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Florin Teleanu

Publications and source records attributed to Florin Teleanu.

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Single-Scan Characterization of $^{14}$N Nuclei via $^1$H-Detected Rotating-Frame Relaxometry

$^{14}$N NMR is notoriously difficult to perform in liquids due to the very fast spin relaxation and the large quadrupolar couplings, which render many signals invisible. We show here how $^{14}$N nuclei of biomolecular constituents can be probed indirectly by reintroducing the scalar relaxation of the second kind contribution to the polarization lifetimes of J-coupled protons in double resonance spin-locking experiments. The enhanced $^1$H relaxation rates in the rotating-frame allow for direct evaluation of nitrogen chemical shift and polarization lifetimes, from which one- and even two-bond $^1$H-$^{14}$N scalar couplings as well as $^{14}$N quadrupolar interactions can be determined. We demonstrate the versatility of this method by characterizing $^1$H-$^{14}$N spin pairs in several molecules of biological importance, showing proton relaxation enhancements beyond one order of magnitude. We further observe a pronounced effect from intermolecular hydrogen bonding. Our approach can be readily integrated into existing biomolecular NMR methodologies, as demonstrated here for $^1$H-detected relaxation-editing experiments with water suppression. This method provides access to nitrogen's picosecond-modulated quadrupolar interaction via single-scan proton detection in systems that would otherwise yield almost no detectable direct $^{14}$N signal even after averaging over thousands of transients.

physics.chem-ph

Nuclear spin relaxation in zero- to ultralow-field magnetic resonance spectroscopy

Nuclear-magnetic-resonance experiments can interrogate a broad spectrum of molecular-tumbling regimes and can accurately measure interatomic distances in solution with sub-nanometer resolution. In the zero- to ultralow-field (ZULF) regime, population and coherence decay reveal nontrivial behavior due to strong coupling between nuclear spins. We note, in particular, the surprising effects that different resonances show different relaxation rates, depending on (i) the (pre)polarizing magnet field and the shuttling trajectory to the detection region at nano- and microtesla fields, (ii) the strength of the measurement field, (iii) the detection method (single-channel or quadrature), and even (iv) the nutation angle induced by the excitation pulse. We describe herein experimental data of relaxation rates measured for a 13C-labeled formic acid sample, with an atomic-magnetometer-based ZULF setup, and develop a theoretical framework to explain the detected effects and extract molecular properties. The observed effects could be used for spectral assignment, for the establishment of specific motional regimes, for image contrast, and for the characterization of relaxation processes at nano- to microtesla magnetic fields.

physics.chem-ph

Over four minutes relaxation of pyruvate using chemically and physically induced deceleration of relaxation

[1-13C]pyruvate is the most widely used tracer for hyperpolarized metabolic magnetic resonance imaging, with profound applications in tumor and inflammation diagnosis as well as treatment monitoring. The most fundamental hurdle to broader application, however, remains the rapid polarization relaxation and the associated signal loss. Here, we report a method to address this challenge. Studying the nuclear spin relaxation dispersion of [1-13C]pyruvate across magnetic fields from 8 {\mu}T to 9.4 T, as a function of additives, solvents, and preparation methods, allowed us to achieve relaxation times of up to four minutes. Such a long time could enable reliable quality control and nearly polarization loss-free transport, further boosting the power of hyperpolarized metabolic MRI.

physics.chem-ph