The contribution of protons in or near biradical polarizing agents in Dynamic Nuclear Polarization (DNP) has recently been under scrutiny. Results from selective deuteration and simulations have previously suggested that the role of protons in the biradical molecule depends on the strength of the electron-electron coupling. Here we use the cross effect DNP mechanism to identify and acquire H solid-state NMR spectra of the protons that contribute to propagation of the hyperpolarization, via an experimental approach dubbed Nuclear-Nuclear Double Resonance (NUDOR).
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http://dx.doi.org/10.1021/acs.jpclett.4c03254 | DOI Listing |
J Phys Chem Lett
January 2025
National High Magnetic Field Laboratory, Florida State University, 1800 E. Paul Dirac Dr, Tallahassee, Florida 32310, United States.
The contribution of protons in or near biradical polarizing agents in Dynamic Nuclear Polarization (DNP) has recently been under scrutiny. Results from selective deuteration and simulations have previously suggested that the role of protons in the biradical molecule depends on the strength of the electron-electron coupling. Here we use the cross effect DNP mechanism to identify and acquire H solid-state NMR spectra of the protons that contribute to propagation of the hyperpolarization, via an experimental approach dubbed Nuclear-Nuclear Double Resonance (NUDOR).
View Article and Find Full Text PDFChem Sci
September 2024
Centre de RMN à Hauts Champs de Lyon, UMR 5082, Université de Lyon (CNRS/ENS Lyon/UCBL) 5 rue de la Doua Villeurbanne 69100 France
Dynamic Nuclear Polarization (DNP) can significantly enhance the sensitivity of solid-state NMR. In DNP, microwave irradiation induces polarization transfer from unpaired electron spins to H nuclear spins hyperfine couplings and spin-diffusion. The structure of the polarizing agents that host the electron spins is key for DNP efficiency.
View Article and Find Full Text PDFInt J Mol Sci
August 2024
Manchester Institute of Biotechnology, Department of Chemical Engineering, The University of Manchester, 131 Princess Street, Manchester M1 7DN, UK.
During gliotoxin biosynthesis in fungi, the cytochrome P450 GliF enzyme catalyzes an unusual C-N ring-closure step while also an aromatic ring is hydroxylated in the same reaction cycle, which may have relevance to drug synthesis reactions in biotechnology. However, as the details of the reaction mechanism are still controversial, no applications have been developed yet. To resolve the mechanism of gliotoxin biosynthesis and gain insight into the steps leading to ring-closure, we ran a combination of molecular dynamics and density functional theory calculations on the structure and reactivity of P450 GliF and tested a range of possible reaction mechanisms, pathways and models.
View Article and Find Full Text PDFJ Phys Chem Lett
February 2024
National High Magnetic Field Laboratory, Florida State University, 1800 East Paul Dirac Drive, Tallahassee, Florida 32310, United States.
In magic angle spinning dynamic nuclear polarization (DNP), biradicals such as bis-nitroxides are used to hyperpolarize protons under microwave irradiation through the cross-effect mechanism. This mechanism relies on electron-electron spin interactions (dipolar coupling and exchange interaction) and electron-nuclear spin interactions (hyperfine coupling) to hyperpolarize the protons surrounding the biradical. This hyperpolarization is then transferred to the bulk sample via nuclear spin diffusion.
View Article and Find Full Text PDFPhys Chem Chem Phys
February 2024
Univ. Grenoble Alpes, CEA, CNRS, IRIG, MEM, 38000 Grenoble, France.
Two polarizing agents from the AsymPol family, AsymPol-TEK and cAsymPol-TEK (methyl-free version) are introduced for MAS-DNP applications in non-aqueous solvents. The performance of these new biradicals is rationalized in detail using a combination of electron paramagnetic resonance spectroscopy, density functional theory, molecular dynamics and quantitative MAS-DNP spin dynamics simulations. By slightly modifying the experimental protocol to keep the sample temperature low at insertion, we are able to obtain reproducable DNP-NMR data with 1,1,2,2-tetrachloroethane (TCE) at 100 K, which facilitates optimization and comparison of different polarizing agents.
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