Articles | Volume 4, issue 1
https://doi.org/10.5194/mr-4-47-2023
© Author(s) 2023. This work is distributed under
the Creative Commons Attribution 4.0 License.
the Creative Commons Attribution 4.0 License.
https://doi.org/10.5194/mr-4-47-2023
© Author(s) 2023. This work is distributed under
the Creative Commons Attribution 4.0 License.
the Creative Commons Attribution 4.0 License.
Paramagnetic relaxivity of delocalized long-lived states of protons in chains of CH2 groups
Aiky Razanahoera
Department of Chemistry, École Normale Supérieure, PSL University,
75005 Paris, France
Anna Sonnefeld
Department of Chemistry, École Normale Supérieure, PSL University,
75005 Paris, France
Geoffrey Bodenhausen
Department of Chemistry, École Normale Supérieure, PSL University,
75005 Paris, France
Kirill Sheberstov
CORRESPONDING AUTHOR
Department of Chemistry, École Normale Supérieure, PSL University,
75005 Paris, France
Related authors
No articles found.
Sebastiaan Van Dyck, Coline Wiame, Kirill F. Sheberstov, and Geoffrey Bodenhausen
Magn. Reson. Discuss., https://doi.org/10.5194/mr-2026-5, https://doi.org/10.5194/mr-2026-5, 2026
Preprint under review for MR
Short summary
Short summary
It is shown that proton long-lived states can be observed on benchtop NMR spectrometers in molecules containing short aliphatic chains. The effects of strong coupling between methylene groups can be mitigated by optimizing the amplitude and duration of the excitation pulse.
Coline Wiame, Sebastiaan Van Dyck, Kirill Sheberstov, Aiky Razanahoera, and Geoffrey Bodenhausen
Magn. Reson., 6, 273–279, https://doi.org/10.5194/mr-6-273-2025, https://doi.org/10.5194/mr-6-273-2025, 2025
Short summary
Short summary
In achiral polyfluoroalkyl substances with two to three CF₂ groups, long-lived ¹⁹F spin states (TLLS) were measured and found to last about three times longer than T₁ in a static 11.6 T field. These lifetimes are sensitive to macromolecular binding, making them useful for screening fluorinated drugs.
Quentin Stern and Kirill Sheberstov
Magn. Reson., 4, 87–109, https://doi.org/10.5194/mr-4-87-2023, https://doi.org/10.5194/mr-4-87-2023, 2023
Short summary
Short summary
This tutorial paper shows how to simulate NMR spectra at zero to ultralow fields. The process is presented in detail, including the tricks that are usually omitted from research papers and assuming as little prior knowledge from the reader as possible. In this attempt to make NMR simulation approachable, the authors wish to pay tribute to the late Prof. Konstantin L’vovich Ivanov.
Alexandra Yurkovskaya and Geoffrey Bodenhausen
Magn. Reson., 2, 341–342, https://doi.org/10.5194/mr-2-341-2021, https://doi.org/10.5194/mr-2-341-2021, 2021
Short summary
Cited articles
Ardenkjær-Larsen, J. H., Fridlund, B., Gram, A., Hansson, G., Hansson,
L., Lerche, M. H., Servin, R., Thaning, M., and Golman, K.: Increase in
signal-to-noise ratio of > 10,000 times in liquid-state NMR,
P. Natl. Acad. Sci. USA, 100, 10158–10163, https://doi.org/10.1073/pnas.1733835100, 2003.
Bengs, C. and Levitt, M. H.: SpinDynamica: Symbolic and numerical magnetic
resonance in a Mathematica environment, Magn. Reson. Chem., 56, 374–414,
https://doi.org/10.1002/mrc.4642, 2018.
Borah, B. and Bryant, R. G.: NMR relaxation dispersion in an aqueous
nitroxide system, J. Chem. Phys., 75, 3297–3300,
https://doi.org/10.1063/1.442480, 1981.
Bornet, A., Ji, X., Mammoli, D., Vuichoud, B., Milani, J., Bodenhausen, G.,
and Jannin, S.: Long-Lived States of Magnetically Equivalent Spins Populated
by Dissolution-DNP and Revealed by Enzymatic Reactions, Eur. J. Chem., 20,
17113–17118, https://doi.org/10.1002/chem.201404967, 2014.
Buratto, R., Bornet, A., Milani, J., Mammoli, D., Vuichoud, B., Salvi, N.,
Singh, M., Laguerre, A., Passemard, S., Gerber-Lemaire, S., Jannin, S., and
Bodenhausen, G.: Drug Screening Boosted by Hyperpolarized Long-Lived States
in NMR, ChemMedChem, 9, 2509–2515, https://doi.org/10.1002/cmdc.201402214,
2014a.
Buratto, R., Mammoli, D., Chiarparin, E., Williams, G., and Bodenhausen, G.:
Exploring Weak Ligand–Protein Interactions by Long-Lived NMR States:
Improved Contrast in Fragment-Based Drug Screening, Angew. Chem. Int. Edit.,
53, 11376–11380, https://doi.org/10.1002/anie.201404921, 2014b.
Buratto, R., Mammoli, D., Canet, E., and Bodenhausen, G.: Ligand–Protein
Affinity Studies Using Long-Lived States of Fluorine-19 Nuclei, J. Med.
Chem., 59, 1960–1966, https://doi.org/10.1021/acs.jmedchem.5b01583, 2016.
Carravetta, M. and Levitt, M. H.: Long-Lived Nuclear Spin States in
High-Field Solution NMR, J. Am. Chem. Soc., 126, 6228–6229,
https://doi.org/10.1021/ja0490931, 2004.
Carravetta, M., Johannessen, O. G., and Levitt, M. H.: Beyond the T1 Limit:
Singlet Nuclear Spin States in Low Magnetic Fields, Phys. Rev. Lett., 92,
153003, https://doi.org/10.1103/PhysRevLett.92.153003, 2004.
DeVience, S. J., Walsworth, R. L., and Rosen, M. S.: Preparation of Nuclear
Spin Singlet States Using Spin-Lock Induced Crossing, Phys. Rev. Lett., 111,
173002, https://doi.org/10.1103/PhysRevLett.111.173002, 2013.
Eichhorn, T. R., Takado, Y., Salameh, N., Capozzi, A., Cheng, T., Hyacinthe,
J.-N., Mishkovsky, M., Roussel, C., and Comment, A.: Hyperpolarization
without persistent radicals for in vivo real-time metabolic imaging, P. Natl. Acad. Sci. USA,
110, 18064–18069, https://doi.org/10.1073/pnas.1314928110, 2013.
El Daraï, T., Cousin, S. F., Stern, Q., Ceillier, M., Kempf, J.,
Eshchenko, D., Melzi, R., Schnell, M., Gremillard, L., Bornet, A., Milani,
J., Vuichoud, B., Cala, O., Montarnal, D., and Jannin, S.: Porous
functionalized polymers enable generating and transporting hyperpolarized
mixtures of metabolites, Nat. Commun., 12, 4695,
https://doi.org/10.1038/s41467-021-24279-2, 2021.
Elliott, S. J., Kadeøávek, P., Brown, L. J., Sabba, M., Glöggler,
S., O'Leary, D. J., Brown, R. C. D., Ferrage, F., and Levitt, M. H.:
Field-cycling long-lived-state NMR of 15N2 spin pairs, Mol. Phys., 117,
861–867, https://doi.org/10.1080/00268976.2018.1543906, 2019.
Erriah, B. and Elliott, S. J.: Experimental evidence for the role of
paramagnetic oxygen concentration on the decay of long-lived nuclear spin
order, RSC Adv., 9, 23418–23424, https://doi.org/10.1039/C9RA03748A, 2019.
Feng, Y., Theis, T., Liang, X., Wang, Q., Zhou, P., and Warren, W. S.:
Storage of Hydrogen Spin Polarization in Long-Lived 13C2 Singlet Order and
Implications for Hyperpolarized Magnetic Resonance Imaging, J. Am. Chem.
Soc., 135, 9632–9635, https://doi.org/10.1021/ja404936p, 2013.
Franzoni, M. B., Buljubasich, L., Spiess, H. W., and Münnemann, K.:
Long-Lived 1H Singlet Spin States Originating from Para-Hydrogen in
Cs-Symmetric Molecules Stored for Minutes in High Magnetic Fields, J. Am.
Chem. Soc., 134, 10393–10396, https://doi.org/10.1021/ja304285s, 2012.
Gajan, D., Bornet, A., Vuichoud, B., Milani, J., Melzi, R., van Kalkeren, H.
A., Veyre, L., Thieuleux, C., Conley, M. P., Grüning, W. R.,
Schwarzwälder, M., Lesage, A., Copéret, C., Bodenhausen, G., Emsley,
L., and Jannin, S.: Hybrid polarizing solids for pure hyperpolarized liquids
through dissolution dynamic nuclear polarization, P. Natl. Acad. Sci. USA, 111, 14693–14697,
https://doi.org/10.1073/pnas.1407730111, 2014.
Hogben, H. J., Hore, P. J., and Kuprov, I.: Multiple decoherence-free states
in multi-spin systems, J. Magn. Reson., 211, 217–220,
https://doi.org/10.1016/j.jmr.2011.06.001, 2011.
Ji, X., Bornet, A., Vuichoud, B., Milani, J., Gajan, D., Rossini, A. J.,
Emsley, L., Bodenhausen, G., and Jannin, S.: Transportable hyperpolarized
metabolites, Nat. Commun., 8, 13975, https://doi.org/10.1038/ncomms13975,
2017.
Kharkov, B., Duan, X., Rantaharju, J., Sabba, M., Levitt, M. H., Canary, J.
W., and Jerschow, A.: Weak nuclear spin singlet relaxation mechanisms
revealed by experiment and computation, Phys. Chem. Chem. Phys., 24,
7531–7538, https://doi.org/10.1039/D1CP05537B, 2022.
Kim, Y., Liu, M., and Hilty, C.: Parallelized Ligand Screening Using
Dissolution Dynamic Nuclear Polarization, Anal. Chem., 88, 11178–11183,
https://doi.org/10.1021/acs.analchem.6b03382, 2016.
Kiryutin, A. S., Rodin, B. A., Yurkovskaya, A. V., Ivanov, K. L., Kurzbach,
D., Jannin, S., Guarin, D., Abergel, D., and Bodenhausen, G.: Transport of
hyperpolarized samples in dissolution-DNP experiments, Phys. Chem. Chem.
Phys., 21, 13696–13705, https://doi.org/10.1039/C9CP02600B, 2019.
Kouøil, K., Kouøilová, H., Bartram, S., Levitt, M. H., and Meier,
B.: Scalable dissolution-dynamic nuclear polarization with rapid transfer of
a polarized solid, Nat. Commun., 10, 1733,
https://doi.org/10.1038/s41467-019-09726-5, 2019.
Kress, T., Walrant, A., Bodenhausen, G., and Kurzbach, D.: Long-Lived States
in Hyperpolarized Deuterated Methyl Groups Reveal Weak Binding of Small
Molecules to Proteins, J. Phys. Chem. Lett., 10, 1523–1529,
https://doi.org/10.1021/acs.jpclett.9b00149, 2019.
Lee, Y., Zeng, H., Ruedisser, S., Gossert, A. D., and Hilty, C.: Nuclear
Magnetic Resonance of Hyperpolarized Fluorine for Characterization of
Protein–Ligand Interactions, J. Am. Chem. Soc., 134, 17448–17451,
https://doi.org/10.1021/ja308437h, 2012.
Miéville, P., Ahuja, P., Sarkar, R., Jannin, S., Vasos, P. R.,
Gerber-Lemaire, S., Mishkovsky, M., Comment, A., Gruetter, R., Ouari, O.,
Tordo, P., and Bodenhausen, G.: Scavenging Free Radicals To Preserve
Enhancement and Extend Relaxation Times in NMR using Dynamic Nuclear
Polarization, Angew. Chem. Int. Edit., 49, 6182–6185,
https://doi.org/10.1002/anie.201000934, 2010.
Miéville, P., Jannin, S., and Bodenhausen, G.: Relaxometry of
insensitive nuclei: Optimizing dissolution dynamic nuclear polarization, J.
Magn. Reson., 210, 137–140, https://doi.org/10.1016/j.jmr.2011.02.006,
2011.
Negroni, M., Turhan, E., Kress, T., Ceillier, M., Jannin, S., and Kurzbach,
D.: Frémy's Salt as a Low-Persistence Hyperpolarization Agent: Efficient
Dynamic Nuclear Polarization Plus Rapid Radical Scavenging, J. Am. Chem.
Soc., 144, 20680–20686, https://doi.org/10.1021/jacs.2c07960, 2022.
Nelson, S. J., Kurhanewicz, J., Vigneron, D. B., Larson, P. E. Z.,
Harzstark, A. L., Ferrone, M., van Criekinge, M., Chang, J. W., Bok, R.,
Park, I., Reed, G., Carvajal, L., Small, E. J., Munster, P., Weinberg, V.
K., Ardenkjaer-Larsen, J. H., Chen, A. P., Hurd, R. E., Odegardstuen, L.-I.,
Robb, F. J., Tropp, J., and Murray, J. A.: Metabolic Imaging of Patients
with Prostate Cancer Using Hyperpolarized [1-13C]Pyruvate, Sci. Transl.
Med., 5, 198ra108, https://doi.org/10.1126/scitranslmed.3006070, 2013.
Pileio, G., Hill-Cousins, J. T., Mitchell, S., Kuprov, I., Brown, L. J.,
Brown, R. C. D., and Levitt, M. H.: Long-Lived Nuclear Singlet Order in
Near-Equivalent 13C Spin Pairs, J. Am. Chem. Soc., 134, 17494–17497,
https://doi.org/10.1021/ja3089873, 2012.
Razanahoera, A., Sonnefeld, A., Bodenhausen, G., and Sheberstov, K.: Paramagnetic relaxivity of delocalized long-lived states of protons in chains of CH2 groups, Zenodo [data set], https://doi.org/10.5281/zenodo.7432635, 2022.
Salvi, N., Buratto, R., Bornet, A., Ulzega, S., Rentero Rebollo, I.,
Angelini, A., Heinis, C., and Bodenhausen, G.: Boosting the Sensitivity of
Ligand–Protein Screening by NMR of Long-Lived States, J. Am. Chem. Soc.,
134, 11076–11079, https://doi.org/10.1021/ja303301w, 2012.
Sarkar, R., Vasos, P. R., and Bodenhausen, G.: Singlet-State Exchange NMR
Spectroscopy for the Study of Very Slow Dynamic Processes, J. Am. Chem.
Soc., 129, 328–334, https://doi.org/10.1021/ja0647396, 2007.
Sheberstov, K. F., Vieth, H.-M., Zimmermann, H., Rodin, B. A., Ivanov, K.
L., Kiryutin, A. S., and Yurkovskaya, A. V.: Generating and sustaining
long-lived spin states in 15N, 15N'-azobenzene, Sci. Rep., 9, 20161, https://doi.org/10.1038/s41598-019-56734-y, 2019.
Sonnefeld, A., Razanahoera, A., Pelupessy, P., Bodenhausen, G., and
Sheberstov, K.: Long-lived states of methylene protons in achiral molecules,
Sci. Adv., 8, eade2113, https://doi.org/10.1126/sciadv.ade2113, 2022a.
Sonnefeld, A., Bodenhausen, G., and Sheberstov, K.: Polychromatic Excitation
of Delocalized Long-Lived Proton Spin States in Aliphatic Chains, Phys. Rev.
Lett., 129, 183203, https://doi.org/10.1103/PhysRevLett.129.183203, 2022b.
Stevanato, G., Hill-Cousins, J. T., Håkansson, P., Roy, S. S., Brown, L.
J., Brown, R. C. D., Pileio, G., and Levitt, M. H.: A Nuclear Singlet
Lifetime of More than One Hour in Room-Temperature Solution, Angew. Chem.
Int. Edit., 54, 3740–3743, https://doi.org/10.1002/anie.201411978, 2015.
Tayler, M. C. D.: Chapter 10: Filters for Long-lived Spin Order, in:
Long-lived Nuclear Spin Order, edited by: Pileio, G., RSC publishing, 188–208,
https://books.rsc.org/books/edited-volume/850/chapter-abstract/599446/Filters-for-Long-lived-Spin-Order?redirectedFrom=fulltext (last access: 14 February 2023), 2020.
Tayler, M. C. D. and Levitt, M. H.: Paramagnetic relaxation of nuclear
singlet states, Phys. Chem. Chem. Phys., 13, 9128–9130,
https://doi.org/10.1039/C1CP20471H, 2011.
Tayler, M. C. D. and Levitt, M. H.: Accessing Long-Lived Nuclear Spin Order
by Isotope-Induced Symmetry Breaking, J. Am. Chem. Soc., 135, 2120–2123,
https://doi.org/10.1021/ja312227h, 2013.
Tayler, M. C. D., Marco-Rius, I., Kettunen, M. I., Brindle, K. M., Levitt,
M. H., and Pileio, G.: Direct Enhancement of Nuclear Singlet Order by
Dynamic Nuclear Polarization, J. Am. Chem. Soc., 134, 7668–7671,
https://doi.org/10.1021/ja302814e, 2012.
Wokaun, A. and Ernst, R. R.: The use of multiple quantum transitions for
relaxation studies in coupled spin systems, Mol. Phys., 36, 317–341,
https://doi.org/10.1080/00268977800101601, 1978.
Short summary
In this work, we study the relaxivity of long-lived states (LLSs) excited across two to three CH2 groups in four different compounds and find that a commonly used polarising agent in dissolution dynamic nuclear polarization (d-DNP) does not enhance relaxation significantly. This result is important for the future implementation of d-DNP hyperpolarization of LLS.
In this work, we study the relaxivity of long-lived states (LLSs) excited across two to three...