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

Title: Chemical Analysis of Fluorobenzenes via Multinuclear Detection in the Strong Heteronuclear J-Coupling Regime

Abstract

Chemical analysis via nuclear magnetic resonance (NMR) spectroscopy using permanent magnets, rather than superconducting magnets, is a rapidly developing field. Performing the NMR measurement in the strong heteronuclear J-coupling regime has shown considerable promise for the chemical analysis of small molecules. Typically, the condition for the strong heteronuclear J-coupling regime is satisfied at µT magnetic field strengths and enables high resolution J-coupled spectra (JCS) to be acquired. However, the JCS response to systematic chemical structural changes has largely not been investigated. In this report, we investigate the JCS of C6H6-xFx (x = 0, 1, 2, …, 6) fluorobenzene compounds via simultaneous excitation and detection of 19F and 1H at 51.5 µT. The results demonstrate that JCS are quantitative, and the common NMR observables, including Larmor frequency, heteronuclear and homonuclear J-couplings, relative signs of the J-coupling, chemical shift, and relaxation, are all measurable and are differentiable between molecules at low magnetic fields. The results, corroborated by ab initio calculations, provide new insights into the impact of chemical structure and their corresponding spin systems on JCS. In several instances, the JCS provided more chemical information than traditional high field NMR, demonstrating that JCS can be used for robust chemical analysis.

Authors:
ORCiD logo; ; ; ; ; ORCiD logo; ; ;
Publication Date:
Research Org.:
Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
Sponsoring Org.:
USDOE Laboratory Directed Research and Development (LDRD) Program
OSTI Identifier:
1631393
Alternate Identifier(s):
OSTI ID: 1739934
Report Number(s):
LA-UR-19-30126
Journal ID: ISSN 2076-3417; ASPCC7; PII: app10113836
Grant/Contract Number:  
20190641PRD3; 20170048DR; 89233218CNA000001
Resource Type:
Published Article
Journal Name:
Applied Sciences
Additional Journal Information:
Journal Name: Applied Sciences Journal Volume: 10 Journal Issue: 11; Journal ID: ISSN 2076-3417
Publisher:
MDPI
Country of Publication:
Switzerland
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; low field NMR; J-coupled spectroscopy; strong-heteronuclear J-coupling regime; fluorobenzene; Pople notation; strong coupling

Citation Formats

Kaseman, Derrick C., Janicke, Michael T., Frankle, Rachel K., Nelson, Tammie, Angles-Tamayo, Gary, Batrice, Rami J., Magnelind, Per E., Espy, Michelle A., and Williams, Robert F. Chemical Analysis of Fluorobenzenes via Multinuclear Detection in the Strong Heteronuclear J-Coupling Regime. Switzerland: N. p., 2020. Web. doi:10.3390/app10113836.
Kaseman, Derrick C., Janicke, Michael T., Frankle, Rachel K., Nelson, Tammie, Angles-Tamayo, Gary, Batrice, Rami J., Magnelind, Per E., Espy, Michelle A., & Williams, Robert F. Chemical Analysis of Fluorobenzenes via Multinuclear Detection in the Strong Heteronuclear J-Coupling Regime. Switzerland. doi:https://doi.org/10.3390/app10113836
Kaseman, Derrick C., Janicke, Michael T., Frankle, Rachel K., Nelson, Tammie, Angles-Tamayo, Gary, Batrice, Rami J., Magnelind, Per E., Espy, Michelle A., and Williams, Robert F. Sun . "Chemical Analysis of Fluorobenzenes via Multinuclear Detection in the Strong Heteronuclear J-Coupling Regime". Switzerland. doi:https://doi.org/10.3390/app10113836.
@article{osti_1631393,
title = {Chemical Analysis of Fluorobenzenes via Multinuclear Detection in the Strong Heteronuclear J-Coupling Regime},
author = {Kaseman, Derrick C. and Janicke, Michael T. and Frankle, Rachel K. and Nelson, Tammie and Angles-Tamayo, Gary and Batrice, Rami J. and Magnelind, Per E. and Espy, Michelle A. and Williams, Robert F.},
abstractNote = {Chemical analysis via nuclear magnetic resonance (NMR) spectroscopy using permanent magnets, rather than superconducting magnets, is a rapidly developing field. Performing the NMR measurement in the strong heteronuclear J-coupling regime has shown considerable promise for the chemical analysis of small molecules. Typically, the condition for the strong heteronuclear J-coupling regime is satisfied at µT magnetic field strengths and enables high resolution J-coupled spectra (JCS) to be acquired. However, the JCS response to systematic chemical structural changes has largely not been investigated. In this report, we investigate the JCS of C6H6-xFx (x = 0, 1, 2, …, 6) fluorobenzene compounds via simultaneous excitation and detection of 19F and 1H at 51.5 µT. The results demonstrate that JCS are quantitative, and the common NMR observables, including Larmor frequency, heteronuclear and homonuclear J-couplings, relative signs of the J-coupling, chemical shift, and relaxation, are all measurable and are differentiable between molecules at low magnetic fields. The results, corroborated by ab initio calculations, provide new insights into the impact of chemical structure and their corresponding spin systems on JCS. In several instances, the JCS provided more chemical information than traditional high field NMR, demonstrating that JCS can be used for robust chemical analysis.},
doi = {10.3390/app10113836},
journal = {Applied Sciences},
number = 11,
volume = 10,
place = {Switzerland},
year = {2020},
month = {5}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
DOI: https://doi.org/10.3390/app10113836

Save / Share:

Works referenced in this record:

Spinach – A software library for simulation of spin dynamics in large spin systems
journal, February 2011

  • Hogben, H. J.; Krzystyniak, M.; Charnock, G. T. P.
  • Journal of Magnetic Resonance, Vol. 208, Issue 2
  • DOI: 10.1016/j.jmr.2010.11.008

Earth field NMR with chemical shift spectral resolution: Theory and proof of concept
journal, June 2012


Nuclear magnetism of liquid systems in the earth field range
journal, February 1980


The analysis of complex nuclear magnetic resonance spectra: I. Systems with one pair of strongly coupled nuclei
journal, November 1960


Nuclear magnetic resonance in the earth’s magnetic field using a nitrogen-cooled superconducting quantum interference device
journal, August 2007

  • Qiu, Longqing; Zhang, Yi; Krause, Hans-Joachim
  • Applied Physics Letters, Vol. 91, Issue 7
  • DOI: 10.1063/1.2771060

Paths from weak to strong coupling in NMR
journal, February 2010


Electron Coupling of Nuclear Spins. I. Proton and Fluorine Magnetic Resonance Spectra of Some Substituted Benzenes 1,2
journal, September 1957

  • Gutowsky, H. S.; Holm, C. H.; Saika, A.
  • Journal of the American Chemical Society, Vol. 79, Issue 17
  • DOI: 10.1021/ja01574a007

Calculation of Nuclear Spin−Spin Coupling Constants of Molecules with First and Second Row Atoms in Study of Basis Set Dependence
journal, May 2006

  • Deng, Wei; Cheeseman, James R.; Frisch, Michael J.
  • Journal of Chemical Theory and Computation, Vol. 2, Issue 4
  • DOI: 10.1021/ct600110u

NMR at earth’s magnetic field using para-hydrogen induced polarization
journal, September 2011

  • Hamans, Bob C.; Andreychenko, Anna; Heerschap, Arend
  • Journal of Magnetic Resonance, Vol. 212, Issue 1
  • DOI: 10.1016/j.jmr.2011.06.011

NMR in Magnetic Field of the Earth: Pre-Polarization of Nuclei with Alternating Magnetic Field
journal, June 2014

  • Chizhik, Vladimir I.; Kupriyanov, Pavel A.; Mozzhukhin, George V.
  • Applied Magnetic Resonance, Vol. 45, Issue 7
  • DOI: 10.1007/s00723-014-0543-5

Accurate measurement of small heteronuclear coupling constants from pure-phase α/β HSQMBC cross-peaks
journal, December 2011

  • Gil, Sergi; Espinosa, Juan Félix; Parella, Teodor
  • Journal of Magnetic Resonance, Vol. 213, Issue 1
  • DOI: 10.1016/j.jmr.2011.09.036

Solvent effects on the1H1H,1H19F and19F19F coupling constants of fluorobenzene and 1,2-difluorobenzene
journal, May 1992

  • Suntioinen, Sirpa; Laatikainen, Reino
  • Magnetic Resonance in Chemistry, Vol. 30, Issue 5
  • DOI: 10.1002/mrc.1260300512

Sensitive J -coupling spectroscopy using high- T c superconducting quantum interference devices in magnetic fields as low as microteslas
journal, March 2009


Nuclear magnetic resonance in the nanoTesla range
journal, August 2005

  • Burghoff, Martin; Hartwig, Stefan; Trahms, Lutz
  • Applied Physics Letters, Vol. 87, Issue 5
  • DOI: 10.1063/1.2006981

Liquid-State NMR and Scalar Couplings in Microtesla Magnetic Fields
journal, March 2002


A dynamic nuclear polarization strategy for multi-dimensional Earth’s field NMR spectroscopy
journal, December 2008


Determination of the Signs of Nuclear Spin‐Spin Indirect Coupling Constants
journal, December 1956

  • Williams, G. A.; Gutowsky, H. S.
  • The Journal of Chemical Physics, Vol. 25, Issue 6
  • DOI: 10.1063/1.1743209

Chemical analysis by ultrahigh-resolution nuclear magnetic resonance in the Earth’s magnetic field
journal, January 2006

  • Appelt, Stephan; Kühn, Holger; Häsing, F. Wolfgang
  • Nature Physics, Vol. 2, Issue 2
  • DOI: 10.1038/nphys211

NMR at very low fields
journal, October 2010


Electron Coupling of Nuclear Spins. II. Molecular Orbital Interpretation of Coupling Constants Observed in Fluorobenzenes
journal, March 1959

  • Williams, G. A.; Gutowsky, H. S.
  • The Journal of Chemical Physics, Vol. 30, Issue 3
  • DOI: 10.1063/1.1730032

A study of J-coupling spectroscopy using the Earth’s field nuclear magnetic resonance inside a laboratory
journal, October 2010

  • Liao, Shu-Hsien; Chen, Ming-Jye; Yang, Hong-Chang
  • Review of Scientific Instruments, Vol. 81, Issue 10
  • DOI: 10.1063/1.3498895

Mobile High Resolution Xenon Nuclear Magnetic Resonance Spectroscopy in the Earth’s Magnetic Field
journal, May 2005


Time-Domain Frequency Correction Method for Averaging Low-Field NMR Signals Acquired in Urban Laboratory Environment
journal, October 2012


SQUID-Detected Liquid State NMR in Microtesla Fields
journal, February 2004

  • Trabesinger, Andreas H.; McDermott, Robert; Lee, SeungKyun
  • The Journal of Physical Chemistry A, Vol. 108, Issue 6
  • DOI: 10.1021/jp035181g

Two-dimensional NMR spectroscopy in Earth’s magnetic field
journal, October 2006

  • Robinson, Jeremy N.; Coy, Andrew; Dykstra, Robin
  • Journal of Magnetic Resonance, Vol. 182, Issue 2, p. 343-347
  • DOI: 10.1016/j.jmr.2006.06.027

Efficient and fast sign-sensitive determination of heteronuclear coupling constants
journal, November 2013


Microtesla NMR J-coupling spectroscopy with an unshielded atomic magnetometer
journal, February 2016

  • Bevilacqua, Giuseppe; Biancalana, Valerio; Baranga, Andrei Ben-Amar
  • Journal of Magnetic Resonance, Vol. 263
  • DOI: 10.1016/j.jmr.2015.12.018

Liquid state nuclear magnetic resonance at low fields using a nitrogen cooled superconducting quantum interference device
journal, April 2007

  • Zhang, Yi; Qiu, Longqing; Krause, Hans-Joachim
  • Applied Physics Letters, Vol. 90, Issue 18
  • DOI: 10.1063/1.2734896

Implementation of Earth’s Field NMR Spectroscopy in an Undergraduate Chemistry Laboratory
journal, September 2019

  • Bergstrom Mann, Patrick; Clark, Samuel; Cahill, Samuel T.
  • Journal of Chemical Education, Vol. 96, Issue 10
  • DOI: 10.1021/acs.jchemed.9b00359

NMR spectrum of para-difluorobenzene
journal, January 1964


Multiple Quantum Coherences Hyperpolarized at Ultra‐Low Fields
journal, October 2019

  • Buckenmaier, Kai; Scheffler, Klaus; Plaumann, Markus
  • ChemPhysChem, Vol. 20, Issue 21
  • DOI: 10.1002/cphc.201900757

J -Coupling Nuclear Magnetic Resonance Spectroscopy of Liquids in nT Fields
journal, January 2006

  • Bernarding, Johannes; Buntkowsky, Gerd; Macholl, Sven
  • Journal of the American Chemical Society, Vol. 128, Issue 3
  • DOI: 10.1021/ja055273e

Phenomena in J -coupled nuclear magnetic resonance spectroscopy in low magnetic fields
journal, August 2007


Progress in low-field benchtop NMR spectroscopy in chemical and biochemical analysis
journal, August 2019


NMR Subspectral Analysis Applied to Polyfluorobenzenes C 6 H n F 6−n . IV. 1,2,4‐Trifluorobenzene
journal, September 1969

  • Lustig, Ernest; Hansen, Elizabeth A.; Diehl, Peter
  • The Journal of Chemical Physics, Vol. 51, Issue 5
  • DOI: 10.1063/1.1672267

A primer for nuclear magnetic relaxation in liquids
journal, January 2003

  • Murali, Nagarajan; Krishnan, V. V.
  • Concepts in Magnetic Resonance, Vol. 17A, Issue 1
  • DOI: 10.1002/cmr.a.10060

Analysis of molecular structures by homo- and hetero-nuclear J-coupled NMR in ultra-low field
journal, June 2007


IPAP–HSQMBC: Measurement of long-range heteronuclear coupling constants from spin-state selective multiplets
journal, December 2010

  • Gil, Sergi; Espinosa, Juan Félix; Parella, Teodor
  • Journal of Magnetic Resonance, Vol. 207, Issue 2
  • DOI: 10.1016/j.jmr.2010.09.017

Relative Signs of Spin‐Spin Interactions in Nuclear Magnetic Resonance. II
journal, June 1960

  • Alexander, S.
  • The Journal of Chemical Physics, Vol. 32, Issue 6
  • DOI: 10.1063/1.1731007

Relative Signs of Spin‐Spin Interactions in Nuclear Magnetic Resonance
journal, February 1958

  • Alexander, S.
  • The Journal of Chemical Physics, Vol. 28, Issue 2
  • DOI: 10.1063/1.1744132

NMR Subspectral Analysis Applied to Polyfluorobenzenes C 6 H n F 6– n . II. 1,2,3,4‐Tetrafluorobenzene
journal, June 1968

  • Lustig, Ernest; Duy, Nicholas; Diehl, Peter
  • The Journal of Chemical Physics, Vol. 48, Issue 11
  • DOI: 10.1063/1.1668170

A first principles theory of nuclear magnetic resonance J-coupling in solid-state systems
journal, November 2007

  • Joyce, Siân A.; Yates, Jonathan R.; Pickard, Chris J.
  • The Journal of Chemical Physics, Vol. 127, Issue 20
  • DOI: 10.1063/1.2801984

Detection of nuclear magnetic resonance in the microtesla range using a high T c dc-SQUID
journal, December 2012


NMR spectroscopy with compact instruments
journal, October 2016


Quantitative analysis of Earth’s field NMR spectra of strongly-coupled heteronuclear systems
journal, September 2009

  • Halse, Meghan E.; Callaghan, Paul T.; Feland, Brett C.
  • Journal of Magnetic Resonance, Vol. 200, Issue 1
  • DOI: 10.1016/j.jmr.2009.06.012

NMR Chemical Shifts of Common Laboratory Solvents as Trace Impurities
journal, October 1997

  • Gottlieb, Hugo E.; Kotlyar, Vadim; Nudelman, Abraham
  • The Journal of Organic Chemistry, Vol. 62, Issue 21
  • DOI: 10.1021/jo971176v

Design and implementation of a J -coupled spectrometer for multidimensional structure and relaxation detection at low magnetic fields
journal, May 2020

  • Kaseman, Derrick C.; Magnelind, Per E.; Widgeon Paisner, Scarlett
  • Review of Scientific Instruments, Vol. 91, Issue 5
  • DOI: 10.1063/1.5130391

Two-dimensional NMR spectroscopy of 13C methanol at less than 5μT
journal, September 2014


Strong Coupling in Nuclear Resonance Spectra. II. Field Dependence of Some Unsymmetrical Three‐Spin Spectra
journal, October 1959

  • Fessenden, R. W.; Waugh, J. S.
  • The Journal of Chemical Physics, Vol. 31, Issue 4
  • DOI: 10.1063/1.1730563

196. High-resolution fluorine magnetic resonance spectra of some pentafluorophenyl derivatives
journal, January 1965


Spin Echo Measurements of Nuclear Spin Coupling in Molecules
journal, December 1952