Nuclear magnetic resonance (NMR) spectroscopy is a well-established analytical technique used to study chemicals and their transformations. However, high-field NMR spectroscopy necessitates advanced ...infrastructure, and even cryogen-free benchtop NMR spectrometers cannot be readily assembled from commercially available components. We demonstrate construction of a portable zero-field NMR spectrometer employing a commercially available magnetometer and investigate its applications in analytical chemistry. In particular, J-spectra of small representative biomolecules 13C-formic acid, 1-13C-glycine, 2,3-13C-fumarate, and 1-13C-d-glucose were acquired, and an approach relying on the presence of a transverse magnetic field during the detection was investigated for relaxometry purposes. We found that the water relaxation time strongly depends on the concentration of dissolved d-glucose in the range of 1–10 mM suggesting opportunities for indirect assessment of glucose concentration in aqueous solutions. Extending analytical capabilities of zero-field NMR to aqueous solutions of simple biomolecules (amino acids, sugars, and metabolites) and relaxation studies of aqueous solutions of glucose highlights the analytical potential of noninvasive and portable ZULF NMR sensors for applications outside of research laboratories.
The reaction of fluorine atoms with hydrogen molecules has long provided a window into the subtle effects of quantum mechanics on chemical dynamics. Kim et al. now show that the system still has some ...secrets left to reveal. The authors applied photodetachment to FH2- anions and their deuterated analogs. This allowed them to intercept the reaction trajectory in the middle and thereby uncover unanticipated weakly bound resonances. Theoretical calculations explain these observations and predict additional similar features that have yet to be seen. Science, this issue p. 510 Photodetachment spectroscopy of the FH2- and FD2- anions allows for the direct observation of reactive resonances in the benchmark reaction F + H2 arrow right HF + H. Using cooled anion precursors and a high-resolution electron spectrometer, we observe several narrow peaks not seen in previous experiments. Theoretical calculations, based on a highly accurate F + H2 potential energy surface, convincingly assign these peaks to resonances associated with quasibound states in the HF + H and DF + D product arrangements and with a quasibound state in the transition state region of the F + H2 reaction. The calculations also reveal quasibound states in the reactant arrangement, which have yet to be resolved experimentally.
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•Demonstration of two-dimensional correlation spectroscopy in zero-field NMR.•First observation of multiple-quantum transition in liquid-state zero-field NMR.•Theory of coherence ...transfer for heteronuclear zero-field NMR J-spectroscopy.•Resolution improved by separating otherwise overlapping resonances.
We present single- and multiple-quantum correlation J-spectroscopy detected in zero (<1μG) magnetic field using a 87Rb vapor-cell magnetometer. At zero field the spectrum of ethanol appears as a mixture of 13C isotopomers, and correlation spectroscopy is useful in separating the two composite spectra. We also identify and observe the zero-field equivalent of a double-quantum transition in 13C2-acetic acid, and show that such transitions are of use in spectral assignment. Two-dimensional spectroscopy further improves the high resolution attained in zero-field NMR since selection rules on the coherence-transfer pathways allow for the separation of otherwise overlapping resonances into distinct cross-peaks.
Here we demonstrate that a term in the nuclear spin Hamiltonian, the antisymmetric J-coupling, is fundamentally connected to molecular chirality. We propose and simulate a nuclear magnetic resonance ...(NMR) experiment to observe this interaction and differentiate between enantiomers without adding any additional chiral agent to the sample. The antisymmetric J-coupling may be observed in the presence of molecular orientation by an external electric field. The opposite parity of the antisymmetric coupling tensor and the molecular electric dipole moment yields a sign change of the observed coupling between enantiomers. We show how this sign change influences the phase of the NMR spectrum and may be used to discriminate between enantiomers.
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•Field cycling is performed over the nanotesla to millitesla range.•Spin-selective NMR pulse sequences are applied.•A swept-frequency adiabatic pulse demonstrates combined use of ...high-field and ultra-low-field NMR methods.
We describe new analytical capabilities for nuclear magnetic resonance (NMR) experiments in which signal detection is performed with chemical resolution (via spin–spin J couplings) in the zero to ultra-low magnetic field region, below 1μT. Using magnetic fields in the 100μT to 1mT range, we demonstrate the implementation of conventional NMR pulse sequences with spin-species selectivity.
Transition-Selective Pulses in Zero-Field Nuclear Magnetic Resonance Sjolander, Tobias F; Tayler, Michael C. D; King, Jonathan P ...
The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory,
06/2016, Letnik:
120, Številka:
25
Journal Article
Recenzirano
We use low-amplitude, ultralow frequency pulses to drive nuclear spin transitions in zero and ultralow magnetic fields. In analogy to high-field NMR, a range of sophisticated experiments becomes ...available as these allow narrow-band excitation. As a first demonstration, pulses with excitation bandwidths 0.5–5 Hz are used for population redistribution, selective excitation, and coherence filtration. These methods are helpful when interpreting zero- and ultralow-field NMR spectra that contain a large number of transitions.
We present a two-dimensional method for obtaining
C-decoupled,
H-coupled nuclear magnetic resonance (NMR) spectra in zero magnetic field using coherent spin-decoupling. The result is a spectrum ...determined only by the proton-proton J-coupling network. Detection of NMR signals in zero magnetic field requires at least two different nuclear spin species, but the proton J-spectrum is independent of isotopomer, thus potentially simplifying spectra and thereby improving the analytical capabilities of zero-field NMR. The protocol does not rely on a difference in Larmor frequency between the coupled nuclei, allowing for the direct determination of J-coupling constants between chemically equivalent spins. We obtain the
C-decoupled zero-field spectrum of 1-
C-propionic acid and identify conserved quantum numbers governing the appearance of cross peaks in the two-dimensional spectrum.
The weak interaction does not conserve parity, which is apparent in many nuclear and atomic phenomena. However, thus far, parity nonconservation has not been observed in molecules. Here we consider ...nuclear-spin-dependent parity-nonconserving contributions to the molecular Hamiltonian. These contributions give rise to a parity-nonconserving indirect nuclear spin-spin coupling which can be distinguished from parity-conserving interactions in molecules of appropriate symmetry, including diatomic molecules. We estimate the magnitude of the coupling, taking into account relativistic corrections. Finally, we propose and simulate an experiment to detect the parity-nonconserving coupling using liquid- or gas-state zero-field nuclear magnetic resonance of electrically oriented molecules and show that ^{1}H^{19}F should give signals within the detection limits of current atomic vapor-cell magnetometers.
We present a two-dimensional method for obtaining 13C-decoupled, 1H-coupled nuclear magnetic resonance (NMR) spectra in zero magnetic field using coherent spin-decoupling. The result is a spectrum ...determined only by the proton–proton J-coupling network. Detection of NMR signals in zero magnetic field requires at least two different nuclear spin species, but the proton J-spectrum is independent of isotopomer, thus potentially simplifying spectra and thereby improving the analytical capabilities of zero-field NMR. The protocol does not rely on a difference in Larmor frequency between the coupled nuclei, allowing for the direct determination of J-coupling constants between chemically equivalent spins. We obtain the 13C-decoupled zero-field spectrum of 1–13C-propionic acid and identify conserved quantum numbers governing the appearance of cross peaks in the two-dimensional spectrum.
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