non-enzymatic sensor

Jeong, Hun,Nguyen, Dang Mao,Lee, Min Sang,Kim, Hong Gun,Ko, Sang Cheol,Kwac, Lee Ku Elsevier 2018 Materials science & engineering. C, Materials for Vol.90 No.-

<P><B>Abstract</B></P> <P>Herein, we successfully developed a novel three dimensional (3D) opened networks based on nitrogen doped graphene‑carbon nanotubes attaching with gold nanoparticles (N-GR-CNTs/AuNPs) to apply for non-enzymatic glucose determination. It was demonstrated that the N-GR-CNTs/AuNPs modified electrode exhibited good behavior for glucose detection with a long linear range of 2 μM to 19.6 mM, high sensitivity of 0.9824 μA·mM<SUP>−1</SUP>·cm<SUP>−2</SUP>, low detection limit of 500 nM, and negligible interference effect. The high performance of the N-GR-CNTs/AuNPs based sensor was assumed due to the outstanding catalytic activity of AuNPs well dispersing on N-GR-CNTs networks, which exhibited as a perfect supporting scaffold due to the enhanced electrical conductivity and large surface area. The obtained results indicated that the N-GR-CNTs/AuNPs hybrid is highly promising for sensitive and selective detection of glucose in sensor application.</P> <P><B>Highlights</B></P> <P> <UL> <LI> 3D network of N-GR-CNT-deposited Au NPs was synthesized for electrochemical sensor. </LI> <LI> The glucose was detected with linear detection range of 2 μM to 19.6 mM and low detection limit of 500 nM. </LI> <LI> The hybrid based sensor showed good stability and selectivity. </LI> </UL> </P> <P><B>Graphical abstract</B></P> <P>[DISPLAY OMISSION]</P>