Parahydrogen-Induced Polarization in Hydrogenation Reactions Mediated by a Metal-Free Catalyst

We report nuclear spin hyperpolarization of various alkenes achieved in alkyne hydrogenations with parahydrogen over a metal-free hydroborane catalyst (HCAT). Being an intramolecular frustrated Lewis pair aminoborane, HCAT utilizes a non-pairwise mechanism of H₂ transfer to alkynes that normally prevents parahydrogen-induced polarization (PHIP) from being observed. Nevertheless, the specific spin dynamics in catalytic intermediates leads to the hyperpolarization of predominantly one hydrogen in alkene. PHIP enabled the detection of important HCAT-alkyne-H₂ intermediates through substantial ¹H, ¹¹B and ¹⁵N signal enhancement and allowed advanced characterization of the catalytic process.     

A note on simultaneous Diophantine approximation on planar curves

Let denote the set of simultaneously - approximable points in and denote the set of multiplicatively ψ-approximable points in . Let be a manifold in . The aim is to develop a metric theory for the sets and analogous to the classical theory in which is simply . In this note, we mainly restrict our attention to the case that is a planar curve . A complete Hausdorff dimension theory is established for the sets and . A divergent Khintchine type result is obtained for ; i.e. if a certain sum diverges then the one-dimensional Lebesgue measure on of is full. Furthermore, in the case that is a rational quadric the convergent Khintchine type result is obtained for both types of approximation. Our results for naturally generalize the dimension and Lebesgue measure statements of Beresnevich et al. (Mem AMS, 179 (846), 1–91 (2006)). Moreover, within the multiplicative framework, our results for constitute the first of their type. The research of Victor V. Beresnevich was supported by an EPSRC Grant R90727/01. Sanju L. Velani is a Royal Society University Research Fellow. For Iona and Ayesha on No. 3.     

Pilot Quality-Assurance Study of a Third-Generation Batch-Mode Clinical-Scale Automated Xenon-129 Hyperpolarizer

We present a pilot quality assurance (QA) study of a clinical-scale, automated, third-generation (GEN-3) ¹²⁹Xe hyperpolarizer employing batch-mode spin-exchange optical pumping (SEOP) with high-Xe densities (50% natural abundance Xe and 50% N₂ in ~2.6 atm total pressure sourced from Nova Gas Technologies) and rapid temperature ramping enabled by an aluminum heating jacket surrounding the 0.5 L SEOP cell. ¹²⁹Xe hyperpolarization was performed over the course of 700 gas loading cycles of the SEOP cell, simulating long-term hyperpolarized contrast agent production in a clinical lung imaging setting. High levels of ¹²⁹Xe polarization (avg. %P_Xe = 51.0% with standard deviation σ_PXe = 3.0%) were recorded with fast ¹²⁹Xe polarization build-up time constants (avg. T_b = 25.1 min with standard deviation σ_Tb = 3.1 min) across the first 500 SEOP cell refills, using moderate temperatures of 75 °C. These results demonstrate a more than 2-fold increase in build-up rate relative to previously demonstrated results in a comparable QA study on a second-generation (GEN-2) ¹²⁹Xe hyperpolarizer device, with only a minor reduction in maximum achievable %P_Xe and with greater consistency over a larger number of SEOP cell refill processes at a similar polarization lifetime duration (avg. T₁ = 82.4 min, standard deviation σ_T1 = 10.8 min). Additionally, the effects of varying SEOP jacket temperatures, distribution of Rb metal, and preparation and operation of the fluid path are quantified in the context of device installation, performance optimization and maintenance to consistently produce high ¹²⁹Xe polarization values, build-up rates (T_b as low as 6 min) and lifetimes over the course of a typical high-throughput ¹²⁹Xe polarization SEOP cell life cycle. The results presented further demonstrate the significant potential for hyperpolarized ¹²⁹Xe contrast agent in imaging and bio-sensing applications on a clinical scale.     

Bridging the Gap: From Homogeneous to Heterogeneous Parahydrogen-induced Hyperpolarization and Beyond

Demonstration of parahydrogen-induced polarization effects in hydrogenations catalyzed by heterogeneous catalysts instead of metal complexes in a homogeneous solution has opened an entirely new dimension for parahydrogen-based research, demonstrating its applicability not only for the production of catalyst-free hyperpolarized liquids and gases and long-lived non-equilibrium spin states for potential biomedical applications, but also for addressing challenges of modern fundamental and industrial catalysis including advanced mechanistic studies of catalytic reactions and operando NMR and MRI of reactors. This essay summarizes the progress achieved in this field by highlighting the research contributed to it by our colleague and friend Kirill V. Kovtunov whose scientific career ended unexpectedly and tragically at the age of 37. His role in this research was certainly crucial, further enhanced by a vast network of his contacts and collaborations at the national and international level.     

Long-Term Generation of Longitudinal Spin Order Controlled by Ammonia Ligation Enables Rapid SABRE Hyperpolarized 2D NMR

Symmetry breaking of parahydrogen using iridium catalysts converts singlet spin order into observable hyperpolarization. In this contribution, iridium catalysts are designed to exhibit asymmetry in their hydrides, regulated by in situ generation of deuterated ammonia governed by ammonium buffers. The concentrations of ammonia (N) and pyridine (P) provide a handle to generate a variety of stereo-chemically asymmetric N-heterocyclic carbene iridium complexes, ligating either [3xP], [2xP;N], [P;2xN] or [3xN] in an octahedral SABRE type configuration. The non-equivalent hydride positions, in correspondence with the ammonium buffer solutions, enables to extend singlet-triplet or mixing at high magnetic field and experimentally induce prolonged generation of non-equilibrium longitudinal two-spin order. This long-lasting magnetization can be exploited in hyperpolarized 2D-OPSY-COSY experiments providing direct structural information on the catalyst using a single contact with parahydrogen. Separately, field cycling revealed hyperpolarization properties in low-field conditions. Controlling catalyst stereochemistry by introducing small and deuterated ligands, such as deuterated ammonia, simplifies the spin-system. This is shown to unify experimental and theoretically derived field-sweep experiments for four-spin systems.     

Catalytic Hydrogenation of Trivinyl Orthoacetate: Mechanisms Elucidated by Parahydrogen Induced Polarization

Parahydrogen (pH₂) induced polarization (PHIP) is a unique method that is used in analytical chemistry to elucidate catalytic hydrogenation pathways and to increase the signal of small metabolites in MRI and NMR. PHIP is based on adding or exchanging at least one pH₂ molecule with a target molecule. Thus, the spin order available for hyperpolarization is often limited to that of one pH₂ molecule. To break this limit, we investigated the addition of multiple pH₂ molecules to one precursor. We studied the feasibility of the simultaneous hydrogenation of three arms of trivinyl orthoacetate (TVOA) intending to obtain hyperpolarized acetate. It was found that semihydrogenated TVOA underwent a fast decomposition accompanied by several minor reactions including an exchange of geminal methylene protons of a vinyl ester with pH₂. The study shows that multiple vinyl ester groups are not suitable for a fast and clean (without any side products) hydrogenation and hyperpolarization that is desired in biochemical applications.