Feasibility study on detection of fungicides on agricultural produces with SERS

• Project/Area Number: 16K05823
• Research Category: Grant-in-Aid for Scientific Research (C)
• Allocation Type: Multi-year Fund
• Section: 一般
• Research Field: Analytical chemistry
• Research Institution: Toyo University
• Principal Investigator: Takei Hiroyuki 東洋大学, 生命科学部, 教授 (40520789)
• Co-Investigator(Kenkyū-buntansha): 岡本 隆之 国立研究開発法人理化学研究所, 開拓研究本部, 特別嘱託研究員 (40185476)
• Research Collaborator: Gölzhäuser Armin ビーレフェルト大学, 物理学部, 教授
• Project Period (FY): 2016-04-01 – 2019-03-31
• Project Status: Completed (Fiscal Year 2018)
• Budget Amount: ¥4,680,000 (Direct Cost: ¥3,600,000、Indirect Cost: ¥1,080,000); Fiscal Year 2018: ¥1,690,000 (Direct Cost: ¥1,300,000、Indirect Cost: ¥390,000); Fiscal Year 2017: ¥1,690,000 (Direct Cost: ¥1,300,000、Indirect Cost: ¥390,000); Fiscal Year 2016: ¥1,300,000 (Direct Cost: ¥1,000,000、Indirect Cost: ¥300,000)
• Keywords: ラマン分光 / 貴金属ナノ構造体 / 置換反応 / 残留農薬 / プラズモニクス / in-situ計測 / 防かび剤 / 柑橘類 / 表面増強ラマン分光法 / SERS / 銀ナノ構造 / in-situ検出 / 近接場 / 迅速検出 / 貴金属ナノ構造 / 粘着テープ / 環境分析 / 計測工学 / ナノ材料 / マイクロ・ナノデバイス / モニタリング

Outline of Final Research Achievements

We aimed to develop a SERS system for in situ, simple and rapid detection of residual fungicides on agricultural produces by producing a flexible surface decorated by noble metal nano structures and transferring the fungicides by pressing the flexible surface onto the produce. To produce nano structures that can withstand the pressure during the transfer process, we used a galvanic displacement reaction of surface-adsorbed base metal nanoparticles upon exposure to AgNO3 solution. By controlling the size and thickness of the base metal, metal species and reaction temperature, we optimized the silver nano structure on basis of evaluation of SERS spectra of model compounds R6G and BPE. The optimized nano structure was grown on an adhesive tape, which was pressed against an orange treated with 1000 ppm ferbam. Two characteristic peaks at 551 and 1368 cm-1 were detected.

Academic Significance and Societal Importance of the Research Achievements

食の安全は永遠の課題である。輸入される柑橘類等の農作物は、輸送中の劣化を抑制するために、収穫後に防カビ剤で処理されている。関連法案が遵守されていれば健康上の問題はないとされる。しかし、残留基準値（MRL）を越える農薬の使用、使用が認められなくなった農薬、さらに非合法の農薬の使用を防ぐことは急務である。今後、TPP等の条約を通して輸入作物量が増加することが予想されるので、簡便なスクリーニング手法が望まれる。

Research Products

• [Int'l Joint Research] University of Bielefeld(ドイツ)
• [Int'l Joint Research] Bielefeld University(Germany)
• [Int'l Joint Research] ビーレフェルト大学(ドイツ)
• [Journal Article] Protection of silver and gold LSPR biosensors in corrosive NaCl environment by short alkanethiol molecules; characterization by extincdtion spectrum, helium ion microscopy and SERS (2019)
  • Author(s): Hazuki Haraguchi, Natalie Frese, Armin Goelzhaeuser, Hiroyuki Takei
  • Journal Title: RSC Advances Volume: 9 Pages: 9565-9576
  • Peer Reviewed / Open Access / Int'l Joint Research
• [Presentation] Galvanically grown nanodendrites from cap-shaped base metals for surface-enhanced Raman spectroscopy (2019)
  • Author(s): Hiroyuki Takei, S. Hoshino, H. Hazuki, T. Okamoto and A. Goelzhaeuser
  • Organizer: 3S719 Surface science 2019
• [Presentation] 特定利用状況を考慮したSERS基板：食品、農業、水産において (2018)
  • Author(s): 竹井弘之、岡本隆之、アルミン・ゲルツホイザー
  • Organizer: 第78回分析化学討論会
• [Presentation] Three SERS platforms for detecdtion of target molecules in a mixture, in a flow system, and on a surface (2018)
  • Author(s): H. Takei, T. Okamoto, A. Goelzhaeuser
  • Organizer: NFO 15
  • Int'l Joint Research
• [Presentation] 農作物表面の残留農薬検出用の新規SERS基板の作製：ナノ銀樹のSERS応用 (2018)
  • Author(s): 星野翔平、米田真吾、落合悠太、岡本隆之、竹井弘之
  • Organizer: 日本分析化学会第67年会
• [Presentation] Three types of noble metal nanostructures for three types of near-field spectroscopic techniques: how can plasmonics help advance life sciences? (2018)
  • Author(s): Hiroyuki Takei
  • Organizer: The 10th International Forum on Post-Genome Technologies and 11th International Workshop on Approaches to Single-Cell Analysis
  • Int'l Joint Research / Invited
• [Presentation] Application Specific SERS Substrates (2017)
  • Author(s): Hiroyuki Takei, Junichiro Saito, Keiko Kato, Kosuke Watanabe, Takayuki Okamoto, Armin Goelzhaeuser
  • Organizer: Pittcon 2017
  • Place of Presentation: 米国イリノイ州シカゴ
  • Year and Date: 2017-03-08
  • Int'l Joint Research
• [Presentation] SERSの実用化に向けた貴金属ナノ構造体作製の試み (2017)
  • Author(s): H. Takei, K. Nagata, J. Saito, K. Kato, H. Takasawa, K. Watanabe, T. Fujiki, S. Yoneda, T. Okamoto, N. Frese, H. Vieker, A. Beyer, A. Goelzhaeuser
  • Organizer: 第14回プラズモニクスシンポジウム
  • Place of Presentation: 福井大学（福井県・福井市）
  • Year and Date: 2017-01-28
• [Presentation] Three types of plasmonics nanostrucutres as bioanalytical SERS platforms (2017)
  • Author(s): H. Takei, K. Nagata, J. Saito, K. Watanabe, S. Yoneda, T. Okamoto, N. Frese, H. Vieker, A. Beyer, and A. Golzhauser
  • Organizer: The 8th International Conference on Surface Plasmon Photonics, Taipei, Taiwan, May 22-26, 2017
  • Int'l Joint Research
• [Presentation] Three types of nanostructures platforms for plasmonics detection of target molecules on a solid surface or in a complex medium. (2017)
  • Author(s): H. Takei
  • Organizer: The 7th Euro Biosensors and Bioeletronics, July 10-11, 2017
  • Int'l Joint Research
• [Presentation] 固体表面吸着物質同定用の圧着型SERS基板 (2017)
  • Author(s): 竹井弘之、渡辺康介、藤木啓、相原凜花、岡本隆之
  • Organizer: 日本分析化学会第66年会 東京 平成29年9月10日
• [Presentation] 置換反応により作製した貴金属ナノ構造体を用いた表面増強ラマン分光法の検討 (2016)
  • Author(s): 岡田有貴、米田真吾、竹井弘之、岡本隆之、Armin Goelzhaeuser
  • Organizer: 日本分析化学会第65年会
  • Place of Presentation: 北海道大学工学部（北海道・札幌市）
  • Year and Date: 2016-09-14
• [Patent(Industrial Property Rights)] 表面増強ラマン分光用基板およびその製造方法 (2017)
  • Inventor(s): 竹井弘之、藤木啓
  • Industrial Property Rights Holder: 竹井弘之、藤木啓
  • Industrial Property Rights Type: 特許
  • Industrial Property Number: 2017-024502
  • Filing Date: 2017-02-13