Department of Chemistry

The Ito Research Laboratory

Our research involves (A) design and fabrication of novel nanoporous materials having controlled sizes, shapes, and chemical properties; (B) single-molecule observation of separation processes in the nanoporous materials; and (C) their applications for chemical sensing and membrane separations. Here are our recent achievements and current interests.

(A) Fabrication of controlled nanostructures. (Recent reviews: [1-3])

We have established means to prepare nanoporous structures having controlled sizes, shapes, and surface properties. These structures are formed via self-organization (e.g., microphase separation of block copolymers (upper left) [4,5], metal anodization (lower left) [6,7], and self-assembly of amphiphile molecules (upper right) [8]), or by track-etching processes (lower right) [9]. More recently, we investigate details on the electrochemical thin film formation of metal organic frameworks (MOFs) [10] and also have established a unique electrochemistry-based approach to the patterned deposition of thin MOF films [11]. We clarify their unique structural and chemical properties using a series of spectroscopic, microscopic, X-ray, and electrochemical techniques.

materials

(B) Single-molecule observations of separation processes in nanoporous media. (Recent reviews: [3, 12-14])

We seek molecular-level scientific origins of highly efficient molecular separations in nanoporous media using single-molecule fluorescence techniques (in collaboration with Prof. Higgins (KSU, Chemistry)).

single-molecule fluorescence

(C) Chemical sensing and membrane separations. (Recent reviews: [1,2,15])

We explore to apply these nanoporous structures for chemical sensing [16,17] and membrane separations. Our current primary targets are critical elements (e.g., lanthanides, actinides) as well as anionic and organic pollutants.

EC sensing

References

  1. Ito,* G. Ghimire “Electrochemical Applications of Microphase-Separated Block Copolymer Thin Films” (Review), ChemElectroChem 2018, 5, 2937-2953 (DOI: 10.1002/celc.201800576).
  2. Ito,* A. Nathani “Electrochemical Sensing at Nanoporous Film-Coated Electrodes”, Electrochem. Sci. Adv. 2022, 2, e2100126 (DOI: 10.1002/elsa.202100126).
  3. Ito,* D. A. Higgins* “Fluorescence Microscopic Investigations of Molecular Dynamics in Self-Assembled Nanostructures”, Chem. Rec. 2021, 21, 1417–1429 (DOI: 10.1002/tcr.202000173).
  4. Ito,* H. Coceancigh, Y. Yi,* J. N. Sharma, F. C. Parks, A. H. Flood “Nanoporous Thin Films Formed from Photocleavable Diblock Copolymers on Gold Substrates Modified with Thiolate Self-Assembled Monolayers”, Langmuir 2020, 36, 9259-9268 (DOI: 10.1021/acs.langmuir.0c01572).
  5. Coceancigh, L. Xue, S. Nagasaka, D. A. Higgins,* T. Ito* “Solvent-Induced Swelling Behaviors of Microphase-Separated Polystyrene-block-Poly(ethylene oxide) Thin Films Investigated Using In Situ Spectroscopic Ellipsometry and Single-Molecule Fluorescence Microscopy”, J. Phys. Chem. B, 2022, 126, 8338–8349 (DOI:10.1021/acs.jpcb.2c05025).
  6. Pandey, P. S. Thapa, D. A. Higgins, T. Ito* “Formation of Self-Organized Nanoporous Anodic Oxide from Metallic Gallium” Langmuir 2012, 28, 13705-13711 (DOI: 10.1021/la302672a).
  7. Pandey, C. B. Cox, P. S. Thapa, T. Ito* “Potentiometric Response Characteristics of Oxide-Coated Gallium Electrodes in Aqueous Solutions” Electrochim. Acta, 2014, 142, 378-385 (DOI:10.1016/j.electacta.2014.07.083).
  8. Ghimire, M. M. Moore, R. Leuschen, S. Nagasaka, N. Kameta, M. Masuda, D. A. Higgins,* T. Ito* “Influences of Hydrogen Bonding-Based Stabilization of Bolaamphiphile Layers on Molecular Diffusion within Organic Nanotubes Having Inner Carboxyl Groups”, Langmuir 2020, 36, 6145-6153 (DOI: 10.1021/acs.langmuir.0c00556).
  9. Coceancigh, K.-H. Tran-Ba, N. Siepser, L. A. Baker, T. Ito* “Longitudinally Controlled Modification of Cylindrical and Conical Track-Etched Poly(ethylene terephthalate) Pores Using Electrochemically-Assisted Click Reaction” Langmuir 2017, 33, 11998-12006 (DOI: 10.1021/acs.langmuir.7b02778).
  10. Ito,* S. Seifert, K. N. Moeller, A. Uysal “In Situ Synchrotron X-Ray Scattering Investigation of Cathodic ZIF-8 Deposition on Graphite Using 3D-Printed Cells”, Anal. Chem. 2023, 95, 8206-8213 (DOI: 10.1021/acs.analchem.2c05668).
  11. Ito,* S. G. Jenkins, S. Seifert, A. Uysal “Electrochemistry-Induced Direct Deposition of Nanoscale Thin Zeolitic Imidazolate Framework-8 Films on Insulator Substrates”, Cryst. Growth Des. 2023, DOI: 10.1021/acs.cgd.3c00329.
  12. A. Higgins,* S. C. Park, K.-H. Tran-Ba, T. Ito* “Single-Molecule Investigations of Morphology and Mass Transport Dynamics in Nanostructured Materials” Annu. Rev. Anal. Chem. 2015, 8, 193-216 (DOI: 10.1146/annurev-anchem-071114-040153).
  13. Coceancigh, D. A. Higgins,* T. Ito* “Optical Microscopic Techniques for Synthetic Polymer Characterization”, Anal. Chem. 2019, 91, 405-424 (DOI: 10.1021/acs.analchem.8b04694).
  14. Ito* “Single-Molecule Fluorescence Investigations of Solute Transport Dynamics in Nanostructured Membrane Separation Materials”, J. Phys. Chem. B 2023, 127, 5733-5741 (DOI: 10.1021/acs.jpcb.3c02807).
  15. Ito* “Block Copolymer-Derived Monolithic Polymer Films and Membranes Comprising Self-Organized Cylindrical Nanopores for Chemical Sensing and Separations”, Chem.–Asian J. 2014, 9, 2708-2718 (DOI: 10.1002/asia.201402136).
  16. Li, T. Ito* “Complexation-Induced Control of Electron Propagation Based on Bounded Diffusion through Nanopore-Tethered Ferrocenes” J. Am. Chem. Soc. 2013, 135, 16260-16263 (DOI:10.1021/ja407002d).
  17. Harandizadeh, T. Ito* “Block Copolymer-Derived Recessed Nanodisk-Array Electrodes as Platforms for Folding-Based Electrochemical DNA Sensors”, ChemElectroChem 2019, 6, 5627-5632 (DOI: 10.1002/celc.201901562).

 

Funding

We gratefully acknowledge the following organizations for providing financial support to our research.

• The U.S. Department of Energy, Office of Basic Energy Sciences, the Division of Chemical Sciences, Geosciences, and Biosciences (DE-SC0002362; DE-AC02-06CH11357 through Argonne National Laboratory)

• National Science Foundation, Division of Chemistry and Kansas EPSCoR (CHE-1709285 and CHE-2305013)

• American Chemical Society Petroleum Research Funds (ACS PRF #46192-G5)

• NSF Kansas EPSCoR RFP Planning and Innovation Grants (NSF43529)

• Terry C. Johnson Center for Basic Cancer Research, KSU

• Targeted Excellence Funds, KSU

• University Small Research Grant (USRG), KSU