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대한화학회 제124회 학술발표회 및 총회 Design of nanocarbon film electrodes with extended analyte zones

등록일
2019년 9월 25일 10시 30분 34초
접수번호
3208
발표코드
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발표시간
목 10시 : 00분
발표형식
심포지엄
발표분야
Analytical Chemistry - [KCS-JAIMA Joint Symposium] Analytical Chemistry with JAIMA: Biosensor Development
저자 및
공동저자
Dai Kato
Biomedical Research Institute, National Institute of Advanced Industrial Science and Technology, Japan
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승인 1건
We have been studying nanocarbon film electrodes formed by an electron cyclotron resonance (ECR) sputtering or an unbalanced magnetron (UBM) sputtering method.1) The film provides a nanocrystalline sp2 and sp3 mixed bond structure with an atomically flat surface (surface roughness of 0.05 – 0.1 nm) and high conductivity without doping. The film electrode has excellent properties including a low background current, a wide electrochemical potential window, and little surface fouling, while maintaining relatively high electrode activity for various analytes. These characteristics allow the detection of various analytes, which are difficult to measure at the conventional carbon electrodes. For example, this film electrode can measure all DNA bases (including DNA base derivatives e.g., 5’-methylcytosine) quantitatively.2) Moreover, due to their good electrochemical stability and low background current, the nanocarbon film electrode is suitable for long-term analysis including as the electrode of an HPLC detector for detecting cerebral gliotransmitter from real samples.3)
The nanocarbon film surface can be easily modified with other atoms/nanoparticle without losing its ultraflatness.4) For example, we previously developed electrochemically stable fluorinated nanocarbon (F-nanocarbon) film by CF4 plasma treatment. We applied for quantitative measurements of lipophilic antioxidants (α-tocopherol) with maintaining the suppression for the responses of hydrophilic antioxidants (ascorbic acid) in liquid food samples. We observed irreversible oxidation peaks for vitamin E, but electrochemical response for vitamin C was effectively suppressed. Moreover, even in the mixed solution, the peak current at the F-nanocarbon film electrode was in good agreement with that for the vitamin E alone.5) These results indicate that there is no interference. This is highly advantageous in terms of constructing a simple assay of antioxidant because an extraction process is usually required prior to the conventional assay.
Our sputtering method can also be applied to develop metal nanoparticle-embedded nanocarbon film electrodes by using UBM co-sputtering methods for detecting some analytes (geosmin, arsenic ions and sugars), which are difficult to detect at the nanocarbon film itself.6) For example, the co-sputtering of Pt and carbon formed Pt nanoparticle (typically 2.5 nm in diameter) spontaneously in the carbon films, owing to the poor intermiscibility of Pt with carbon. With the optimized condition, we achieved excellent performance for detecting geosmin with high sensitivity solely by direct oxidation.
The most significant and implicative point of these works, is that the nanocarbon film-based electrodes can expand possibility to detect analytes, which is previously unattainable for measurements (due to electrode problem such as narrow potential window, large background noise, and low electrode activity).

References
1) (a) O. Niwa, J. Jia, Y. Sato, D. Kato, R. Kurita, K. Maruyama, K. Suzuki, S. Hirono, J. Am. Chem. Soc., 128, 7144 (2006), (b) T. Kamata, D. Kato, H. Ida, O. Niwa, Diamond. Relat. Mater., 49, 25 (2014).
2) (a) D. Kato, N. Sekioka, A. Ueda, R. Kurita, S. Hirono, K. Suzuki, O. Niwa, Angew. Chem. Int. Ed., 47, 6681 (2008), (b) D. Kato, N. Sekioka, A. Ueda, R. Kurita, S. Hirono, K. Suzuki, O. Niwa, J. Am. Chem. Soc., 130, 3716 (2008).
3) S. Yamamura, M. Hoshikawa, D. Kato, H. Saito, N. Suzuki, O. Niwa, M. Okada, Br. J. Pharmacol., 168 1088 (2013).
4) (a) A. Ueda, D. Kato, N. Sekioka, T. Kamata, R. Kurita, H. Uetsuka, Y. Hattori, S. Hirono, S. Umemura, O. Niwa, Carbon, 47, 1943 (2009)
5) (a) E. Kuraya, S. Nagatomo, K. Sakata, D. Kato, O. Niwa, T. Nishimi, M. Kunitake, Anal. Chem., 87, 1489 (2015), (b) E. Kuraya, S. Nagatomo, K. Sakata, D. Kato, O. Niwa, T. Nishimi, M. Kunitake, Anal Chem., 88, 1202 (2016).
6) (a) T. Kamata, M. Sumimoto, S. Shiba, R. Kurita, O. Niwa, D. Kato, Nanoscale, 11, 8845 (2019), (b) D. Kato, T. Kamata, D. Kato, H. Yanagisawa, O. Niwa, Anal. Chem., 88, 2944 (2016), (c) S. Shiba, D. Kato, T. Kamata, O. Niwa, Nanoscale, 8, 12887 (2016).

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