Effects of Magnetic Field Cycle on the Polarization Transfer from Parahydrogen to Heteronuclei through Long-Range J‑Couplings

Hyperpolarization of 13C carboxylate signals of metabolically relevant molecules, such as acetate and pyruvate, was recently obtained by means of ParaHydrogen Induced Polarization by Side Arm Hydrogenation (PHIP-SAH). This method relies on functionalization of the carboxylic acid with an unsaturated...

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Bibliographic Details
Published in:The journal of physical chemistry. B 2015-08, Vol.119 (31), p.10035-10041
Main Authors: Cavallari, Eleonora, Carrera, Carla, Boi, Tommaso, Aime, Silvio, Reineri, Francesca
Format: Article
Language:English
Subjects:
Alcohols
Alcohols - chemistry
Carbon Isotopes
Carboxylates
Carboxylic Acids - chemistry
Esters
Hydrogen - chemistry
Hydrogenation
Magnetic Fields
Magnetic Resonance Spectroscopy - standards
Molecular Structure
Polarization
Protons
Pyruvates
Reference Standards
Unsaturated
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Summary:Hyperpolarization of 13C carboxylate signals of metabolically relevant molecules, such as acetate and pyruvate, was recently obtained by means of ParaHydrogen Induced Polarization by Side Arm Hydrogenation (PHIP-SAH). This method relies on functionalization of the carboxylic acid with an unsaturated alcohol (side arm), hydrogenation of the unsaturated alcohol using parahydrogen, and polarization transfer to the target 13C signal. In this case, parahydrogen protons are added three to four bonds away from the target 13C nucleus, while biologically relevant molecules had been hyperpolarized, using parahydrogen, through hydrogenation of an unsaturated bond adjacent to the target 13C signal. The herein reported results show that the same polarization level can be obtained on the 13C carboxylate signal of an ester by means of addition of parahydrogen to the acidic or to the alcoholic moiety and successive application of magnetic field cycle (MFC). Experimental results are supported by calculations that allow one to predict that, upon accurate control of magnetic field strength and speed of the passages, more than 20% polarization can be achieved on the 13C-carboxylate resonance of the esters by means of side arm hydrogenation and MFC.
ISSN:1520-6106
1520-5207
DOI:10.1021/acs.jpcb.5b06222