Excitation of singlet–triplet coherences in pairs of nearly-equivalent spins

We present approaches for an efficient excitation of singlet–triplet coherences in pairs of nearly-equivalent spins. Standard Nuclear Magnetic Resonance (NMR) pulse sequences do not excite these coherences at all or with very low efficiency. The single quantum singlet–triplet coherences, here termed the outer singlet–triplet coherences, correspond to lines of low intensity in the NMR spectrum of a strongly-coupled spin pair (they are sometimes referred to as “forbidden transitions”), whereas the zero-quantum coherences, here termed the inner singlet–triplet coherences, do not have a direct spectral manifestation. In the present study, we investigated singlet–triplet coherences in a pair of …

Singulett‐Kontrast‐Magnetresonanztomographie: Freisetzung der Hyperpolarisation durch den Metabolismus**

Singlet‐Contrast Magnetic Resonance Imaging: Unlocking Hyperpolarization with Metabolism

Abstract Hyperpolarization‐enhanced magnetic resonance imaging can be used to study biomolecular processes in the body, but typically requires nuclei such as 13C, 15N, or 129Xe due to their long spin‐polarization lifetimes and the absence of a proton‐background signal from water and fat in the images. Here we present a novel type of 1H imaging, in which hyperpolarized spin order is locked in a nonmagnetic long‐lived correlated (singlet) state, and is only liberated for imaging by a specific biochemical reaction. In this work we produce hyperpolarized fumarate via chemical reaction of a precursor molecule with para‐enriched hydrogen gas, and the proton singlet order in fumarate is released a…

Photochemically induced dynamic nuclear polarization of heteronuclear singlet order

Photochemically induced dynamic nuclear polarization (photo-CIDNP) is a method to hyperpolarize nuclear spins using light. In most cases, CIDNP experiments are performed in high magnetic fields and the sample is irradiated by light inside a nuclear magnetic resonance (NMR) spectrometer. Here we demonstrate photo-CIDNP hyperpolarization generated in the Earth's magnetic field and under zero- to ultralow-field (ZULF) conditions. Irradiating a sample containing tetraphenylporphyrin and para-benzoquinone for several seconds with light-emitting diodes produces strong hyperpolarization of 1H and 13C nuclear spins, enhancing the NMR signals more than 200 times. The hyperpolarized spin states at th…

Chapter 23. Singlet Order in Heteronuclear Spin Systems

The concept of heteronuclear Long-Lived spin States (LLSs) is introduced. In the simplest case of a pair of heteronuclei, such states are given by the singlet order of the spin pair, which can be efficiently sustained under Zero or Ultra-Low Field (ZULF) conditions. Here we describe two possible ways of detecting long-lived singlet order of heteronuclei: detection at ZULF conditions and NMR (Nuclear Magnetic Resonance) detection at high field utilising fast field-cycling. A theoretical description of the underlying spin dynamics is presented for both cases; the discussion is supported by experimental examples of LLSs in 13CH groups. The generality of these phenomena is discussed, as well as…

Algorithmic cooling of nuclear spins using long-lived singlet order

Algorithmic cooling methods manipulate an open quantum system in order to lower its temperature below that of the environment. We achieve significant cooling of an ensemble of nuclear spin-pair systems by exploiting the long-lived nuclear singlet state, which is an antisymmetric quantum superposition of the "up" and "down" Zeeman states. The effect is demonstrated by nuclear magnetic resonance (NMR) experiments on a molecular system containing a coupled pair of near-equivalent 13C nuclei. The populations of the system are subjected to a repeating sequence of cyclic permutations separated by relaxation intervals. The long-lived nuclear singlet order is pumped well beyond the unitary limit. T…

Correlation of high-field and zero- to ultralow-field NMR properties using 2D spectroscopy

The field of zero- to ultralow-field (ZULF) nuclear magnetic resonance (NMR) is currently experiencing a rapid growth, owing to the progress in optical magnetometry, and also attractive features of ZULF NMR, such as low hardware cost and excellent spectral resolution achieved under ZULF conditions. In this work, an approach is proposed and demonstrated for simultaneous acquisition of ZULF-NMR spectra of individual 13C-containing isotopomers of chemical compounds in a complex mixture. The method makes use of fast field cycling, so that the spin evolution takes place at ZULF conditions, whereas signal detection is performed in a high-field NMR spectrometer. This method has excellent sensitivi…

Constant-adiabaticity ultralow magnetic field manipulations of parahydrogen-induced polarization: application to an AA'X spin system

The field of magnetic resonance imaging with hyperpolarized contrast agents is rapidly expanding, and parahydrogen-induced polarization (PHIP) is emerging as an inexpensive and easy-to-implement method for generating the required hyperpolarized biomolecules. Hydrogenative PHIP delivers hyperpolarized proton spin order to a substrate via chemical addition of H2 in the spin-singlet state, but it is typically necessary to transfer the proton polarization to a heteronucleus (usually 13C) which has a longer spin lifetime. Adiabatic ultralow magnetic field manipulations can be used to induce the polarization transfer, but this is necessarily a slow process, which is undesirable since the spins co…

Hyperpolarization of cis ‐ 15 N 2 ‐Azobenzene by Parahydrogen at Ultralow Magnetic Fields**

The development of nuclear spins hyperpolarization, and the search for molecules that can be efficiently hyperpolarized is an active area in nuclear magnetic resonance. In this work we present a detailed study of SABRE SHEATH (signal amplification by reversible exchange in shield enabled alignment transfer to heteronuclei) experiments on 15 N2 -azobenzene. In SABRE SHEATH experiments the nuclear spins of the target are hyperpolarized through transfer of spin polarization from parahydrogen at ultralow fields during a reversible chemical process. Azobenzene exists in two isomers, trans and cis. We show that all nuclear spins in cis-azobenzene can be efficiently hyperpolarized by SABRE at suit…

Constant-adiabaticity pulse schemes for manipulating singlet order in 3-spin systems with weak magnetic non-equivalence

Abstract Parahydrogen-induced polarization (PHIP) is a source of nuclear spin hyperpolarization, and this technique allows for the preparation of biomolecules for in vivo metabolic imaging. PHIP delivers hyperpolarization in the form of proton singlet order to a molecule, but most applications require that a heteronuclear (e.g. 13C or 15N) spin in the molecule is hyperpolarized. Here we present high field pulse methods to manipulate proton singlet order in the [1-13C]fumarate, and in particular to transfer the proton singlet order into 13C magnetization. We exploit adiabatic pulses, i.e., pulses with slowly ramped amplitude, and use constant-adiabaticity variants: the spin Hamiltonian is va…

Algorithmic Cooling of Nuclear Spin Pairs using a Long-Lived Singlet State

Algorithmic cooling methods manipulate an open quantum system in order to lower its temperature below that of the environment. We show that significant cooling is achieved on an ensemble of spin-pair systems by exploiting the long-lived nuclear singlet state, which is an antisymmetric quantum superposition of the "up" and "down" qubit states. The effect is demonstrated by nuclear magnetic resonance (NMR) experiments on a molecular system containing a coupled pair of near-equivalent 13C nuclei. The populations of the system are subjected to a repeating sequence of cyclic permutations separated by relaxation intervals. The long-lived nuclear singlet order is pumped well beyond the unitary lim…