skip to main content
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Identification of site-specific isotopic labels by vibrational spectroscopy in the electron microscope

Abstract

The identification of isotopic labels by conventional macroscopic techniques lacks spatial resolution and requires relatively large quantities of material for measurements. We recorded the vibrational spectra of an α amino acid, l -alanine, with damage-free “aloof” electron energy-loss spectroscopy in a scanning transmission electron microscope to directly resolve carbon-site–specific isotopic labels in real space with nanoscale spatial resolution. An isotopic red shift of 4.8 ± 0.4 milli–electron volts in C–O asymmetric stretching modes was observed for 13 C-labeled l -alanine at the carboxylate carbon site, which was confirmed by macroscopic infrared spectroscopy and theoretical calculations. The accurate measurement of this shift opens the door to nondestructive, site-specific, spatially resolved identification of isotopically labeled molecules with the electron microscope.

Authors:
ORCiD logo; ORCiD logo; ORCiD logo; ORCiD logo; ORCiD logo; ORCiD logo; ; ORCiD logo; ORCiD logo; ORCiD logo
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1528642
Alternate Identifier(s):
OSTI ID: 1493991
Grant/Contract Number:  
AC05-00OR22725
Resource Type:
Published Article
Journal Name:
Science
Additional Journal Information:
Journal Name: Science Journal Volume: 363 Journal Issue: 6426; Journal ID: ISSN 0036-8075
Publisher:
American Association for the Advancement of Science (AAAS)
Country of Publication:
United States
Language:
English
Subject:
74 ATOMIC AND MOLECULAR PHYSICS

Citation Formats

Hachtel, Jordan A., Huang, Jingsong, Popovs, Ilja, Jansone-Popova, Santa, Keum, Jong K., Jakowski, Jacek, Lovejoy, Tracy C., Dellby, Niklas, Krivanek, Ondrej L., and Idrobo, Juan Carlos. Identification of site-specific isotopic labels by vibrational spectroscopy in the electron microscope. United States: N. p., 2019. Web. doi:10.1126/science.aav5845.
Hachtel, Jordan A., Huang, Jingsong, Popovs, Ilja, Jansone-Popova, Santa, Keum, Jong K., Jakowski, Jacek, Lovejoy, Tracy C., Dellby, Niklas, Krivanek, Ondrej L., & Idrobo, Juan Carlos. Identification of site-specific isotopic labels by vibrational spectroscopy in the electron microscope. United States. doi:10.1126/science.aav5845.
Hachtel, Jordan A., Huang, Jingsong, Popovs, Ilja, Jansone-Popova, Santa, Keum, Jong K., Jakowski, Jacek, Lovejoy, Tracy C., Dellby, Niklas, Krivanek, Ondrej L., and Idrobo, Juan Carlos. Thu . "Identification of site-specific isotopic labels by vibrational spectroscopy in the electron microscope". United States. doi:10.1126/science.aav5845.
@article{osti_1528642,
title = {Identification of site-specific isotopic labels by vibrational spectroscopy in the electron microscope},
author = {Hachtel, Jordan A. and Huang, Jingsong and Popovs, Ilja and Jansone-Popova, Santa and Keum, Jong K. and Jakowski, Jacek and Lovejoy, Tracy C. and Dellby, Niklas and Krivanek, Ondrej L. and Idrobo, Juan Carlos},
abstractNote = {The identification of isotopic labels by conventional macroscopic techniques lacks spatial resolution and requires relatively large quantities of material for measurements. We recorded the vibrational spectra of an α amino acid, l -alanine, with damage-free “aloof” electron energy-loss spectroscopy in a scanning transmission electron microscope to directly resolve carbon-site–specific isotopic labels in real space with nanoscale spatial resolution. An isotopic red shift of 4.8 ± 0.4 milli–electron volts in C–O asymmetric stretching modes was observed for 13 C-labeled l -alanine at the carboxylate carbon site, which was confirmed by macroscopic infrared spectroscopy and theoretical calculations. The accurate measurement of this shift opens the door to nondestructive, site-specific, spatially resolved identification of isotopically labeled molecules with the electron microscope.},
doi = {10.1126/science.aav5845},
journal = {Science},
number = 6426,
volume = 363,
place = {United States},
year = {2019},
month = {1}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
DOI: 10.1126/science.aav5845

Citation Metrics:
Cited by: 22 works
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

Exploring the capabilities of monochromated electron energy loss spectroscopy in the infrared regime
journal, April 2018


Nanoscale momentum-resolved vibrational spectroscopy
journal, June 2018

  • Hage, Fredrik S.; Nicholls, Rebecca J.; Yates, Jonathan R.
  • Science Advances, Vol. 4, Issue 6
  • DOI: 10.1126/sciadv.aar7495

Vibrational spectroscopy with neutrons—Where are we now?
journal, May 2010


First-Principles Vibrational Electron Energy Loss Spectroscopy of β -Guanine
journal, July 2017


Isotope analysis in the transmission electron microscope
journal, October 2016

  • Susi, Toma; Hofer, Christoph; Argentero, Giacomo
  • Nature Communications, Vol. 7, Issue 1
  • DOI: 10.1038/ncomms13040

Vibrational spectroscopy in the electron microscope
journal, October 2014

  • Krivanek, Ondrej L.; Lovejoy, Tracy C.; Dellby, Niklas
  • Nature, Vol. 514, Issue 7521
  • DOI: 10.1038/nature13870

Probing low-energy hyperbolic polaritons in van der Waals crystals with an electron microscope
journal, July 2017

  • Govyadinov, Alexander A.; Konečná, Andrea; Chuvilin, Andrey
  • Nature Communications, Vol. 8, Issue 1
  • DOI: 10.1038/s41467-017-00056-y

Scattering delocalization and radiation damage in STEM-EELS
journal, September 2017


Hyperpolarized 13C Lactate, Pyruvate, and Alanine: Noninvasive Biomarkers for Prostate Cancer Detection and Grading
journal, October 2008


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

Monochromated STEM with a 30 meV-wide, atom-sized electron probe
journal, January 2013

  • Krivanek, Ondrej L.; Lovejoy, Tracy C.; Dellby, Niklas
  • Microscopy, Vol. 62, Issue 1
  • DOI: 10.1093/jmicro/dfs089

Local low rank denoising for enhanced atomic resolution imaging
journal, April 2018


Vibrational Spectroscopy of Water with High Spatial Resolution
journal, July 2018

  • Jokisaari, Jacob R.; Hachtel, Jordan A.; Hu, Xuan
  • Advanced Materials, Vol. 30, Issue 36
  • DOI: 10.1002/adma.201802702

Precision neutron diffraction structure determination of protein and nucleic acid components. I. Crystal and molecular structure of the amino acid L-alanine
journal, April 1972

  • Lehmann, M. S.; Koetzle, T. F.; Hamilton, W. C.
  • Journal of the American Chemical Society, Vol. 94, Issue 8
  • DOI: 10.1021/ja00763a016

Identification of individual isotopes in a polymer blend using tip enhanced Raman spectroscopy: Identification of individual isotopes in a polymer blend
journal, March 2015

  • Agapov, Rebecca L.; Scherger, Jacob D.; Sokolov, Alexei P.
  • Journal of Raman Spectroscopy, Vol. 46, Issue 5
  • DOI: 10.1002/jrs.4671

Uncertainties in Scaling Factors for ab Initio Vibrational Frequencies
journal, September 2005

  • Irikura, Karl K.; Johnson, Russell D.; Kacker, Raghu N.
  • The Journal of Physical Chemistry A, Vol. 109, Issue 37
  • DOI: 10.1021/jp052793n

The effect of pressure on the crystal structure of l-alanine
journal, January 2010

  • Funnell, Nicholas P.; Dawson, Alice; Francis, Duncan
  • CrystEngComm, Vol. 12, Issue 9
  • DOI: 10.1039/c001296c

Towards weighing individual atoms by high-angle scattering of electrons
journal, April 2015


Transparent Window Vibrational Probes for the Characterization of Proteins With High Structural and Temporal Resolution
journal, January 2017


The infrared absorption of amino acid side chains
journal, January 2000


Advances in molecular quantum chemistry contained in the Q-Chem 4 program package
journal, September 2014


Structure and Vibrational Spectra of the Zwitterion l -Alanine in the Presence of Explicit Water Molecules:  A Density Functional Analysis
journal, July 1998

  • Tajkhorshid, Emadeddin; Jalkanen, K. J.; Suhai, Sándor
  • The Journal of Physical Chemistry B, Vol. 102, Issue 30
  • DOI: 10.1021/jp9803135

The 3.8 A resolution cryo-EM structure of Zika virus
journal, March 2016


Two-dimensional IR spectroscopy and isotope labeling defines the pathway of amyloid formation with residue-specific resolution
journal, April 2009

  • Shim, S. -H.; Gupta, R.; Ling, Y. L.
  • Proceedings of the National Academy of Sciences, Vol. 106, Issue 16
  • DOI: 10.1073/pnas.0805957106

Mapping vibrational surface and bulk modes in a single nanocube
journal, March 2017

  • Lagos, Maureen J.; Trügler, Andreas; Hohenester, Ulrich
  • Nature, Vol. 543, Issue 7646
  • DOI: 10.1038/nature21699

Stable-isotope probing of nucleic acids: a window to the function of uncultured microorganisms
journal, June 2003

  • Radajewski, Stefan; McDonald, Ian R.; Murrell, J. Colin
  • Current Opinion in Biotechnology, Vol. 14, Issue 3, p. 296-302
  • DOI: 10.1016/S0958-1669(03)00064-8

Damage-free vibrational spectroscopy of biological materials in the electron microscope
journal, March 2016

  • Rez, Peter; Aoki, Toshihiro; March, Katia
  • Nature Communications, Vol. 7, Issue 1
  • DOI: 10.1038/ncomms10945

Electron-Beam Mapping of Vibrational Modes with Nanometer Spatial Resolution
journal, December 2016


Development of electron energy-loss spectroscopy in the biological sciences
journal, January 2012


Temperature Measurement by a Nanoscale Electron Probe Using Energy Gain and Loss Spectroscopy
journal, March 2018


    Works referencing / citing this record:

    Emerging Electron Microscopy Techniques for Probing Functional Interfaces in Energy Materials
    journal, October 2019

    • Zachman, Michael J.; Hachtel, Jordan A.; Idrobo, Juan Carlos
    • Angewandte Chemie, Vol. 132, Issue 4
    • DOI: 10.1002/ange.201902993

    Spectrally tunable infrared plasmonic F,Sn:In 2 O 3 nanocrystal cubes
    journal, January 2020

    • Cho, Shin Hum; Roccapriore, Kevin M.; Dass, Chandriker Kavir
    • The Journal of Chemical Physics, Vol. 152, Issue 1
    • DOI: 10.1063/1.5139050

    Far-field midinfrared superresolution imaging and spectroscopy of single high aspect ratio gold nanowires
    journal, January 2020

    • Aleshire, Kyle; Pavlovetc, Ilia M.; Collette, Robyn
    • Proceedings of the National Academy of Sciences, Vol. 117, Issue 5
    • DOI: 10.1073/pnas.1916433117

    Polarization Selectivity in Vibrational Electron-Energy-Loss Spectroscopy
    journal, December 2019


    Efficient and Versatile Model for Vibrational STEM-EELS
    journal, January 2020


    Isotopic compositions, nitrogen functional chemistry, and low‐loss electron spectroscopy of complex organic aggregates at the nanometer scale in the carbonaceous chondrite Renazzo
    journal, October 2019

    • Vollmer, Christian; Leitner, Jan; Kepaptsoglou, Demie
    • Meteoritics & Planetary Science, Vol. 55, Issue 6
    • DOI: 10.1111/maps.13389