DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: In Liquid Infrared Scattering Scanning Near-Field Optical Microscopy for Chemical and Biological Nanoimaging

Abstract

Imaging biological systems with simultaneous intrinsic chemical specificity and nanometer spatial resolution in their typical native liquid environment has remained a long-standing challenge. In this paper we demonstrate a general approach of chemical nanoimaging in liquid based on infrared scattering scanning near-field optical microscopy (IR $s$-SNOM). It is enabled by combining AFM operation in a fluid cell with evanescent IR illumination via total internal reflection, which provides spatially confined excitation for minimized IR water absorption, reduced far-field background, and enhanced directional signal emission and sensitivity. We demonstrate in-liquid IR $s$-SNOM vibrational nanoimaging and conformational identification of catalase nano-crystals and spatio-spectral analysis of biomimetic peptoid sheets with monolayer sensitivity and chemical specificity at the few zeptomole level. This work establishes the principles of in-liquid and in-situ IR $s$-SNOM spectroscopic chemical nano-imaging and its general applicability to biomolecular, cellular, catalytic, electrochemical, or other interfaces and nano-systems in liquids or solutions.

Authors:
ORCiD logo [1]; ORCiD logo [2];  [1]; ORCiD logo [3]; ORCiD logo [3]; ORCiD logo [4]; ORCiD logo [3]; ORCiD logo [4]; ORCiD logo [1]
  1. Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Environmental Molecular Sciences Lab. (EMSL)
  2. Ulsan National Inst. of Science and Technology (UNIST) (Republic of Korea)
  3. Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
  4. Univ. of Colorado, Boulder, CO (United States)
Publication Date:
Research Org.:
Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Environmental Molecular Sciences Lab. (EMSL)
Sponsoring Org.:
USDOE Office of Science (SC), Biological and Environmental Research (BER); National Science Foundation (NSF); USDOE Office of Science (SC), Basic Energy Sciences (BES); National Research Foundation of Korea (NRF)
OSTI Identifier:
1631996
Report Number(s):
PNNL-SA-152805
Journal ID: ISSN 1530-6984
Grant/Contract Number:  
AC05-76RL01830; DMR 1548924; NRF-2019R1F1A1059892
Resource Type:
Accepted Manuscript
Journal Name:
Nano Letters
Additional Journal Information:
Journal Volume: 20; Journal Issue: 6; Journal ID: ISSN 1530-6984
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
77 NANOSCIENCE AND NANOTECHNOLOGY; nano-spectroscopy; bio-nanoimaging; in-liquid; in-situ

Citation Formats

O’Callahan, Brian T., Park, Kyoung-Duck, Novikova, Irina V., Jian, Tengyue, Chen, Chun-Long, Muller, Eric A., El-Khoury, Patrick Z., Raschke, Markus B., and Lea, A. Scott. In Liquid Infrared Scattering Scanning Near-Field Optical Microscopy for Chemical and Biological Nanoimaging. United States: N. p., 2020. Web. doi:10.1021/acs.nanolett.0c01291.
O’Callahan, Brian T., Park, Kyoung-Duck, Novikova, Irina V., Jian, Tengyue, Chen, Chun-Long, Muller, Eric A., El-Khoury, Patrick Z., Raschke, Markus B., & Lea, A. Scott. In Liquid Infrared Scattering Scanning Near-Field Optical Microscopy for Chemical and Biological Nanoimaging. United States. https://doi.org/10.1021/acs.nanolett.0c01291
O’Callahan, Brian T., Park, Kyoung-Duck, Novikova, Irina V., Jian, Tengyue, Chen, Chun-Long, Muller, Eric A., El-Khoury, Patrick Z., Raschke, Markus B., and Lea, A. Scott. Fri . "In Liquid Infrared Scattering Scanning Near-Field Optical Microscopy for Chemical and Biological Nanoimaging". United States. https://doi.org/10.1021/acs.nanolett.0c01291. https://www.osti.gov/servlets/purl/1631996.
@article{osti_1631996,
title = {In Liquid Infrared Scattering Scanning Near-Field Optical Microscopy for Chemical and Biological Nanoimaging},
author = {O’Callahan, Brian T. and Park, Kyoung-Duck and Novikova, Irina V. and Jian, Tengyue and Chen, Chun-Long and Muller, Eric A. and El-Khoury, Patrick Z. and Raschke, Markus B. and Lea, A. Scott},
abstractNote = {Imaging biological systems with simultaneous intrinsic chemical specificity and nanometer spatial resolution in their typical native liquid environment has remained a long-standing challenge. In this paper we demonstrate a general approach of chemical nanoimaging in liquid based on infrared scattering scanning near-field optical microscopy (IR $s$-SNOM). It is enabled by combining AFM operation in a fluid cell with evanescent IR illumination via total internal reflection, which provides spatially confined excitation for minimized IR water absorption, reduced far-field background, and enhanced directional signal emission and sensitivity. We demonstrate in-liquid IR $s$-SNOM vibrational nanoimaging and conformational identification of catalase nano-crystals and spatio-spectral analysis of biomimetic peptoid sheets with monolayer sensitivity and chemical specificity at the few zeptomole level. This work establishes the principles of in-liquid and in-situ IR $s$-SNOM spectroscopic chemical nano-imaging and its general applicability to biomolecular, cellular, catalytic, electrochemical, or other interfaces and nano-systems in liquids or solutions.},
doi = {10.1021/acs.nanolett.0c01291},
journal = {Nano Letters},
number = 6,
volume = 20,
place = {United States},
year = {2020},
month = {5}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 1 work
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

Structure of Wet Specimens in Electron Microscopy
journal, November 1974


Observation of Single Colloidal Platinum Nanocrystal Growth Trajectories
journal, June 2009


Nanometer-resolution electron microscopy through micrometers-thick water layers
journal, August 2010


Recent advances in electron imaging, image interpretation and applications: environmental scanning electron microscopy
journal, November 2003

  • Stokes, Debbie J.
  • Philosophical Transactions of the Royal Society of London. Series A: Mathematical, Physical and Engineering Sciences, Vol. 361, Issue 1813
  • DOI: 10.1098/rsta.2003.1279

Electron Diffraction of Wet Biological Membranes
journal, April 1974


Opportunities and challenges in liquid cell electron microscopy
journal, December 2015


Structure of the mitochondrial inner membrane AAA+ protease YME1 gives insight into substrate processing
journal, November 2017


Interferometric fluorescent super-resolution microscopy resolves 3D cellular ultrastructure
journal, February 2009

  • Shtengel, G.; Galbraith, J. A.; Galbraith, C. G.
  • Proceedings of the National Academy of Sciences, Vol. 106, Issue 9, p. 3125-3130
  • DOI: 10.1073/pnas.0813131106

Fluorescence microscopy with diffraction resolution barrier broken by stimulated emission
journal, July 2000

  • Klar, T. A.; Jakobs, S.; Dyba, M.
  • Proceedings of the National Academy of Sciences, Vol. 97, Issue 15
  • DOI: 10.1073/pnas.97.15.8206

On/off blinking and switching behaviour of single molecules of green fluorescent protein
journal, July 1997

  • Dickson, Robert M.; Cubitt, Andrew B.; Tsien, Roger Y.
  • Nature, Vol. 388, Issue 6640
  • DOI: 10.1038/41048

Live-cell photoactivated localization microscopy of nanoscale adhesion dynamics
journal, April 2008

  • Shroff, Hari; Galbraith, Catherine G.; Galbraith, James A.
  • Nature Methods, Vol. 5, Issue 5
  • DOI: 10.1038/nmeth.1202

Sub-diffraction-limit imaging by stochastic optical reconstruction microscopy (STORM)
journal, August 2006

  • Rust, Michael J.; Bates, Mark; Zhuang, Xiaowei
  • Nature Methods, Vol. 3, Issue 10
  • DOI: 10.1038/nmeth929

Nanoscale Chemical Reaction Imaging at the Solid–Liquid Interface via TERS
journal, May 2019

  • Bhattarai, Ashish; El-Khoury, Patrick Z.
  • The Journal of Physical Chemistry Letters, Vol. 10, Issue 11
  • DOI: 10.1021/acs.jpclett.9b00935

Nano-Chemical Infrared Imaging of Membrane Proteins in Lipid Bilayers
journal, November 2013

  • Berweger, Samuel; Nguyen, Duc M.; Muller, Eric A.
  • Journal of the American Chemical Society, Vol. 135, Issue 49
  • DOI: 10.1021/ja409815g

Tip-enhanced infrared nanospectroscopy via molecular expansion force detection
journal, January 2014


Taking the Plunge: Nanoscale Chemical Imaging of Functionalized Gold Triangles in H 2 O via TERS
journal, February 2019

  • Bhattarai, Ashish; Joly, Alan G.; Krayev, Andrey
  • The Journal of Physical Chemistry C, Vol. 123, Issue 12
  • DOI: 10.1021/acs.jpcc.9b00867

Nanoscale chemical imaging of solid–liquid interfaces using tip-enhanced Raman spectroscopy
journal, January 2018

  • Kumar, Naresh; Su, Weitao; Veselý, Martin
  • Nanoscale, Vol. 10, Issue 4
  • DOI: 10.1039/C7NR08257F

UV Resonance Raman-Selective Amide Vibrational Enhancement:  Quantitative Methodology for Determining Protein Secondary Structure
journal, March 1998

  • Chi, Zhenhuan; Chen, X. G.; Holtz, Janet S. W.
  • Biochemistry, Vol. 37, Issue 9
  • DOI: 10.1021/bi971160z

Real-Time In Situ Secondary Structure Analysis of Protein Monolayer with Mid-Infrared Plasmonic Nanoantennas
journal, May 2018


Using Fourier transform IR spectroscopy to analyze biological materials
journal, July 2014

  • Baker, Matthew J.; Trevisan, Júlio; Bassan, Paul
  • Nature Protocols, Vol. 9, Issue 8
  • DOI: 10.1038/nprot.2014.110

Sub-100 nm IR spectromicroscopy of living cells
journal, January 2008


High-sensitivity infrared vibrational nanospectroscopy in water
journal, July 2017

  • Jin, Mingzhou; Lu, Feng; Belkin, Mikhail A.
  • Light: Science & Applications, Vol. 6, Issue 7
  • DOI: 10.1038/lsa.2017.96

Determination of Polypeptide Conformation with Nanoscale Resolution in Water
journal, June 2018


Probing Mid-Infrared Phonon Polaritons in the Aqueous Phase
journal, April 2020


Structural analysis and mapping of individual protein complexes by infrared nanospectroscopy
journal, December 2013

  • Amenabar, Iban; Poly, Simon; Nuansing, Wiwat
  • Nature Communications, Vol. 4, Issue 1
  • DOI: 10.1038/ncomms3890

Graphene-Based Platform for Infrared Near-Field Nanospectroscopy of Water and Biological Materials in an Aqueous Environment
journal, July 2015


Infrared Nanospectroscopy at the Graphene–Electrolyte Interface
journal, July 2019


Synchrotron infrared nanospectroscopy on a graphene chip
journal, January 2019

  • Meireles, Leonel M.; Barcelos, Ingrid D.; Ferrari, Gustavo A.
  • Lab on a Chip, Vol. 19, Issue 21
  • DOI: 10.1039/C9LC00686A

Imaging Nanoscale Heterogeneity in Ultrathin Biomimetic and Biological Crystals
journal, September 2018

  • O’Callahan, Brian T.; Crampton, Kevin T.; Novikova, Irina V.
  • The Journal of Physical Chemistry C, Vol. 122, Issue 43
  • DOI: 10.1021/acs.jpcc.8b06681

Apertureless near-field optical microscopy: Tip–sample coupling in elastic light scattering
journal, December 2003

  • Raschke, Markus B.; Lienau, Christoph
  • Applied Physics Letters, Vol. 83, Issue 24
  • DOI: 10.1063/1.1632023

Highly stable and self-repairing membrane-mimetic 2D nanomaterials assembled from lipid-like peptoids
journal, July 2016

  • Jin, Haibao; Jiao, Fang; Daily, Michael D.
  • Nature Communications, Vol. 7, Issue 1
  • DOI: 10.1038/ncomms12252

Structure of catalase determined by MicroED
journal, October 2014


Three-dimensional structure of catalase from Penicillium vitale at 2.0 Å resolution
journal, March 1986


Light emission by magnetic and electric dipoles close to a plane dielectric interface II Radiation patterns of perpendicular oriented dipoles
journal, January 1977

  • Lukosz, W.; Kunz, R. E.
  • Journal of the Optical Society of America, Vol. 67, Issue 12
  • DOI: 10.1364/JOSA.67.001615

Infrared spectroscopy of proteins
journal, September 2007


Mid-IR Plasmonics: Near-Field Imaging of Coherent Plasmon Modes of Silver Nanowires
journal, July 2009

  • Jones, Andrew C.; Olmon, Robert L.; Skrabalak, Sara E.
  • Nano Letters, Vol. 9, Issue 7
  • DOI: 10.1021/nl900638p

Vibrational near-field mapping of planar and buried three-dimensional plasmonic nanostructures
journal, July 2013

  • Dregely, Daniel; Neubrech, Frank; Duan, Huigao
  • Nature Communications, Vol. 4, Issue 1
  • DOI: 10.1038/ncomms3237

Surface-Enhanced Infrared Spectroscopy Using Resonant Nanoantennas
journal, February 2017


Ultrasensitive Tip- and Antenna-Enhanced Infrared Nanoscopy of Protein Complexes
journal, June 2019

  • O’Callahan, Brian T.; Hentschel, Mario; Raschke, Markus B.
  • The Journal of Physical Chemistry C, Vol. 123, Issue 28
  • DOI: 10.1021/acs.jpcc.9b05777

Accessing the Optical Magnetic Near-Field through Babinet’s Principle
journal, August 2014

  • Yang, Honghua U.; Olmon, Robert L.; Deryckx, Kseniya S.
  • ACS Photonics, Vol. 1, Issue 9
  • DOI: 10.1021/ph5001988

Electron microscopy of whole cells in liquid with nanometer resolution
journal, January 2009

  • Jonge, N. d.; Peckys, D. B.; Kremers, G. J.
  • Proceedings of the National Academy of Sciences, Vol. 106, Issue 7
  • DOI: 10.1073/pnas.0809567106

High-Resolution Electron Microscopy and Spectroscopy of Ferritin in Biocompatible Graphene Liquid Cells and Graphene Sandwiches
journal, February 2014

  • Wang, Canhui; Qiao, Qiao; Shokuhfar, Tolou
  • Advanced Materials, Vol. 26, Issue 21
  • DOI: 10.1002/adma.201306069

Electron microscopy of specimens in liquid
journal, October 2011

  • de Jonge, Niels; Ross, Frances M.
  • Nature Nanotechnology, Vol. 6, Issue 11, p. 695-704
  • DOI: 10.1038/nnano.2011.161

Imaging of DNA molecules by scanning near-field microscope
journal, August 2000

  • Muramatsu, Hiroshi; Homma, Katsunori; Yamamoto, Noritaka
  • Materials Science and Engineering: C, Vol. 12, Issue 1-2
  • DOI: 10.1016/S0928-4931(00)00153-3

A scanning near-field middle-infrared microscope for the study of objects submerged in water
journal, March 2008

  • Platkov, Max; Tsun, Alexander; Nagli, Lev
  • Applied Physics Letters, Vol. 92, Issue 10
  • DOI: 10.1063/1.2891060

Near-Field Imaging of Cell Membranes in Liquid Enabled by Active Scanning Probe Mechanical Resonance Control
journal, July 2016

  • Park, Kyoung-Duck; Raschke, Markus B.; Jang, Min Jung
  • The Journal of Physical Chemistry C, Vol. 120, Issue 37
  • DOI: 10.1021/acs.jpcc.6b06563

Square ice in graphene nanocapillaries
journal, March 2015

  • Algara-Siller, G.; Lehtinen, O.; Wang, F. C.
  • Nature, Vol. 519, Issue 7544
  • DOI: 10.1038/nature14295

In-situ near-field probe microscopy of plasma processing
journal, December 2018

  • Tselev, Alexander; Fagan, Jeffrey; Kolmakov, Andrei
  • Applied Physics Letters, Vol. 113, Issue 26
  • DOI: 10.1063/1.5049592

Seeing through Walls at the Nanoscale: Microwave Microscopy of Enclosed Objects and Processes in Liquids
journal, February 2016


Vibrational exciton nanoimaging of phases and domains in porphyrin nanocrystals
journal, March 2020

  • Muller, Eric A.; Gray, Thomas P.; Zhou, Zhou
  • Proceedings of the National Academy of Sciences, Vol. 117, Issue 13
  • DOI: 10.1073/pnas.1914172117

Infrared nanospectroscopic imaging in the rotating frame
journal, January 2019


AFM-IR: Technology and Applications in Nanoscale Infrared Spectroscopy and Chemical Imaging
journal, December 2016


In Vitro Monitoring Conformational Changes of Polypeptide Monolayers Using Infrared Plasmonic Nanoantennas
journal, August 2018


The Chemistry of Electrolyte Reduction on Silicon Electrodes Revealed by in Situ ATR-FTIR Spectroscopy
journal, June 2017

  • Shi, Feifei; Ross, Philip N.; Somorjai, Gabor A.
  • The Journal of Physical Chemistry C, Vol. 121, Issue 27
  • DOI: 10.1021/acs.jpcc.7b04132