$^{31}$P NMR and MRI are commonly used to study organophosphates that are central to cellular energy metabolism. In some molecules of interest, such as adenosine diphosphate (ADP) and nicotinamide adenine dinucleotide (NAD), pairs of coupled $^{31}$P
nuclei in the diphosphate moiety should enable the creation of nuclear spin singlet states, which may be long-lived and can be selectively detected via quantum filters. Here, we show that $^{31}$P singlet states can be created on ADP and NAD, but their lifetimes are shorter than T$_{1}$ and are strongly sensitive to pH. Nevertheless, the singlet states were used with a quantum filter to successfully isolate the $^{31}$P NMR spectra of those molecules from the adenosine triphosphate (ATP) background signal.
Nuclear magnetic resonance (NMR) spectroscopy usually requires high magnetic fields to create spectral resolution among different proton species. At low fields, chemical shift dispersion is insufficient to separate the species, and the spectrum exhib
its just a single line. In this work, we demonstrate that spectra can nevertheless be acquired at low field using a novel pulse sequence called spin-lock induced crossing (SLIC). This probes energy level crossings induced by a weak spin-locking pulse and produces a unique J-coupling spectrum for most organic molecules. Unlike other forms of low-field J-coupling spectroscopy, our technique does not require the presence of heteronuclei and can be used for most compounds in their native state. We performed SLIC spectroscopy on a number of small molecules at 276 kHz and 20.8 MHZ, and we show that SLIC spectra can be simulated in good agreement with measurements.
We probe small scalar coupling differences via the coherent interactions between two nuclear spin singlet states in organic molecules. We show that the spin-lock induced crossing (SLIC) technique enables the coherent transfer of singlet order between
one spin pair and another. The transfer is mediated by the difference in cis and trans vicinal J couplings among the spins. By measuring the transfer rate, we calculate a J coupling difference of $8 pm 2$ mHz in phenylalanine-glycine-glycine and $2.57 pm 0.04$ Hz in glutamate. We also characterize a coherence between two singlet states in glutamate, which may enable the creation of a long-lived quantum memory.
Nuclear magnetic resonance (NMR) and magnetic resonance imaging (MRI) are well-established techniques that provide valuable information in a diverse set of disciplines but are currently limited to macroscopic sample volumes. Here we demonstrate nanos
cale NMR spectroscopy and imaging under ambient conditions of samples containing multiple nuclear species, using nitrogen-vacancy (NV) colour centres in diamond as sensors. With single, shallow NV centres in a diamond chip and samples placed on the diamond surface, we perform NMR spectroscopy and one-dimensional MRI on few-nanometre-sized samples containing $^1$H and $^{19}$F nuclei. Alternatively, we employ a high-density NV layer near the surface of a diamond chip to demonstrate wide-field optical NMR spectroscopy of nanoscale samples containing $^1$H, $^{19}$F, and $^{31}$P nuclei, as well as multi-species two-dimensional optical MRI with sub-micron resolution. For all diamond samples exposed to air, we identify a ubiquitous $^1$H NMR signal, consistent with a $sim 1$ nm layer of adsorbed hydrocarbons or water on the diamond surface and below any sample placed on the diamond. This work lays the foundation for nanoscale NMR and MRI applications such as studies of single proteins and functional biological imaging with subcellular resolution, as well as characterization of thin films with sub-nanometre resolution.
We introduce a broadly applicable technique to create nuclear spin singlet states in organic molecules and other many-atom systems. We employ a novel pulse sequence to produce a spin-lock induced crossing (SLIC) of the spin singlet and triplet energy
levels, which enables triplet/singlet polarization transfer and singlet state preparation. We demonstrate the utility of the SLIC method by producing a long-lived nuclear spin singlet state on two strongly-coupled proton pairs in the tripeptide molecule phenylalanine-glycine-glycine dissolved in D2O, and by using SLIC to measure the J-couplings, chemical shift differences, and singlet lifetimes of the proton pairs. We show that SLIC is more efficient at creating nearly-equivalent nuclear spin singlet states than previous pulse sequence techniques, especially when triplet/singlet polarization transfer occurs on the same timescale as spin-lattice relaxation.
We measure the lifetime of long-lived nuclear spin singlet states as a function of the strength of the RF spin-locking field and present a simple theoretical model that agrees well with our measurements, including the low-RF-power regime. We also mea
sure the lifetime of a long-lived coherence between singlet and triplet states that does not require a spin-locking field for preservation. Our results indicate that for many molecules, singlet states can be created using weak RF spin-locking fields: more than two orders of magnitude lower RF power than in previous studies. Our findings suggest that in many biomolecules, singlets and related states with enhanced lifetimes might be achievable in vivo with safe levels of RF power.
