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:
- 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. https://doi.org/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. https://doi.org/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 = {Thu Jan 31 00:00:00 EST 2019},
month = {Thu Jan 31 00:00:00 EST 2019}
}
https://doi.org/10.1126/science.aav5845
Web of Science
Works referenced in this record:
Exploring the capabilities of monochromated electron energy loss spectroscopy in the infrared regime
journal, April 2018
- Hachtel, Jordan A.; Lupini, Andrew R.; Idrobo, Juan Carlos
- Scientific Reports, Vol. 8, Issue 1
Nanoscale momentum-resolved vibrational spectroscopy
journal, June 2018
- Hage, Fredrik S.; Nicholls, Rebecca J.; Yates, Jonathan R.
- Science Advances, Vol. 4, Issue 6
Vibrational spectroscopy with neutrons—Where are we now?
journal, May 2010
- Kearley, G. J.; Johnson, M. R.
- Vibrational Spectroscopy, Vol. 53, Issue 1
First-Principles Vibrational Electron Energy Loss Spectroscopy of -Guanine
journal, July 2017
- Radtke, G.; Taverna, D.; Lazzeri, M.
- Physical Review Letters, Vol. 119, Issue 2
Isotope analysis in the transmission electron microscope
journal, October 2016
- Susi, Toma; Hofer, Christoph; Argentero, Giacomo
- Nature Communications, Vol. 7, Issue 1
Vibrational spectroscopy in the electron microscope
journal, October 2014
- Krivanek, Ondrej L.; Lovejoy, Tracy C.; Dellby, Niklas
- Nature, Vol. 514, Issue 7521
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
Scattering delocalization and radiation damage in STEM-EELS
journal, September 2017
- Egerton, R. F.
- Ultramicroscopy, Vol. 180
Nanoscale Probing of Local Hydrogen Heterogeneity in Disordered Carbon Nitrides with Vibrational Electron Energy-Loss Spectroscopy
journal, May 2018
- Haiber, Diane M.; Crozier, Peter A.
- ACS Nano, Vol. 12, Issue 6
Hyperpolarized 13C Lactate, Pyruvate, and Alanine: Noninvasive Biomarkers for Prostate Cancer Detection and Grading
journal, October 2008
- Albers, M. J.; Bok, R.; Chen, A. P.
- Cancer Research, Vol. 68, Issue 20
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
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
Local low rank denoising for enhanced atomic resolution imaging
journal, April 2018
- Spiegelberg, Jakob; Idrobo, Juan Carlos; Herklotz, Andreas
- Ultramicroscopy, Vol. 187
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
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
Vibrational and valence aloof beam EELS: A potential tool for nondestructive characterization of nanoparticle surfaces
journal, September 2017
- Crozier, Peter A.
- Ultramicroscopy, Vol. 180
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
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
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
Towards weighing individual atoms by high-angle scattering of electrons
journal, April 2015
- Argentero, G.; Mangler, C.; Kotakoski, J.
- Ultramicroscopy, Vol. 151
Transparent Window Vibrational Probes for the Characterization of Proteins With High Structural and Temporal Resolution
journal, January 2017
- Adhikary, Ramkrishna; Zimmermann, Jörg; Romesberg, Floyd E.
- Chemical Reviews, Vol. 117, Issue 3
The infrared absorption of amino acid side chains
journal, January 2000
- Barth, Andreas
- Progress in Biophysics and Molecular Biology, Vol. 74, Issue 3-5
Advances in molecular quantum chemistry contained in the Q-Chem 4 program package
journal, September 2014
- Shao, Yihan; Gan, Zhengting; Epifanovsky, Evgeny
- Molecular Physics, Vol. 113, Issue 2
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
The 3.8 A resolution cryo-EM structure of Zika virus
journal, March 2016
- Sirohi, D.; Chen, Z.; Sun, L.
- Science, Vol. 352, Issue 6284
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
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
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
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
Electron-Beam Mapping of Vibrational Modes with Nanometer Spatial Resolution
journal, December 2016
- Dwyer, C.; Aoki, T.; Rez, P.
- Physical Review Letters, Vol. 117, Issue 25
Development of electron energy-loss spectroscopy in the biological sciences
journal, January 2012
- Aronova, M. A.; Leapman, R. D.
- MRS Bulletin, Vol. 37, Issue 1
Temperature Measurement by a Nanoscale Electron Probe Using Energy Gain and Loss Spectroscopy
journal, March 2018
- Idrobo, Juan Carlos; Lupini, Andrew R.; Feng, Tianli
- Physical Review Letters, Vol. 120, Issue 9
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
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
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
Polarization Selectivity in Vibrational Electron-Energy-Loss Spectroscopy
journal, December 2019
- Radtke, G.; Taverna, D.; Menguy, N.
- Physical Review Letters, Vol. 123, Issue 25
Efficient and Versatile Model for Vibrational STEM-EELS
journal, January 2020
- Zeiger, Paul M.; Rusz, Ján
- Physical Review Letters, Vol. 124, Issue 2
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