Development and application of in situ spectromicroscopy using soft X-ray inner-shell excitation

• Project/Area Number: 26248010
• Research Category: Grant-in-Aid for Scientific Research (A)
• Allocation Type: Single-year Grants
• Section: 一般
• Research Field: Physical chemistry
• Research Institution: Institute for Molecular Science
• Principal Investigator: KOSUGI Nobuhiro 分子科学研究所, 光分子科学研究領域, 教授 (20153546)
• Co-Investigator(Kenkyū-buntansha): 大東 琢治 分子科学研究所, 極端紫外光研究施設, 助教 (50375169) ; 繁政 英治 分子科学研究所, 極端紫外光研究施設, 准教授 (90226118)
• Co-Investigator(Renkei-kenkyūsha): NAGASAKA Masanari 分子科学研究所, 光分子科学研究領域, 助教 (90455212) ; YAMANE Hiroyuki 分子科学研究所, 光分子科学研究領域, 助教 (50402459)
• Project Period (FY): 2014-04-01 – 2017-03-31
• Project Status: Completed (Fiscal Year 2016)
• Budget Amount: ¥37,050,000 (Direct Cost: ¥28,500,000、Indirect Cost: ¥8,550,000); Fiscal Year 2016: ¥11,310,000 (Direct Cost: ¥8,700,000、Indirect Cost: ¥2,610,000); Fiscal Year 2015: ¥11,310,000 (Direct Cost: ¥8,700,000、Indirect Cost: ¥2,610,000); Fiscal Year 2014: ¥14,430,000 (Direct Cost: ¥11,100,000、Indirect Cost: ¥3,330,000)
• Keywords: 量子ビーム / 内殻励起 / Ｘ線顕微分光 / その場観測 / 薬物伝達

Outline of Final Research Achievements

In order to apply soft X-ray absorption spectroscopy (XAS) to chemical materials with the spatial resolution of 30 nm, we have developed transmission-type in situ cells installed into scanning transmission X-ray microscopy (STXM). By using the spatially-resolved XAS, we have investigated the reaction mechanism of inhomogeneous chemical materials such as phase separation of aqueous triethylamine solutions, electrochemical reactions, and drug delivery systems. The local structure of microfluidics, which realizes highly efficient solution reactions, is also analyzed by using XAS with the spatial resolution of 30 micron.

Research Products

• [Int'l Joint Research] ヘルムホルツ協会ベルリン研究センター/ベルリン自由大学(ドイツ)
• [Int'l Joint Research] ローレンス・バークレー国立研究所(米国)
• [Int'l Joint Research] マックマスター大学/カナダ放射光源施設(カナダ)
• [Int'l Joint Research] 国家同歩輻射研究センター/淡江大学(台湾)
• [Int'l Joint Research] オウル大学(フィンランド)
• [Int'l Joint Research] ベルリン自由大学/ヘルムホルツ協会ベルリン研究センター(HZB)(ドイツ)
• [Int'l Joint Research] 淡江大学/台湾国立放射光研究センター(NSRRC)(台湾)
• [Int'l Joint Research] マックマスター大学/カナダ放射光施設(CLS)(カナダ)
• [Journal Article] Unusual Water Hydrogen Bond Network around Hydrogenated Nanodiamonds (2017)
  • Author(s): T. Petit, L. Puskar, T. Dolenko, S. Choudhury, E. Ritter, S. Burikov, K. Laptinskiy, Q. Brzustowski, U. Schade, H. Yuzawa, M. Nagasaka, N. Kosugi, M. Kurzyp, A. Venerosy, H. Girard, J.-C. Arnault, E. Osawa, N. Nunn, O. Shenderova, E. F. Aziz
  • Journal Title: Journal of Physical Chemistry C Volume: 121 Issue: 9 Pages: 5185-5194
  • DOI: 10.1021/acs.jpcc.7b00721
  • Peer Reviewed / Open Access / Int'l Joint Research / Acknowledgement Compliant
• [Journal Article] Integration of Active Nickel Oxide Clusters by Amino Acids for Water Oxidation (2017)
  • Author(s): M. Yoshida, S. Onishi, Y. Mitsutomi, F. Yamamoto, M. Nagasaka, H. Yuzawa, N. Kosugi, H. Kondoh
  • Journal Title: Journal of Physical Chemistry C Volume: 121 Issue: 1 Pages: 255-260
  • DOI: 10.1021/acs.jpcc.6b08796
  • Peer Reviewed
• [Journal Article] Development of In-Situ/Operando Sample Cells for Soft X-ray Transmission Spectromicroscopy at UVSOR-III Synchrotron (2017)
  • Author(s): M. Nagasaka, T. Ohigashi, N. Kosugi
  • Journal Title: Synchrotron Radiation News Volume: 30(2) Issue: 2 Pages: 3-7
  • DOI: 10.1080/08940886.2017.1289798
  • Peer Reviewed / Open Access / Acknowledgement Compliant
• [Journal Article] X-ray and Electron Spectroscopy of Water (2016)
  • Author(s): T. Fransson, Y. Harada, N. Kosugi, N. A. Besley, B. Winter, J. J. Rehr, L. G. M. Pettersson, A. Nilsson
  • Journal Title: Chemical Review Volume: 116 Issue: 13 Pages: 7551-7569
  • DOI: 10.1021/acs.chemrev.5b00672
  • Peer Reviewed / Open Access / Int'l Joint Research
• [Journal Article] Impacts of Conformational Geometries in Fluorinated Alkanes (2016)
  • Author(s): T. Brandenburg, R. Golnak, M. Nagasaka, K. Atak, S.S.N. Lalithambika, N. Kosugi, E. F. Aziz
  • Journal Title: Scientific Reports Volume: 6 Issue: 1
  • DOI: 10.1038/srep31382
  • Peer Reviewed / Open Access / Int'l Joint Research / Acknowledgement Compliant
• [Journal Article] Improve Hole Collection by Interfacial Chemical Redox Reaction at a Mesoscopic NiO/CH3NH3PbI3 Heterojunction for Efficient Photovoltaic Cells (2016)
  • Author(s): M.W. Lin, K. C. Wang, J.H. Wang, M. H. Li, Y.L. Lai, T. Ohigashi, N. Kosugi, P. Chen, D.H. Wei, T.F. Guo, Y.J. Hsu
  • Journal Title: Advanced Materials Interfaces Volume: 3 Issue: 17
  • DOI: 10.1002/admi.201600135
  • Peer Reviewed / Int'l Joint Research / Acknowledgement Compliant
• [Journal Article] Core-multishell nanocarriers: Transport and release of dexamethasone probed by soft X-ray spectromicroscopy (2016)
  • Author(s): K. Yamamoto, A. Klossek, R. Flesch, T. Ohigashi, E. Fleige, F. Rancan, J. Frombach, A. Vogt, U. Blume-Peytavi, P. Schrade, S. Bachmann, R. Haag, S. Hedtrich, M. Schaefer-Korting, N. Kosugi, E. Ruehl
  • Journal Title: Journal of Controlled Release Volume: 242 Pages: 64-70
  • DOI: 10.1016/j.jconrel.2016.08.028
  • Peer Reviewed / Int'l Joint Research / Acknowledgement Compliant
• [Journal Article] Soft X-ray Absorption Spectroscopy in Transmission Mode: Chemical Shifts and Technical Developments for Chemical State Analysis of Interacting Molecular Systems (2016)
  • Author(s): 長坂将成, 小杉信博
  • Journal Title: Journal of the Vacuum Society of Japan Volume: 59 Issue: 11 Pages: 301-306
  • DOI: 10.3131/jvsj2.59.301
  • NAID: 130005282120
  • ISSN: 1882-2398, 1882-4749
  • Open Access
• [Journal Article] UVSOR-IIIの走査型透過Ｘ線顕微鏡における化学状態分析法の開発 (2016)
  • Author(s): 大東琢治、小杉信博
  • Journal Title: 日本放射光学会誌 Volume: 19 Pages: 287-293
  • Open Access
• [Journal Article] Observation of DNA and protein distributions in mammalian cell nuclei using STXM (2016)
  • Author(s): T. Ohigashi, A. Ito, K. Shinohara, S. Tone, M. Kado, Y. Inagaki, Y.-F. Wang, N. Kosugi
  • Journal Title: AIP Conference Proceedings Volume: 1696 Pages: 020027-020027
  • DOI: 10.1063/1.4937521
  • Peer Reviewed / Open Access / Int'l Joint Research
• [Journal Article] Development and application of in situ/operando soft X-ray transmission cells to aqueous solutions and catalytic and electrochemical reactions (2015)
  • Author(s): Masanari Nagasaka, Hayato Yuzawa, Nobuhiro Kosugi
  • Journal Title: J. Electron Spectrosc. Relat. Phenom. Volume: 200 Pages: 293-310
  • DOI: 10.1016/j.elspec.2015.05.012
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Selective Probing of the Penetration of Dexamethasone into Human Skin by Soft X-ray Spectromicroscopy (2015)
  • Author(s): K .Yamamoto, R. Flesch, T. Ohigashi, S. Hedtrich, A. Klossek, P. Patoka, G. Ulrich, S. Ahlberg, F. Rancan, A. Vogt, U. Blume-Peytavi, P. Schrade, S. Bachmann, M. Schaefer-Korting, N. Kosugi, E. Ruehl
  • Journal Title: Analytical Chemistry Volume: 87 Issue: 12 Pages: 6173-6179
  • DOI: 10.1021/acs.analchem.5b00800
  • Peer Reviewed / Int'l Joint Research / Acknowledgement Compliant
• [Journal Article] In situ soft X-ray absorption spectroscopy applied to solid-liquid heterogeneous cyanopyrazine hydration reaction on titanium oxide catalyst (2015)
  • Author(s): Hayato Yuzawa, Masanari Nagasaka, Nobuhiro Kosugi
  • Journal Title: J. Phys. Chem. C Volume: 119 Issue: 14 Pages: 7738-7745
  • DOI: 10.1021/jp512891t
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] 軟Ｘ線吸収分光法による電気化学反応の局所構造解析 (2015)
  • Author(s): 長坂将成、大東琢治、小杉信博
  • Journal Title: 分析化学 Volume: 64 Pages: 163-172
  • NAID: 130005060602
  • Peer Reviewed / Acknowledgement Compliant
• [Presentation] 軟X線吸収分光法による液体と液液界面の局所電子状態の解明 (2017)
  • Author(s): 長坂将成
  • Organizer: 日本化学会第97春季年会・若い世代の特別講演会
  • Place of Presentation: 慶應大学日吉キャンパス、横浜（神奈川県）
  • Year and Date: 2017-03-16
  • Invited
• [Presentation] Liquid and liquid-liquid interface studied by soft X-ray absorption in transmission mode (2017)
  • Author(s): N. Kosugi
  • Organizer: International Workshop on Liquid X-ray Spectroscopy, LiXS2017
  • Place of Presentation: SOLEIL, Saclay, France
  • Year and Date: 2017-01-17
  • Int'l Joint Research / Invited
• [Presentation] Development of Scanning Transmission X-ray Microscopy for in situ/operando Chemical Analysis at UVSOR-III (2016)
  • Author(s): T. Ohigashi, Y. Inagaki, N. Kosugi
  • Organizer: Mechanical Engineering Design of Synchrotron Radiation Equipment and Instrumentation, MEDSI 2016
  • Place of Presentation: Barcelona, Spain
  • Year and Date: 2016-09-11
  • Int'l Joint Research
• [Presentation] Optimal Energy and Spatial Resolutions for in situ/operando Soft X-ray Absorption Spectroscopy (2016)
  • Author(s): N. Kosugi
  • Organizer: 2nd International Workshop on Soft X-ray Science Opportunities using Diffraction-limited Storage Rings
  • Place of Presentation: Hefei, China
  • Year and Date: 2016-08-17
  • Int'l Joint Research / Invited
• [Presentation] A QUANTITATIVE 3-DIMENSIONAL OBSERVATION METHOD FOR SCANNING TRANSMISSION X-RAY MICROSCOPY (2016)
  • Author(s): T. Ohigashi, Y. Inagaki, A. Ito, K. Shinohara, N. Kosugi
  • Organizer: International Conference X-ray Microscopy, XRM 2016
  • Place of Presentation: Oxford, U.K.
  • Year and Date: 2016-08-15
  • Int'l Joint Research
• [Presentation] Chemical Applications of a Scanning Transmission X-ray Microscope Developed at UVSOR-III Synchrotron (2016)
  • Author(s): T. Ohigashi, Y. Inagaki, N. Kosugi
  • Organizer: 39th International Conference on Vacuum Ultraviolet and X-ray Physics, VUVX 2016
  • Place of Presentation: Zurich, Switzerland
  • Year and Date: 2016-07-03
  • Int'l Joint Research
• [Presentation] Chemical Shifts in Inner-shell Excitations arising from Molecular Interactions (2016)
  • Author(s): N. Kosugi
  • Organizer: International Conference on The Future of X-ray and Electron Spectroscopies, XRAY-2016
  • Place of Presentation: Uppsala, Sweden
  • Year and Date: 2016-06-15
  • Int'l Joint Research / Invited
• [Presentation] 軟Ｘ線吸収分光法によるチオシアン酸カリウム水溶液の局所構造観察 (2016)
  • Author(s): 湯沢勇人、長坂将成、小杉信博
  • Organizer: 日本化学会第９６春季年会
  • Place of Presentation: 同志社大学（京都府京田辺市)
  • Year and Date: 2016-03-27
• [Presentation] 分子の内殻励起に関する先導的実験および理論 (2016)
  • Author(s): 小杉信博
  • Organizer: 日本化学会第９６春季年会
  • Place of Presentation: 同志社大学（京都府京田辺市)
  • Year and Date: 2016-03-25
  • Invited
• [Presentation] 軟Ｘ線吸収分光法と赤外分光法による液体ベンゼンの分子間相互作用の観測 (2016)
  • Author(s): 長坂将成、湯沢勇人、望月健爾、Ruehl, Eckart, 小杉信博
  • Organizer: 日本化学会第９６春季年会
  • Place of Presentation: 同志社大学（京都府京田辺市)
  • Year and Date: 2016-03-24
• [Presentation] Quantum Chemical Approaches to Molecular X-ray Spectroscopy (2015)
  • Author(s): 小杉信博
  • Organizer: Workshop on Prediction and Interpretation of Core-level (K-, L-edge, etc.) Spectroscopy: PICKLES 2015
  • Place of Presentation: ローレンスバークレー国立研究所（アメリカ、バークレー）
  • Year and Date: 2015-10-06
  • Int'l Joint Research / Invited
• [Presentation] Soft X-ray Absorption Spectroscopy of Liquid and Application to In Operando Observations (2015)
  • Author(s): 長坂将成
  • Organizer: International Workshop on Soft X-ray in Energy and Time (SWET2015)
  • Place of Presentation: ヘルムホルツ協会ベルリン研究センター（ドイツ、ベルリン）
  • Year and Date: 2015-08-20
  • Int'l Joint Research / Invited
• [Presentation] 軟X線吸収分光法による溶液の局所構造解析とオペランド観測への展開 (2014)
  • Author(s): 長坂将成
  • Organizer: 第37回溶液化学シンポジウム
  • Place of Presentation: アバンセ（佐賀県佐賀市）
  • Year and Date: 2014-11-12 – 2014-11-14
  • Invited
• [Presentation] Energy Shifts in X-ray Absorption and Photoelectron Spectra of Liquid Water (2014)
  • Author(s): Nobuhiro Kosugi
  • Organizer: NORDITA Conference on Water
  • Place of Presentation: アルバノヴァ研究センター（スウェーデン・ストックホルム）
  • Year and Date: 2014-10-27 – 2014-10-31
  • Invited
• [Presentation] Advanced spectroscopic studies on molecular electronic states at UVSOR-III facility (2014)
  • Author(s): Hiroyuki Yamane
  • Organizer: Asia-Oceania Forum for Synchrotron Radiation Research: AOFSRR 2014
  • Place of Presentation: 台湾放射光研究センター（台湾・新竹市）
  • Year and Date: 2014-09-15 – 2014-09-18
  • Invited
• [Remarks] Information of UVSOR-III STXM Beamline
  • URL: https://www.uvsor.ims.ac.jp/staff/BL4U/index.html
• [Remarks] 新装置紹介 走査型透過軟Ｘ線顕微鏡（STXM）装置
  • URL: https://www.ims.ac.jp/publications/letters70/70-14.pdf
• [Remarks] 放射光を利用した分子科学：分子間相互作用系の局所解析
  • URL: https://www.ims.ac.jp/research/group/kosugi/
• [Remarks] Local Chemical State Analysis Using Soft X-Rays
  • URL: https://www.ims.ac.jp/about/publication/ann_rev_2016/2016kosugi.pdf
• [Remarks] 新装置紹介 走査型透過軟Ｘ線顕微鏡（STXM）装置
  • URL: http://www.ims.ac.jp/about/publication/70-14.pdf