13C Radiofrequency Amplification by Stimulated Emission of Radiation Threshold Sensing of Chemical Reactions

Schmidt, Andreas B.; Adelabu, Isaiah; Nelson, Christopher; Nantogma, Shiraz; Kiselev, Valerij G.; Zaitsev, Maxim; Abdurraheem, Abubakar; de Maissin, Henri; Rosen, Matthew S.; Lehmkuhl, Sören; Appelt, Stephan; Theis, Thomas; Chekmenev, Eduard Y.

doi:10.1021/jacs.3c00776

Title: ¹³C Radiofrequency Amplification by Stimulated Emission of Radiation Threshold Sensing of Chemical Reactions

Journal Article · 11 May 2023 · Journal of the American Chemical Society

DOI: https://doi.org/10.1021/jacs.3c00776 · OSTI ID:2341430

^[1];

^[2]; Nelson, Christopher ^[3]; Nantogma, Shiraz ^[2]; Kiselev, Valerij G. ^[4]; Zaitsev, Maxim ^[4]; Abdurraheem, Abubakar ^[2]; de Maissin, Henri ^[5]; Rosen, Matthew S. ^[6];

^[7]; Appelt, Stephan ^[8];

^[3];

^[9]

Wayne State Univ., Detroit, MI (United States). Karmanos Cancer Institute (KCI); Univ. of Freiburg (Germany); German Cancer Consortium (DKTK), Heidelberg (Germany); North Carolina State University
Wayne State Univ., Detroit, MI (United States). Karmanos Cancer Institute (KCI)
North Carolina State University, Raleigh, NC (United States)
Univ. of Freiburg (Germany)
Univ. of Freiburg (Germany); German Cancer Consortium (DKTK), Heidelberg (Germany)
Massachusetts General Hospital, Boston, MA (United States). A. A. Martinos Center for Biomedical Imaging; Harvard Univ., Cambridge, MA (United States)
Karlsruhe Inst. of Technology (KIT) (Germany)
RWTH Aachen Univ. (Germany); Forschungszentrum Juelich (Germany). Central Institute for Engineering, Electronics and Analytics─Electronic Systems (ZEA-2)
Wayne State Univ., Detroit, MI (United States). Karmanos Cancer Institute (KCI); Russian Academy of Sciences (RAS), Moscow (Russian Federation)

Conventional nuclear magnetic resonance (NMR) enables detection of chemicals and their transformations by exciting nuclear spin ensembles with a radio-frequency pulse followed by detection of the precessing spins at their characteristic frequencies. The detected frequencies report on chemical reactions in real time and the signal amplitudes scale with concentrations of products and reactants. Here, we employ Radiofrequency Amplification by Stimulated Emission of Radiation (RASER), a quantum phenomenon producing coherent emission of ¹³C signals, to detect chemical transformations. The ¹³C signals are emitted by the negatively hyperpolarized biomolecules without external radio frequency pulses and without any background signal from other, nonhyperpolarized spins in the ensemble. Here, we studied the hydrolysis of hyperpolarized ethyl-[1-¹³C]acetate to hyperpolarized [1-¹³C]acetate, which was analyzed as a model system by conventional NMR and ¹³C RASER. The chemical transformation of ¹³C RASER-active species leads to complete and abrupt disappearance of reactant signals and delayed, abrupt reappearance of a frequency-shifted RASER signal without destroying ¹³C polarization. Further, the experimentally observed “quantum” RASER threshold is supported by simulations.

View Accepted Manuscript (DOE)

Cite

Export

Save

Research Organization:: North Carolina State University, Raleigh, NC (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Biological and Environmental Research (BER)

Contributing Organization:: Wayne State University

Grant/Contract Number:: SC0023334

OSTI ID:: 2341430

Journal Information:: Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 20 Vol. 145; ISSN 0002-7863

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

References (42)

Quantification of Prostate Cancer Metabolism Using 3D Multiecho bSSFP and Hyperpolarized [1‐¹³C] Pyruvate: Metabolism Differs Between Tumors of the Same Gleason Grade Chowdhury, Rafat; Mueller, Christoph A.; Smith, Lorna Journal of Magnetic Resonance Imaging, Vol. 57, Issue 6 https://doi.org/10.1002/jmri.28467	journal	October 2022
Background‐Free Proton NMR Spectroscopy with Radiofrequency Amplification by Stimulated Emission Radiation Joalland, Baptiste; Theis, Thomas; Appelt, Stephan Angewandte Chemie International Edition, Vol. 60, Issue 50 https://doi.org/10.1002/anie.202108939	journal	October 2021
Synthesis of Unsaturated Precursors for Parahydrogen-Induced Polarization and Molecular Imaging of 1-¹³C-Acetates and 1-¹³C-Pyruvates via Side Arm Hydrogenation Chukanov, Nikita V.; Salnikov, Oleg G.; Shchepin, Roman V. ACS Omega, Vol. 3, Issue 6 https://doi.org/10.1021/acsomega.8b00983	journal	June 2018
Hyperpolarized 13C MRI: Path to Clinical Translation in Oncology Kurhanewicz, John; Vigneron, Daniel B.; Ardenkjaer-Larsen, Jan Henrik Neoplasia, Vol. 21, Issue 1 https://doi.org/10.1016/j.neo.2018.09.006	journal	January 2019
Toward an in Vivo Neurochemical Profile: Quantification of 18 Metabolites in Short-Echo-Time 1H NMR Spectra of the Rat Brain Pfeuffer, Josef; Tkáč, Ivan; Provencher, Stephen W. Journal of Magnetic Resonance, Vol. 141, Issue 1 https://doi.org/10.1006/jmre.1999.1895	journal	November 1999
Hyperpolarized NMR Spectroscopy: d -DNP, PHIP, and SABRE Techniques Kovtunov, Kirill V.; Pokochueva, Ekaterina V.; Salnikov, Oleg G. Chemistry - An Asian Journal, Vol. 13, Issue 15 https://doi.org/10.1002/asia.201800551	journal	July 2018
From LASER physics to the para-hydrogen pumped RASER Appelt, S.; Kentner, A.; Lehmkuhl, S. Progress in Nuclear Magnetic Resonance Spectroscopy, Vol. 114-115 https://doi.org/10.1016/j.pnmrs.2019.05.003	journal	October 2019
Parahydrogen‐Induced Carbon‐13 Radiofrequency Amplification by Stimulated Emission of Radiation Nelson, Christopher; Schmidt, Andreas B.; Adelabu, Isaiah Angewandte Chemie International Edition, Vol. 62, Issue 5 https://doi.org/10.1002/anie.202215678	journal	December 2022
Three-dimensional H-1 MR spectroscopic imaging of the in situ human prostate with high (0.24-0.7-cm3) spatial resolution. Kurhanewicz, J.; Vigneron, D. B.; Hricak, H. Radiology, Vol. 198, Issue 3 https://doi.org/10.1148/radiology.198.3.8628874	journal	March 1996
Analysis of Cancer Metabolism by Imaging Hyperpolarized Nuclei: Prospects for Translation to Clinical Research Kurhanewicz, John; Vigneron, Daniel B.; Brindle, Kevin Neoplasia, Vol. 13, Issue 2 https://doi.org/10.1593/neo.101102	journal	February 2011
Para-hydrogen raser delivers sub-millihertz resolution in nuclear magnetic resonance Suefke, Martin; Lehmkuhl, Sören; Liebisch, Alexander Nature Physics, Vol. 13, Issue 6 https://doi.org/10.1038/nphys4076	journal	March 2017
Spontaneous Enhancement of Magnetic Resonance Signals Using a RASER Korchak, Sergey; Kaltschnee, Lukas; Dervisoglu, Riza Angewandte Chemie International Edition, Vol. 60, Issue 38 https://doi.org/10.1002/anie.202108306	journal	August 2021
The quality factor of a superconducting rf resonator in a magnetic field Ulmer, S.; Kracke, H.; Blaum, K. Review of Scientific Instruments, Vol. 80, Issue 12 https://doi.org/10.1063/1.3271537	journal	December 2009
Real-time metabolic imaging Golman, Klaes; in ‘t Zandt, René; Thaning, Mikkel Proceedings of the National Academy of Sciences, Vol. 103, Issue 30 https://doi.org/10.1073/pnas.0601319103	journal	July 2006
Pulse-Programmable Magnetic Field Sweeping of Parahydrogen-Induced Polarization by Side Arm Hydrogenation Joalland, Baptiste; Schmidt, Andreas B.; Kabir, Mohammad S. H. Analytical Chemistry, Vol. 92, Issue 1 https://doi.org/10.1021/acs.analchem.9b04501	journal	December 2019
Parametric Amplification of Magnetic Resonance Images Syms, Richard R. A.; Floume, Timmy; Young, Ian R. IEEE Sensors Journal, Vol. 12, Issue 6 https://doi.org/10.1109/JSEN.2011.2176928	journal	June 2012
Scanning Nuclear Spin Level Anticrossings by Constant-Adiabaticity Magnetic Field Sweeping of Parahydrogen-Induced ¹³C Polarization Joalland, Baptiste; Chekmenev, Eduard Y. The Journal of Physical Chemistry Letters, Vol. 13, Issue 8 https://doi.org/10.1021/acs.jpclett.2c00029	journal	February 2022
Liquid-state carbon-13 hyperpolarization generated in an MRI system for fast imaging Schmidt, A. B.; Berner, S.; Schimpf, W. Nature Communications, Vol. 8, Issue 1 https://doi.org/10.1038/ncomms14535	journal	March 2017
Hyperpolarized 13C Lactate, Pyruvate, and Alanine: Noninvasive Biomarkers for Prostate Cancer Detection and Grading Albers, M. J.; Bok, R.; Chen, A. P. Cancer Research, Vol. 68, Issue 20 https://doi.org/10.1158/0008-5472.CAN-08-0749	journal	October 2008
Imaging Metabolism with Hyperpolarized ¹³C-Labeled Cell Substrates Brindle, Kevin M. Journal of the American Chemical Society, Vol. 137, Issue 20 https://doi.org/10.1021/jacs.5b03300	journal	May 2015
SABRE and PHIP pumped RASER and the route to chaos Appelt, Stephan; Lehmkuhl, Sören; Fleischer, Simon Journal of Magnetic Resonance, Vol. 322 https://doi.org/10.1016/j.jmr.2020.106815	journal	January 2021
Clinical-Scale Production of Nearly Pure (>98.5%) Parahydrogen and Quantification by Benchtop NMR Spectroscopy Nantogma, Shiraz; Joalland, Baptiste; Wilkens, Ken Analytical Chemistry, Vol. 93, Issue 7 https://doi.org/10.1021/acs.analchem.0c05129	journal	February 2021
Spontaneous emission of NMR signals in hyperpolarized proton spin systems Chen, Hsueh-Ying; Lee, Youngbok; Bowen, Sean Journal of Magnetic Resonance, Vol. 208, Issue 2 https://doi.org/10.1016/j.jmr.2010.11.002	journal	February 2011
Current and Potential Applications of Clinical ¹³C MR Spectroscopy Kurhanewicz, John; Bok, Robert; Nelson, Sarah J. Journal of Nuclear Medicine, Vol. 49, Issue 3 https://doi.org/10.2967/jnumed.107.045112	journal	March 2008
Parahydrogen‐Induced Radio Amplification by Stimulated Emission of Radiation Joalland, Baptiste; Ariyasingha, Nuwandi M.; Lehmkuhl, Sören Angewandte Chemie, Vol. 132, Issue 22 https://doi.org/10.1002/ange.201916597	journal	March 2020
Imaging considerations for in vivo ¹³C metabolic mapping using hyperpolarized ¹³C‐pyruvate Yen, Y‐F.; Kohler, S. J.; Chen, A. P. Magnetic Resonance in Medicine, Vol. 62, Issue 1 https://doi.org/10.1002/mrm.21987	journal	March 2009
Improved frequency stability of the dual-noble-gas maser Bear, D.; Chupp, T. E.; Cooper, K. Physical Review A, Vol. 57, Issue 6 https://doi.org/10.1103/PhysRevA.57.5006	journal	June 1998
External high-quality-factor resonator tunes up nuclear magnetic resonance Suefke, Martin; Liebisch, Alexander; Blümich, Bernhard Nature Physics, Vol. 11, Issue 9 https://doi.org/10.1038/nphys3382	journal	July 2015
Magnetic shielding of parahydrogen hyperpolarization experiments for the masses Joalland, Baptiste; Nantogma, Shiraz; Chowdhury, Md Raduanul H. Magnetic Resonance in Chemistry, Vol. 59, Issue 12 https://doi.org/10.1002/mrc.5167	journal	May 2021
First hyperpolarized [2-13C]pyruvate MR studies of human brain metabolism Chung, Brian T.; Chen, Hsin-Yu; Gordon, Jeremy Journal of Magnetic Resonance, Vol. 309 https://doi.org/10.1016/j.jmr.2019.106617	journal	December 2019
A Magic Angle Spinning Activated ¹⁷ O DNP Raser Hope, Michael A.; Björgvinsdóttir, Snædís; Grey, Clare P. The Journal of Physical Chemistry Letters, Vol. 12, Issue 1 https://doi.org/10.1021/acs.jpclett.0c03457	journal	December 2020
Detecting tumor response to treatment using hyperpolarized 13C magnetic resonance imaging and spectroscopy Day, Sam E.; Kettunen, Mikko I.; Gallagher, Ferdia A. Nature Medicine, Vol. 13, Issue 11 https://doi.org/10.1038/nm1650	journal	October 2007
Tricarboxylic acid cycle of glia in the in vivo human brain Blüml, S.; Moreno‐Torres, A.; Shic, F. NMR in Biomedicine, Vol. 15, Issue 1 https://doi.org/10.1002/nbm.725	journal	January 2002
In vivo magnetic resonance spectroscopy: basic methodology and clinical applications van der Graaf, Marinette European Biophysics Journal, Vol. 39, Issue 4 https://doi.org/10.1007/s00249-009-0517-y	journal	August 2009
Determination of Choline Concentration in Breast Lesions: Quantitative Multivoxel Proton MR Spectroscopy as a Promising Noninvasive Assessment Tool to Exclude Benign Lesions Dorrius, Monique D.; Pijnappel, Rudolf M.; Jansen-van der Weide, Marijke C. Radiology, Vol. 259, Issue 3 https://doi.org/10.1148/radiol.11101855	journal	June 2011
Continuous Radio Amplification by Stimulated Emission of Radiation using Parahydrogen Induced Polarization (PHIP‐RASER) at 14 Tesla Pravdivtsev, Andrey N.; Sönnichsen, Frank D.; Hövener, Jan‐Bernd ChemPhysChem, Vol. 21, Issue 7 https://doi.org/10.1002/cphc.201901056	journal	February 2020
Through-Space Multinuclear Magnetic Resonance Signal Enhancement Induced by Parahydrogen and Radiofrequency Amplification by Stimulated Emission of Radiation Salnikov, Oleg G.; Trofimov, Ivan A.; Pravdivtsev, Andrey N. Analytical Chemistry, Vol. 94, Issue 43 https://doi.org/10.1021/acs.analchem.2c02929	journal	October 2022
RASER MRI: Magnetic resonance images formed spontaneously exploiting cooperative nonlinear interaction Lehmkuhl, Sören; Fleischer, Simon; Lohmann, Lars Science Advances, Vol. 8, Issue 28 https://doi.org/10.1126/sciadv.abp8483	journal	July 2022
NMR Hyperpolarization Techniques for Biomedicine Nikolaou, Panayiotis; Goodson, Boyd M.; Chekmenev, Eduard Y. Chemistry – A European Journal, Vol. 21, Issue 8 https://doi.org/10.1002/chem.201405253	journal	December 2014
Hyperpolarized ¹³ C allows a direct measure of flux through a single enzyme-catalyzed step by NMR Merritt, Matthew E.; Harrison, Crystal; Storey, Charles Proceedings of the National Academy of Sciences, Vol. 104, Issue 50 https://doi.org/10.1073/pnas.0706235104	journal	December 2007
Tuning high-Q superconducting resonators by magnetic field reorientation Zollitsch, Christoph W.; O’Sullivan, James; Kennedy, Oscar AIP Advances, Vol. 9, Issue 12 https://doi.org/10.1063/1.5129032	journal	December 2019
Investigation of tumor hyperpolarized [1-¹³ C]-pyruvate dynamics using time-resolved multiband RF excitation echo-planar MRSI Larson, Peder E. Z.; Bok, Robert; Kerr, Adam B. Magnetic Resonance in Medicine, Vol. 63, Issue 3 https://doi.org/10.1002/mrm.22264	journal	February 2010

Similar Records

Carbon-13 Radiofrequency Amplification by Stimulated Emission of Radiation of the Hyperpolarized Ketone and Hemiketal Forms of Allyl [1-¹³C]Pyruvate

Journal Article · 2024 · ACS Sensors · OSTI ID:2341454

Nantogma, Shiraz; de Maissin, Henri; Adelabu, Isaiah; +10 more

SQUID-Detected Magnetic Resonance Imaging in MicroteslaFields

Journal Article · 2006 · Annual Review of Biomedical Engineering · OSTI ID:928716

Moessle, Michael; Hatridge, Michael; Clarke, John

High field magnetometry with hyperpolarized nuclear spins

Journal Article · 2022 · Nature Communications · OSTI ID:1888049

Sahin, Ozgur; de Leon Sanchez, Erica; Conti, Sophie; +7 more

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
NMR
MRI
RASER
hyperpolarization
carbon-13
hyperpolarized MRI
sensitivity

Title: 13C Radiofrequency Amplification by Stimulated Emission of Radiation Threshold Sensing of Chemical Reactions

Citation Formats

References (42)

Similar Records

Related Subjects

Title: ¹³C Radiofrequency Amplification by Stimulated Emission of Radiation Threshold Sensing of Chemical Reactions