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Parahydrogen-induced polarization with a metal-free PâP biradicaloid
Metal-free H2 activations are unusual but interesting for catalytic transformations, particularly in parahydrogen-based nuclear spin hyperpolarization techniques. We demonstrate that metal-free singlet phosphorus biradicaloid, [P(Ό-NTer)]2, provides pronounced 1H and 31P hyperpolarization while activating the parahydrogen molecules. A brief analysis of the resulting NMR signals and the important kinetic parameters are presented
27 Al NMR/MRI Studies of the Transport of Granular Al 2 O 3
The NMR/MRI techniques are applicable to the studies of motion of granular solids, providing information on the velocities, effective diffusivities and correlation times of the moving particles. The studies of transport of granular solids reported to-date are based on
the detection of the 1H NMR signal of the liquid phase of liquid-containing solid materials. Yet, the solid phase of many granular solids contains magnetic nuclei, providing in principle an opportunity to study motion of such solids by directly detecting the NMR signal of the solid phase. In this paper, we demonstrate that this can be performed with the use of conventional echo pulse sequences in combination with the conventional motion encoding schemes. The detection of the 27Al NMR signal of the Al2O3 powder
was used to obtain velocity maps of the powder packed in a spinning cylinder, and to measure the velocity distribution (average propagator) for the gravity driven transport of the same powder in a vertical pipe
Ultrafast multidimensional Laplace NMR for a rapid and sensitive chemical analysis
Traditional nuclear magnetic resonance (NMR) spectroscopy relies on the versatile chemical information conveyed by spectra. To complement conventional NMR, Laplace NMR explores diffusion and relaxation phenomena to reveal details on molecular motions. Under a broad concept of ultrafast multidimensional Laplace NMR, here we introduce an ultrafast diffusion-relaxation correlation experiment enhancing the resolution and information content of corresponding 1D experiments as well as reducing the experiment time by one to two orders of magnitude or more as compared with its conventional 2D counterpart. We demonstrate that the method allows one to distinguish identical molecules in different physical environments and provides chemical resolution missing in NMR spectra. Although the sensitivity of the new method is reduced due to spatial encoding, the single-scan approach enables one to use hyperpolarized substances to boost the sensitivity by several orders of magnitude, significantly enhancing the overall sensitivity of multidimensional Laplace NMR
ParahydrogenâInduced Polarization of Amino Acids
Nuclear magnetic resonance (NMR) has become a universal method for biochemical and biomedical studies, including metabolomics, proteomics, and magnetic resonance imaging (MRI). By increasing the signal of selected molecules, the hyperpolarization of nuclear spin has expanded the reach of NMR and MRI even further (e.g. hyperpolarized solid-state NMR and metabolic imaging inâ
vivo). Parahydrogen (pHâ) offers a fast and cost-efficient way to achieve hyperpolarization, and the last decade has seen extensive advances, including the synthesis of new tracers, catalysts, and transfer methods. The portfolio of hyperpolarized molecules now includes amino acids, which are of great interest for many applications. Here, we provide an overview of the current literature and developments in the hyperpolarization of amino acids and peptides
Spontaneous N-15 Nuclear Spin Hyperpolarization in Metal-Free Activation of Parahydrogen by Molecular Tweezers
The ability of frustrated Lewis pairs (FLPs) to activate H-2 is of significant interest for metal-free catalysis. The activation of H-2 is also the key element of parahydrogen-induced polarization (PHIP), one of the nuclear spin hyper polarization techniques. It is demonstrated that o-phenylene-based ansa-aminoboranes (AABs) can produce H-1 nuclear spin hyperpolarization through a reversible interaction with parahydrogen at ambient temperatures. Heteronuclei are useful in NMR and MRI as well because they have a broad chemical shift range and long relaxation times and may act as background-free labels. We report spontaneous formation of N-15 hyperpolarization of the N-H site for a family of AABs. The process is efficient at the high magnetic field of an NMR magnet (7 T), and it provides up to 350-fold N-15 signal enhancements. Different hyperpolarization effects are observed with various AAB structures and in a broad temperature range. Spontaneous hyperpolarization, albeit an order of magnitude weaker than that for N-15, was also observed for B-11 nuclei.Peer reviewe
Possible Applications of Dissolution Dynamic Nuclear Polarization in Conjunction with Zero- to Ultralow-Field Nuclear Magnetic Resonance
The combination of a powerful and broadly applicable nuclear
hyperpolarization technique with emerging (near-)zero-field modalities offer
novel opportunities in a broad range of nuclear magnetic resonance spectroscopy
and imaging applications, including biomedical diagnostics, monitoring
catalytic reactions within metal reactors and many others. These are discussed
along with a roadmap for future developments.Comment: 12 pages, 5 figure
Low-valent homobimetallic Rh complexes: influence of ligands on the structure and the intramolecular reactivity of RhâH intermediates
Supporting two metal binding sites by a tailored polydentate trop-based (trop - 5H-dibenzo[a,d] cyclohepten-5-yl) ligand yields highly unsymmetric homobimetallic rhodium(I) complexes. Their reaction with hydrogen rapidly forms Rh hydrides that undergo an intramolecular semihydrogenation of two CâĄC bonds of the trop ligand. This reaction is chemoselective and converts CâĄC bonds to a bridging carbene and an olefinic ligand in the first and the second semihydrogenation steps, respectively. Stabilization by a bridging diphosphine ligand allows characterization of a Rh hydride species by advanced NMR techniques and may provide insight into possible elementary steps of Hâ activation by interfacial sites of heterogeneous Rh/C catalysts
Modeling Ligand Exchange Kinetics in Iridium Complexes Catalyzing SABRE Nuclear Spin Hyperpolarization
Large signal enhancements can be obtained for NMR analytes using the process of nuclear spin hyperpolarization. Organometallic complexes that bind parahydrogen can themselves become hyperpolarized. Moreover, if parahydrogen and a to-be-hyperpolarized analyte undergo chemical exchange with the organometallic complex it is possible to catalytically sensitize the detection of the analyte via hyperpolarization transfer through spin-spin coupling in this organometallic complex. This process is called Signal Amplification By Reversible Exchange (SABRE). Signal intensity gains of several orders of magnitude can thus be created for various compounds in seconds. The chemical exchange processes play a defining role in controlling the efficiency of SABRE because the lifetime of the complex must match the spin-spin couplings. Here, we show how analyte dissociation rates in the key model substrates pyridine (the simplest six-membered heterocycle), 4-aminopyridine (a drug), and nicotinamide (an essential vitamin biomolecule) can be examined. This is achieved for the most widely employed SABRE motif that is based on IrIMes-derived catalysts by 1H 1D and 2D exchange NMR spectroscopy techniques. Several kinetic models are evaluated for their accuracy and simplicity. By incorporating variable temperature analysis, the data yields key enthalpies and entropies of activation that are critical for understanding the underlying SABRE catalyst properties and subsequently optimizing behavior through rational chemical design. While several studies of chemical exchange in SABRE have been reported, this work also aims to establish a toolkit on how to quantify chemical exchange in SABRE and ensure that data can be compared reliably.(Figure presented.
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