Time-resolved, optically detected NMR of fluids at high magnetic field

Pagliero, Daniela; Dong, Wei; Sakellariou, Dimitrios; Meriles, Carlos A.

doi:10.1063/1.3502484

Cited by 34 publications

(57 citation statements)

References 26 publications

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“…We then coadd these echoes to produce an average signal (8) whose amplitude will be a transverse coherence time-weighted measure of the system density; naturally, subsequent Fourier transform leads to the corresponding lowresolution (∼1 ppm) chemical shift-resolved spectrum. Although this strategy regains part of the sensitivity loss caused by field inhomogeneity and susceptibility broadening, we emphasize that the simpler scheme excitation-acquisition should suffice in a system designed to simultaneously suit the constraints of rf manipulation and optical sensing (8,10). Fig.…”

Section: Resultsmentioning

confidence: 99%

“…We refer the reader to the supplementary material in ref. 8 for a fuller description of this effect.…”

Section: Methodsmentioning

confidence: 99%

“…Initial studies based on a continuous wave (cw) protocol demonstrated OFR-based detection of proton magnetic resonance in prepolarized water at approximately 5 G (7). Recent results at high magnetic field show that it is possible to optically probe nuclear spins in real time after resonant radio frequency (rf) excitation, to determine, after Fourier transform, the corresponding chemical-shift-resolved NMR spectrum (8). Further, ab initio calculations in small molecules predict that nuclear spininduced Faraday rotation should convey distinct signals for nuclei in differing chemical environments (9).…”

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confidence: 99%

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Magneto-optical contrast in liquid-state optically detected NMR spectroscopy

Pagliero

Meriles

2011

Proc. Natl. Acad. Sci. U.S.A.

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We use optical Faraday rotation (OFR) to probe nuclear spins in real time at high-magnetic field in a range of diamagnetic sample fluids.Comparison of OFR-detected NMR spectra reveals a correlation between the relative signal amplitude and the fluid Verdet constant, which we interpret as a manifestation of the variable detuning between the probe beam and the sample optical transitions. The analysis of chemical-shift-resolved, optically detected spectra allows us to set constraints on the relative amplitudes of hyperfine coupling constants, both for protons at chemically distinct sites and other lower-gyromagnetic-ratio nuclei including carbon, fluorine, and phosphorous. By considering a model binary mixture we observe a complex dependence of the optical response on the relative concentration, suggesting that the present approach is sensitive to the solvent-solute dynamics in ways complementary to those known in inductive NMR. Extension of these experiments may find application in solvent suppression protocols, sensitivityenhanced NMR of metalloproteins in solution, the investigation of solvent-solute interactions, or the characterization of molecular orbitals in diamagnetic systems. N uclear Magnetic Resonance is one of the leading analytical tools among material scientists, organic chemists, and structural biologists. One of its main advantages is the spectral dispersion resulting from system-specific chemical shifts, and from dipolar, quadrupolar, and J-couplings (1). In a typical inductively detected NMR spectrum the relative amplitude of a resonance is given by the fraction of nuclei associated with a particular functional group. The greater natural abundance and higher gyromagnetic ratio of protons make 1 H NMR the most sensitive, a feature that has led spectroscopists to develop various schemes of polarization or coherence transfer to more efficiently detect other less favorable nuclei. Conversely, selective deuteration and solvent suppression schemes are the traditional tools at hand to highlight weaker proton resonances from molecules in solution.Unlike inductive detection, where nuclear spins interact directly with a pick-up circuit tuned to the Larmor frequency, optical schemes in general rely on electrons as intermediaries. The resulting signal amplitude depends on the hyperfine coupling between electrons and nuclear spins on the one hand, and on the interaction between electrons and optical photons on the other (the so-called oscillator strength of the system at a given illumination wavelength). Favorable conditions are typically met in select atomic vapors (2-4) and condensed matter systems (5, 6), which explains why optical schemes, normally designed to monitor the sample fluorescence or absorption, have not yet enjoyed a more widespread use. Recent experiments, however, indicate that optical Faraday rotation (OFR) can serve as a more general platform applicable, in principle, to all transparent condensed matter systems. Initial studies based on a continuous wave (cw) protocol demonstrated OFR-base...

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Section: Resultsmentioning

confidence: 99%

“…We refer the reader to the supplementary material in ref. 8 for a fuller description of this effect.…”

Section: Methodsmentioning

confidence: 99%

mentioning

confidence: 99%

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Magneto-optical contrast in liquid-state optically detected NMR spectroscopy

Pagliero

Meriles

2011

Proc. Natl. Acad. Sci. U.S.A.

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“…Various means of creating and controlling the nuclear magnetization in NMOS measurements have been discussed. [9][10][11][12] These include transferring the magnetized sample from a separate polarization vessel to the optical apparatus, 9, 10 a method relying on relatively slow nuclear spin relaxation processes. Alternatively, the optical measurement can be placed transversally to the bore of a nuclear magnetic resonance spectrometer, enabling the creation and manipulation of the magnetization in the same volume.…”

Section: B Nuclear Spin-induced Circular Dichroismmentioning

confidence: 99%

“…10 This phenomenon was predicted using firsta) juha.vaara@iki.fi b) coriani@units.it principles calculations according to the response theory formulation of the underlying antisymmetric polarizability. 6 Further experimental [11][12][13] and theoretical [14][15][16] work has been reported for NSOR. Nuclear spin-and electric quadrupole moment-induced Cotton-Mouton effects have been theoretically investigated in Refs.…”

Section: Introductionmentioning

confidence: 99%

Nuclear spin circular dichroism

Vaara¹,

Rizzo²,

Kauczor³

et al. 2014

The Journal of Chemical Physics

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Articles you may be interested inMagnetic circular dichroism of symmetry and spin forbidden transitions of high-spin metal ions J. Chem. Phys. 113, 5003 (2000) Recent years have witnessed a growing interest in magneto-optic spectroscopy techniques that use nuclear magnetization as the source of the magnetic field. Here we present a formulation of magnetic circular dichroism (CD) due to magnetically polarized nuclei, nuclear spin-induced CD (NSCD), in molecules. The NSCD ellipticity and nuclear spin-induced optical rotation (NSOR) angle correspond to the real and imaginary parts, respectively, of (complex) quadratic response functions involving the dynamic second-order interaction of the electron system with the linearly polarized light beam, as well as the static magnetic hyperfine interaction. Using the complex polarization propagator framework, NSCD and NSOR signals are obtained at frequencies in the vicinity of optical excitations. Hartree-Fock and density-functional theory calculations on relatively small model systems, ethene, benzene, and 1,4-benzoquinone, demonstrate the feasibility of the method for obtaining relatively strong nuclear spin-induced ellipticity and optical rotation signals. Comparison of the proton and carbon-13 signals of ethanol reveals that these resonant phenomena facilitate chemical resolution between non-equivalent nuclei in magneto-optic spectra. © 2014 AIP Publishing LLC.

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Dynamic Nuclear Polarization Enhanced Nuclear Spin Optical Rotation

2021

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Nuclear spin optical rotation (NSOR) has been investigated as a magneto-optical effect, which holds the potential for applications, including hybrid optical-nuclear magnetic resonance (NMR) spectroscopy and gradientless imaging. The intrinsic nature of NSOR renders its detection relatively insensitive, which has prevented it moving from a proof of concept to a method supporting chemical characterizations. In this work, the dissolution dynamic nuclear polarization technique is introduced to provide nuclear spin polarization, increasing the signal-to-noise ratio by several thousand times. NSOR signals of 1 H and 19 F nuclei are observed in a single scan for diluted compounds, which has made this effect suitable for the determination of electronic transitions from a specific nucleus in a large molecule.

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Time-resolved, optically detected NMR of fluids at high magnetic field

Cited by 34 publications

References 26 publications

Magneto-optical contrast in liquid-state optically detected NMR spectroscopy

Magneto-optical contrast in liquid-state optically detected NMR spectroscopy

Nuclear spin circular dichroism

Dynamic Nuclear Polarization Enhanced Nuclear Spin Optical Rotation

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