Photogenerated Radical in Phenylglyoxylic Acid for in Vivo Hyperpolarized 13C MR with Photosensitive Metabolic Substrates

Irene Marco-Rius*, Tian Cheng, Adam P. Gaunt, Saket Patel, Felix Kreis, Andrea Capozzi, Alan J. Wright, Kevin M. Brindle, Olivier Ouari, Arnaud Comment

*Corresponding author for this work

Research output: Contribution to journalJournal articleResearchpeer-review

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Abstract

Whether for 13C magnetic resonance studies in chemistry,biochemistry, or biomedicine, hyperpolarization methods based on dynamicnuclear polarization (DNP) have become ubiquitous. DNP requires asource of unpaired electrons, which are commonly added to the sampleto be hyperpolarized in the form of stable free radicals. Once polarized,the presence of these radicals is unwanted. These radicals can bereplaced by nonpersistent radicals created by the photoirradiationof pyruvic acid (PA), which are annihilated upon dissolution or thermalizationin the solid state. However, since PA is readily metabolized by mostcells, its presence may be undesirable for some metabolic studies.In addition, some 13C substrates are photosensitive andtherefore may degrade during the photogeneration of a PA radical,which requires ultraviolet (UV) light. We show here that the photoirradiationof phenylglyoxylic acid (PhGA) using visible light produces a nonpersistentradical that, in principle, can be used to hyperpolarize any molecule.We compare radical yields in samples containing PA and PhGA upon photoirradiationwith broadband and narrowband UV–visible light sources. Todemonstrate the suitability of PhGA as a radical precursor for DNP,we polarized the gluconeogenic probe 13C-dihydroxyacetone,which is UV-sensitive, using a commercial 3.35 T DNP polarizer andthen injected this into a mouse and followed its metabolism in vivo.
Original languageEnglish
JournalJournal of the American Chemical Society
Number of pages9
ISSN0002-7863
DOIs
Publication statusPublished - 2018

Keywords

  • Photolysis
  • Dynamic Nuclear Polarization
  • Hyperpolarization
  • Benzoylformic acid
  • Dihydroxyacetone

Cite this

Marco-Rius, Irene ; Cheng, Tian ; Gaunt, Adam P. ; Patel, Saket ; Kreis, Felix ; Capozzi, Andrea ; Wright, Alan J. ; Brindle, Kevin M. ; Ouari, Olivier ; Comment, Arnaud. / Photogenerated Radical in Phenylglyoxylic Acid for in Vivo Hyperpolarized 13C MR with Photosensitive Metabolic Substrates. In: Journal of the American Chemical Society. 2018.
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title = "Photogenerated Radical in Phenylglyoxylic Acid for in Vivo Hyperpolarized 13C MR with Photosensitive Metabolic Substrates",
abstract = "Whether for 13C magnetic resonance studies in chemistry,biochemistry, or biomedicine, hyperpolarization methods based on dynamicnuclear polarization (DNP) have become ubiquitous. DNP requires asource of unpaired electrons, which are commonly added to the sampleto be hyperpolarized in the form of stable free radicals. Once polarized,the presence of these radicals is unwanted. These radicals can bereplaced by nonpersistent radicals created by the photoirradiationof pyruvic acid (PA), which are annihilated upon dissolution or thermalizationin the solid state. However, since PA is readily metabolized by mostcells, its presence may be undesirable for some metabolic studies.In addition, some 13C substrates are photosensitive andtherefore may degrade during the photogeneration of a PA radical,which requires ultraviolet (UV) light. We show here that the photoirradiationof phenylglyoxylic acid (PhGA) using visible light produces a nonpersistentradical that, in principle, can be used to hyperpolarize any molecule.We compare radical yields in samples containing PA and PhGA upon photoirradiationwith broadband and narrowband UV–visible light sources. Todemonstrate the suitability of PhGA as a radical precursor for DNP,we polarized the gluconeogenic probe 13C-dihydroxyacetone,which is UV-sensitive, using a commercial 3.35 T DNP polarizer andthen injected this into a mouse and followed its metabolism in vivo.",
keywords = "Photolysis, Dynamic Nuclear Polarization, Hyperpolarization, Benzoylformic acid, Dihydroxyacetone",
author = "Irene Marco-Rius and Tian Cheng and Gaunt, {Adam P.} and Saket Patel and Felix Kreis and Andrea Capozzi and Wright, {Alan J.} and Brindle, {Kevin M.} and Olivier Ouari and Arnaud Comment",
year = "2018",
doi = "10.1021/jacs.8b09326",
language = "English",
journal = "Journal of the American Chemical Society",
issn = "0002-7863",
publisher = "ACS Publications",

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Photogenerated Radical in Phenylglyoxylic Acid for in Vivo Hyperpolarized 13C MR with Photosensitive Metabolic Substrates. / Marco-Rius, Irene; Cheng, Tian; Gaunt, Adam P.; Patel, Saket; Kreis, Felix; Capozzi, Andrea; Wright, Alan J.; Brindle, Kevin M.; Ouari, Olivier; Comment, Arnaud.

In: Journal of the American Chemical Society, 2018.

Research output: Contribution to journalJournal articleResearchpeer-review

TY - JOUR

T1 - Photogenerated Radical in Phenylglyoxylic Acid for in Vivo Hyperpolarized 13C MR with Photosensitive Metabolic Substrates

AU - Marco-Rius, Irene

AU - Cheng, Tian

AU - Gaunt, Adam P.

AU - Patel, Saket

AU - Kreis, Felix

AU - Capozzi, Andrea

AU - Wright, Alan J.

AU - Brindle, Kevin M.

AU - Ouari, Olivier

AU - Comment, Arnaud

PY - 2018

Y1 - 2018

N2 - Whether for 13C magnetic resonance studies in chemistry,biochemistry, or biomedicine, hyperpolarization methods based on dynamicnuclear polarization (DNP) have become ubiquitous. DNP requires asource of unpaired electrons, which are commonly added to the sampleto be hyperpolarized in the form of stable free radicals. Once polarized,the presence of these radicals is unwanted. These radicals can bereplaced by nonpersistent radicals created by the photoirradiationof pyruvic acid (PA), which are annihilated upon dissolution or thermalizationin the solid state. However, since PA is readily metabolized by mostcells, its presence may be undesirable for some metabolic studies.In addition, some 13C substrates are photosensitive andtherefore may degrade during the photogeneration of a PA radical,which requires ultraviolet (UV) light. We show here that the photoirradiationof phenylglyoxylic acid (PhGA) using visible light produces a nonpersistentradical that, in principle, can be used to hyperpolarize any molecule.We compare radical yields in samples containing PA and PhGA upon photoirradiationwith broadband and narrowband UV–visible light sources. Todemonstrate the suitability of PhGA as a radical precursor for DNP,we polarized the gluconeogenic probe 13C-dihydroxyacetone,which is UV-sensitive, using a commercial 3.35 T DNP polarizer andthen injected this into a mouse and followed its metabolism in vivo.

AB - Whether for 13C magnetic resonance studies in chemistry,biochemistry, or biomedicine, hyperpolarization methods based on dynamicnuclear polarization (DNP) have become ubiquitous. DNP requires asource of unpaired electrons, which are commonly added to the sampleto be hyperpolarized in the form of stable free radicals. Once polarized,the presence of these radicals is unwanted. These radicals can bereplaced by nonpersistent radicals created by the photoirradiationof pyruvic acid (PA), which are annihilated upon dissolution or thermalizationin the solid state. However, since PA is readily metabolized by mostcells, its presence may be undesirable for some metabolic studies.In addition, some 13C substrates are photosensitive andtherefore may degrade during the photogeneration of a PA radical,which requires ultraviolet (UV) light. We show here that the photoirradiationof phenylglyoxylic acid (PhGA) using visible light produces a nonpersistentradical that, in principle, can be used to hyperpolarize any molecule.We compare radical yields in samples containing PA and PhGA upon photoirradiationwith broadband and narrowband UV–visible light sources. Todemonstrate the suitability of PhGA as a radical precursor for DNP,we polarized the gluconeogenic probe 13C-dihydroxyacetone,which is UV-sensitive, using a commercial 3.35 T DNP polarizer andthen injected this into a mouse and followed its metabolism in vivo.

KW - Photolysis

KW - Dynamic Nuclear Polarization

KW - Hyperpolarization

KW - Benzoylformic acid

KW - Dihydroxyacetone

U2 - 10.1021/jacs.8b09326

DO - 10.1021/jacs.8b09326

M3 - Journal article

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

SN - 0002-7863

ER -