Development of Chemical Shift Expanding Reagents to Enhance the Resolution of Low Field NMR with Permanent Magnet

• Project/Area Number: 18K05167
• Research Category: Grant-in-Aid for Scientific Research (C)
• Allocation Type: Multi-year Fund
• Section: 一般
• Review Section: Basic Section 34020:Analytical chemistry-related
• Research Institution: University of Toyama
• Principal Investigator: Aizawa Sen-ichi 富山大学, 学術研究部工学系, 教授 (60231099)
• Co-Investigator(Kenkyū-buntansha): 小玉 修嗣 東海大学, 理学部, 教授 (70360807)
• Project Period (FY): 2018-04-01 – 2024-03-31
• Project Status: Completed (Fiscal Year 2023)
• Budget Amount: ¥4,420,000 (Direct Cost: ¥3,400,000、Indirect Cost: ¥1,020,000); Fiscal Year 2020: ¥1,430,000 (Direct Cost: ¥1,100,000、Indirect Cost: ¥330,000); Fiscal Year 2019: ¥1,430,000 (Direct Cost: ¥1,100,000、Indirect Cost: ¥330,000); Fiscal Year 2018: ¥1,560,000 (Direct Cost: ¥1,200,000、Indirect Cost: ¥360,000)
• Keywords: NMR化学シフト / 化学シフト拡張試薬 / ポルフィリン錯体 / キラルシグナル分離 / 低磁場NMR / キラル化合物 / 絶対配置の帰属 / 多核NMR / 可視CDスペクトル / キラルNMRシグナル分離 / キラルランタノイド錯体、 / キラルホスフィン / 31P NMR / NMRキラルシフト試薬 / 低磁場ＮＭＲ / フタロシアニン錯体 / その場分析

Outline of Final Research Achievements

We prepared Co(III) complexes with porphyrins as a reagent for expansion of NMR chemical shifts. These reagents can increase difference in the chemical shifts of the same two substituent groups in the same molecule under different magnetic environments and can enhance the chiral signal separation of NMR chiral shift reagents.

Academic Significance and Societal Importance of the Research Achievements

近年、NMRの分解能向上を目指し、超電導磁石の高磁場化が進められてきた。一方最近になって、維持費やメンテナンスがほとんど不要で、設置場所の制限もない永久磁石型低磁場NMR装置の開発が再び盛んになった。しかしながら、これらの装置開発だけでは限界があるため、本研究で開発した化学シフトの拡張試薬を用いることによって低磁場NMRの分解能を向上できることは、永久磁石型低磁場NMR装置を用いた簡便なNMRのその場分析の価値を高めた。

Research Products

• [Journal Article] Reaction mechanism of decomposition of phosphine-bridged Pd(I)-Pd(I) dimers into Pd(II) monomers by molecular iodine (2024)
  • Author(s): Aizawa Sen-ichi、Taniguchi Ayano、Haruta Yuji
  • Journal Title: Journal of Molecular Liquids Volume: 399 Pages: 124379-124379
  • DOI: 10.1016/j.molliq.2024.124379
  • Peer Reviewed / Open Access
• [Journal Article] Direct chiral separation of abscisic acid by high‐performance liquid chromatography with a phenyl column and a mobile phase containing γ‐cyclodextrin (2023)
  • Author(s): Terashima Hiroyuki、Mutoh Yui、Aizawa Sen‐ichi、Taga Atsushi、Mikami Ikko、Itabashi Yutaka、Tsutsumiuchi Kaname、Yamamoto Atsushi、Kodama Shuji
  • Journal Title: Journal of Separation Science Volume: 46 Issue: 6 Pages: 1-8
  • DOI: 10.1002/jssc.202200827
  • Peer Reviewed
• [Journal Article] Chiral separation of catechin and epicatechin by reversed phase high-performance liquid chromatography with β-cyclodextrin stepwise and linear gradient elution modes (2022)
  • Author(s): Terashima Hiroyuki、Seki Mayuko、Watanabe Saki、Yamamoto Atsushi、Aizawa Sen-ichi、Taga Atsushi、Mikami Ikko、Kodama Shuji
  • Journal Title: Journal of Chromatography A Volume: 1673 Pages: 463029-463029
  • DOI: 10.1016/j.chroma.2022.463029
  • Peer Reviewed
• [Journal Article] Kinetic Investigation of Pd(II)-Catalyzed <i>Ortho</i> C-H Iodination of Benzamide with I₂ (2021)
  • Author(s): Aizawa Sen-ichi、Takeuchi Yoichi
  • Journal Title: Bulletin of the Chemical Society of Japan Volume: 94 Issue: 4 Pages: 1261-1263
  • DOI: 10.1246/bcsj.20210002
  • NAID: 130008037374
  • Peer Reviewed
• [Journal Article] Enantioseparation of phenethylamines by using high‐performance liquid chromatography column permanently coated with methylated β‐cyclodextrin (2021)
  • Author(s): Terashima Hiroyuki、Yamamoto Atsushi、Aizawa Sen‐ichi、Taga Atsushi、Mikami Ikko、Ishihara Yoshimi、Kodama Shuji
  • Journal Title: Journal of Separation Science Volume: 44 Issue: 15 Pages: 2932-2940
  • DOI: 10.1002/jssc.202100343
  • Peer Reviewed
• [Journal Article] Kinetic Investigation of Pd(II)-Catalyzed ortho C-H Iodination of Benzamide with I2 (2021)
  • Author(s): Aizawa Sen-ichi, Takeuchi Yoichi
  • Journal Title: Bulletin of the Chemical Society of Japan Volume: 94
  • NAID: 130008037374
  • Peer Reviewed
• [Journal Article] A Simple Screening Method for Extra Virgin Olive Oil Adulteration by Determining Squalene and Tyrosol (2020)
  • Author(s): Hayakawa Tatsuya、Yanagawa Miran、Yamamoto Atsushi、Aizawa Sen-ichi、Taga Atsushi、Mochizuki Naoki、Itabashi Yutaka、Uchida Hajime、Ishihara Yoshimi、Kodama Shuji
  • Journal Title: Journal of Oleo Science Volume: 69 Issue: 7 Pages: 677-684
  • DOI: 10.5650/jos.ess20033
  • NAID: 130007868853
  • ISSN: 1345-8957, 1347-3352
  • Peer Reviewed
• [Journal Article] Direct enantioseparation of mandelic acid by high‐performance liquid chromatography using a phenyl column precoated with a small amount of cyclodextrin additive in a mobile phase (2020)
  • Author(s): Watanabe Yuri、Mikami Ikko、Yamamoto Atsushi、Aizawa Sen‐ichi、Taga Atsushi、Mochizuki Naoki、Ishihara Yoshimi、Kodama Shuji
  • Journal Title: Chirality Volume: 32 Issue: 7 Pages: 1020-1029
  • DOI: 10.1002/chir.23228
  • Peer Reviewed
• [Journal Article] Enantiomeric NMR signal separation mechanism and prediction of separation behavior for a praseodymium (III) complex with (S,S)-ethylenediamine-N,N-disuccinate (2020)
  • Author(s): Aizawa Sen-ichi、Okano Masaru
  • Journal Title: Magnetic Resonance in Chemistry Volume: 58 Issue: 10 Pages: 941-948
  • DOI: 10.1002/mrc.5062
  • Peer Reviewed
• [Journal Article] A Simple Screening Method for Extra Virgin Olive Oil Adulteration by Determining Squalene and Tyrosol (2020)
  • Author(s): Tatsuya Hayakawa, Miran Yanagawa, Atsushi Yamamoto, Sen-ichi Aizawa, Atsushi Taga, Naoki Mochizuki, Yutaka Itabashi, Yoshimi Ishihara, Shuji Kodama
  • Journal Title: Journal of Olro Science Volume: 69
  • NAID: 130007868853
  • Peer Reviewed
• [Journal Article] Direct Enantioseparation of Mandelic Acid by HPLC using a Phenyl Column pre-coated with a small amount of Cyclodextrin Additive in a Mobile Phase (2020)
  • Author(s): Yuri Watanabe, Ikko Mikami, Atsushi Yamamoto, Sen-ichi Aizawa, Atsushi Taga, Naoki Mochizuki, Yoshimi Ishihara, Shuji Kodama
  • Journal Title: Chirality Volume: 32
  • Peer Reviewed
• [Journal Article] Separation of Synephrine Enantiomers in Citrus Fruits by a Reversed Phase HPLC after Chiral Precolumn Derivatization (2019)
  • Author(s): TANAKA Sohei、SEKIGUCHI Misaki、YAMAMOTO Atsushi、AIZAWA Sen-ichi、SATO Kanta、TAGA Atsushi、TERASHIMA Hiroyuki、ISHIHARA Yoshimi、KODAMA Shuji
  • Journal Title: Analytical Sciences Volume: 35 Issue: 4 Pages: 407-412
  • DOI: 10.2116/analsci.18P441
  • NAID: 130007629974
  • ISSN: 0910-6340, 1348-2246
  • Year and Date: 2019-04-10
  • Peer Reviewed
• [Journal Article] Mechanistic study on substitution reaction of a citrato(p-cymene)Ru(ii) complex with sulfur-containing amino acids (2019)
  • Author(s): Aizawa Sen-ichi、Takizawa Kohei、Aitani Momoko
  • Journal Title: RSC Advances Volume: 9 Issue: 43 Pages: 25177-25183
  • DOI: 10.1039/c9ra05507j
  • Peer Reviewed / Open Access
• [Journal Article] Chiral separation of isoxanthohumol and 8-prenylnaringenin in beer, hop pellets and hops by HPLC with chiral columns (2018)
  • Author(s): Moriya Hyuga、Tanaka Sohei、Iida Yukari、Kitagawa Satomi、Aizawa Sen-ichi、Taga Atsushi、Terashima Hiroyuki、Yamamoto Atsushi、Kodama Shuji
  • Journal Title: Biomedical Chromatography Volume: 32 Issue: 10
  • DOI: 10.1002/bmc.4289
  • Peer Reviewed
• [Presentation] 低濃度のシクロデキストリンを移動相に用いたキラルHPLC法によるマンデル酸の光学異性体分析 (2020)
  • Author(s): 渡邊由梨・三上一行・山本敦・會澤宣一・多賀淳・望月直樹・石原良美・小玉修嗣
  • Organizer: 日本薬学会第140年会
• [Presentation] Cu(I)触媒を用いたジホスフィンの生成とジホスフィンカルコゲニドとPd(II)錯体との新規反応性 (2019)
  • Author(s): 井林優紀、二村伸、松原圭佑、會澤宣一
  • Organizer: 錯体化学会第69回討論会
• [Presentation] トリアゼニド系配位子を有するPd(I)およびPd(II)錯体の合成と触媒活性 (2019)
  • Author(s): 藤澤朋里、中橋有太、會澤宣一
  • Organizer: 錯体化学会第69回討論会
• [Presentation] 31P NMRを用いた不斉リン化合物のキラルランタノイド錯体によるシグナル分離とその応用 (2019)
  • Author(s): 岡野優、佐々木ひなの、會澤宣一
  • Organizer: 錯体化学会第69回討論会
• [Presentation] スクアレン及びチロソールの分析によるエキストラバージンオリーブ油とそのブレンド油とのスクリーニング判別分析 (2019)
  • Author(s): 早川達也、柳川実蘭、山本敦、會澤宣一、多賀淳、望月直樹、板橋豊、石原良美、小玉修嗣
  • Organizer: 日本油化学会第58回年会
• [Presentation] 不斉小分子を有するCo(III)Cl(TPPS)錯体の不斉会合体形成 (2019)
  • Author(s): 太田直希、會澤宣一
  • Organizer: 日本化学会第９９春季年会
• [Presentation] オルト置換ジフェニルトリアゼニド配位子を有するPd(I)-Pd(I)二核錯体の触媒活性 (2018)
  • Author(s): 中橋有太、會澤宣一
  • Organizer: 錯体化学会第68回討論会
• [Presentation] Speciation of Ru(II)(p-cymene) with Amino Acids and Reaction Mechanism of Their Formation (2018)
  • Author(s): Sen-ichi. Aizawa, Kouhei Takizawa
  • Organizer: 43rd International Conference on Coordination Chemistry
  • Int'l Joint Research
• [Presentation] プレカラム誘導体化法による柑橘類中シネフリンのキラルHPLC分析 (2018)
  • Author(s): 田中壮平、山本敦、會澤宣一、多賀淳、寺島弘之、小玉修嗣
  • Organizer: 日本分析化学会第67回年会
• [Presentation] 日本酒中フェルラ酸のHPLC分析 (2018)
  • Author(s): 小玉修嗣、石下雄介、後藤宏章、田中壮平、佐野博之、山本敦、會澤宣一、多賀 淳、寺島 弘之
  • Organizer: 日本分析化学会第67回年会
• [Presentation] アブシシン酸の光学異性体分析 (2018)
  • Author(s): 田中壮平、山本敦、會澤宣一、多賀 淳、小玉修嗣
  • Organizer: 第35回イオンクロマトグラフィー討論会
• [Book] 錯体化合物事典 (2019)
  • Author(s): 會澤宣一他（分担執筆）
  • Total Pages: 4
  • Publisher: 朝倉書店