Abstract Signal Amplification By Reversible Exchange in SHield Enabled Alignment Transfer (SABRE‐SHEATH) is investigated to achieve rapid hyperpolarization of13C1spins of [1‐13C]pyruvate, using parahydrogen as the source of nuclear spin order. Pyruvate exchange with an iridium polarization transfer complex can be modulated via a sensitive interplay between temperature and co‐ligation of DMSO and H2O. Order‐unity13C (>50 %) polarization of catalyst‐bound [1‐13C]pyruvate is achieved in less than 30 s by restricting the chemical exchange of [1‐13C]pyruvate at lower temperatures. On the catalyst bound pyruvate, 39 % polarization is measured using a 1.4 T NMR spectrometer, and extrapolated to >50 % at the end of build‐up in situ. The highest measured polarization of a 30‐mM pyruvate sample, including free and bound pyruvate is 13 % when using 20 mM DMSO and 0.5 M water in CD3OD. Efficient13C polarization is also enabled by favorable relaxation dynamics in sub‐microtesla magnetic fields, as indicated by fast polarization buildup rates compared to theT1spin‐relaxation rates (e. g., ∼0.2 s−1versus ∼0.1 s−1, respectively, for a 6 mM catalyst‐[1‐13C]pyruvate sample). Finally, the catalyst‐bound hyperpolarized [1‐13C]pyruvate can be released rapidly by cycling the temperature and/or by optimizing the amount of water, paving the way to future biomedical applications of hyperpolarized [1‐13C]pyruvate produced via comparatively fast and simple SABRE‐SHEATH‐based approaches.
more »
« less
Twistors, Self-Duality, and Spinc Structures
The fact that every compact oriented 4-manifold admits spinc structures was proved long ago by Hirzebruch and Hopf. However, the usual proof is neither direct nor transparent. This article gives a new proof using twistor spaces that is simpler and more geometric. After using these ideas to clarify various aspects of four-dimensional geometry, we then explain how related ideas can be used to understand both spin and spinc structures in any dimension.
more »
« less
- Award ID(s):
- 1906267
- PAR ID:
- 10337280
- Date Published:
- Journal Name:
- Symmetry, Integrability and Geometry: Methods and Applications
- ISSN:
- 1815-0659
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
More Like this
-
-
Abstract 19F magnetic resonance (MR) based detection coupled with well‐designed inorganic systems shows promise in biological investigations. Two proof‐of‐concept inorganic probes that exploit a novel mechanism for19F MR sensing based on converting from low‐spin (S=0) to high‐spin (S=1) Ni2+are reported. Activation of diamagneticNiL1andNiL2by light or β‐galactosidase, respectively, converts them into paramagneticNiL0, which displays a single19F NMR peak shifted by >35 ppm with accelerated relaxation rates. This spin‐state switch is effective for sensing light or enzyme expression in live cells using19F MR spectroscopy and imaging that differentiate signals based on chemical shift and relaxation times. This general inorganic scaffold has potential for developing agents that can sense analytes ranging from ions to enzymes, opening up diverse possibilities for19F MR based biosensing.more » « less
-
Abstract An in-beam gamma-ray spectroscopy study of the even–even nucleus92Mo has been carried out using the30Si +65Cu,18O +80Se reactions at beam energies of 120 and 99 MeV, respectively. Angular distribution from the oriented state ratio (RADO) and linear polarization (Δasym) measurements have fixed most of the tentatively assigned spin-parity of the high-energy levels. A large-scale shell-model calculation using the GWBXG interaction has been carried out to understand the configuration and structure of both positive and negative parity states up to the highest observed spin. The high-spin states primarily originate from the coupling of excited proton- and neutron-core structures in an almost stretched manner. The systematics of the energy required to form a neutron particle-hole pair excitation,νg9/2→νd5/2, is discussed. The lifetimes of a few high-spin states have been measured using the Doppler shift attenuation method. Additionally, a qualitative argument is proposed to explain the comparatively strong E1 transition feeding the 7310.9 keV level.more » « less
-
Abstract We introduce the heterocumulene ligand [(Ad)NCC(tBu)]−(Ad=1‐adamantyl (C10H15),tBu=tert‐butyl, (C4H9)), which can adopt two forms, the azaalleneyl and ynamide. This ligand platform can undergo a reversible chelotropic shift using Brønsted acid‐base chemistry, which promotes an unprecedented spin‐state change of the [VIII] ion. These unique scaffolds are prepared via addition of 1‐adamantyl isonitrile (C≡NAd) across the alkylidyne in complexes [(BDI)V≡CtBu(OTf)] (A) (BDI−=ArNC(CH3)CHC(CH3)NAr), Ar=2,6‐iPr2C6H3) and [(dBDI)V≡CtBu(OEt2)] (B) (dBDI2−=ArNC(CH3)CHC(CH2)NAr). ComplexAreacts with C≡NAd, to generate the high‐spin [VIII] complex with a κ1‐N‐ynamide ligand, [(BDI)V{κ1‐N‐(Ad)NCC(tBu)}(OTf)] (1). Conversely,Breacts with C≡NAd to generate a low‐spin [VIII] diamagnetic complex having a chelated κ2‐C,N‐azaalleneyl ligand, [(dBDI)V{κ2‐N,C‐(Ad)NCC(tBu)}] (2). Theoretical studies have been applied to better understand the mechanism of formation of2and the electronic reconfiguration upon structural rearrangement by the alteration of ligand denticity between1and2.more » « less
-
Abstract We report the synthesis and spectroscopic characterization of a series of iron‐carbene complexes in redox states {Fe=C(H)Ar}10–11. Pulse EPR studies of the1,2H and13C isotopologues of {Fe=C(H)Ar}11reveal the high covalency of the Fe–carbene bonding, leading to a more even spin distribution than commonly observed for reduced Fischer carbenes.more » « less
An official website of the United States government

