Hyperpolarization techniques, such as Overhauser dynamic nuclear polarization (DNP), can provide a dramatic increase in the signal obtained from nuclear magnetic resonance experiments and may therefore enable new applications where sensitivity is a limiting factor. In this contribution, studies of the (1)H and (19)F Overhauser dynamic nuclear polarization enhancements at 345 mT are presented for three different aromatic solvents with the TEMPO radical for a range of radical concentrations. Furthermore, nuclear magnetic relaxation dispersion measurements of the same solutions are analyzed, showing contributions from dipolar and scalar coupling modulated by translational diffusion and different coupling efficiency for different solvents and nuclei. Measurements of the electron paramagnetic resonance linewidth are included to support the analysis of the DNP saturation factor for varying radical concentration. The results of our study give an insight into the characteristics of nitroxide radicals as polarizing agents for (19)F Overhauser DNP of aromatic fluorinated solvents. Furthermore, we compare our results with the findings of the extensive research on Overhauser DNP that was conducted in the past for a large variety of other radicals.
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http://dx.doi.org/10.1039/c3cp52912f | DOI Listing |
Phys Chem Chem Phys
November 2024
G.A. Krestov Institute of Solution Chemistry, Russian Academy of Sciences, Akademicheskaja st., 1, 153045, Ivanovo, Russia.
Molecules
May 2024
Department of Chemistry and Industrial Chemistry, University of Pisa, Via G. Moruzzi 13, 56124 Pisa, Italy.
A squaramide-based organocatalyst for asymmetric Michael reactions has been tested as a chiral solvating agent (CSA) for 26 carboxylic acids and camphorsulfonic acid, encompassing amino acid derivatives, mandelic acid, as well as some of its analogs, propionic acids like profens (ketoprofen and ibuprofen), butanoic acids and others. In many cases remarkably high enantiodifferentiations at H, C and F nuclei were observed. The interaction likely involves a proton transfer from the acidic substrates to the tertiary amine sites of the organocatalyst, thus allowing for pre-solubilization of the organocatalyst (when a chloroform solution of the substrate is employed) or the simultaneous solubilization of both the catalyst and the substrate.
View Article and Find Full Text PDFJ Org Chem
June 2023
Faculty of Pharmaceutical Sciences, Tokyo University of Science, 2641 Yamazaki, Noda-shi, Chiba 278-8510, Japan.
In this study, the conformational properties of tertiary trifluoroacetamides in dibenzoazepine ( and ) and benzodiazepine ( and ) derivatives, which exist as equilibrated - and amide conformers in solution, were investigated by H and F NMR spectroscopy. In all cases, one of the methylene protons neighboring the nitrogen atom of the minor conformer showed a finely split pattern due to coupling with the trifluoromethyl fluorine atoms, as confirmed by F-decoupling experiments. One-dimensional (1D) and two-dimensional (2D) H-F heteronuclear Overhauser spectroscopy (HOESY) experiments were performed to confirm whether these couplings are attributable to through- spin-spin couplings (TBCs) or through- spin-spin couplings (TSCs).
View Article and Find Full Text PDFMolecules
March 2023
National Research Council, Institute for Chemical and Physical Processes (CNR-IPCF), via G. Moruzzi 1, 56124 Pisa, Italy.
Silylated-acetylated cyclodextrin (CD) derivatives have recently been investigated, via nuclear magnetic resonance (NMR) spectroscopy, as chiral sensors for substrates that are endowed and devoid of fluorine atoms, and the importance of Si-F interaction in the discrimination phenomena has been assessed. Here, the contributions of both superficial interactions and inclusion processes were further evaluated by extending the records to other chiral fluorinated substrates of interest for pharmaceutical applications. Non-equivalences were measured for both the H and F resonances in equimolar mixtures with the CDs; the promising results also supported the use of chiral sensors in -stoichiometric amounts.
View Article and Find Full Text PDFProg Nucl Magn Reson Spectrosc
January 2022
Environmental NMR Center, University of Toronto Scarborough, 1265 Military Trail, Toronto M1C1A4, Canada. Electronic address:
NMR spectroscopy is arguably the most powerful tool for the study of molecular structures and interactions, and is increasingly being applied to environmental research, such as the study of wastewater. With over 97% of the planet's water being saltwater, and two thirds of freshwater being frozen in the ice caps and glaciers, there is a significant need to maintain and reuse the remaining 1%, which is a precious resource, critical to the sustainability of most life on Earth. Sanitation and reutilization of wastewater is an important method of water conservation, especially in arid regions, making the understanding of wastewater itself, and of its treatment processes, a highly relevant area of environmental research.
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