The role of electron polarization on nuclear spin diffusion

Dynamic nuclear polarization (DNP) is capable of boosting signals in nuclear magnetic resonance by orders of magnitude by creating out-of-equilibrium nuclear spin polarization. The diffusion of nuclear spin polarization in the vicinity of paramagnetic dopants is a crucial step for DNP and remains yet not well understood. In this Letter, we show that the polarization of the electron spin controls the rate of proton spin diffusion in a DNP sample at 1.2 K and 7 T; at increasingly high electron polarization, spin diffusion vanishes. We rationalize our results using a 2 nucleus - 1 electron model and Lindblad s Master equation, which generalizes preexisting models in the literature and qualitatively accounts for the experimental observed spin diffusion dynamics.Comment: Main text: 6 pages, 3 figures Supplement: 9 pages, 4 figure

Solid-state 1H spin polarimetry by 13CH3 nuclear magnetic resonance

Abstract. Dissolution dynamic nuclear polarization is used to prepare nuclear spin polarizations approaching unity. At present, 1H polarization quantification in the solid state remains fastidious due to the requirement of measuring thermal equilibrium signals. Line shape polarimetry of solid-state nuclear magnetic resonance spectra is used to determine several useful properties regarding the spin system under investigation. In the case of highly polarized nuclear spins, such as those prepared under the conditions of dissolution dynamic nuclear polarization experiments, the absolute polarization of a particular isotopic species within the sample may be directly inferred from the characteristics of the corresponding resonance line shape. In situations where direct measurements of polarization are complicated by deleterious phenomena, indirect estimates of polarization using coupled heteronuclear spins prove informative. We present a simple analysis of the 13C spectral line shape of [2-13C]sodium acetate based on the normalized deviation of the centre of gravity of the 13C peaks, which can be used to indirectly evaluate the proton polarization of the methyl group moiety and very likely the entire sample in the case of rapid and homogeneous 1H–1H spin diffusion. For the case of positive microwave irradiation, 1H polarization was found to increase with an increasing normalized centre of gravity deviation. These results suggest that, as a dopant, [2-13C]sodium acetate could be used to indirectly gauge 1H polarizations in standard sample formulations, which is potentially advantageous for (i) samples polarized in commercial dissolution dynamic nuclear polarization devices that lack 1H radiofrequency hardware, (ii) measurements that are deleteriously influenced by radiation damping or complicated by the presence of large background signals and (iii) situations where the acquisition of a thermal equilibrium spectrum is not feasible. </jats:p

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

Direct observation of hyperpolarization breaking through the spin diffusion barrier

Dynamic nuclear polarization (DNP) is a widely used tool for overcoming the low intrinsic sensitivity of nuclear magnetic resonance spectroscopy and imaging. Its practical applicability is typically bounded, however, by the so-called 'spin diffusion barrier', which relates to the poor efficiency of polarization transfer from highly polarized nuclei close to paramagnetic centers to bulk nuclei. A quantitative assessment of this barrier has been hindered so far by the lack of general methods for studying nuclear-polarization flow in the vicinity of paramagnetic centers. Here we fill this gap and introduce a general set of experiments based on microwave gating that are readily implemented. We demonstrate the versatility of our approach in experiments conducted between 1.2 – 4.2 K in static mode and at 100 K under magic angle spinning (MAS) — conditions typical for dissolution-DNP and MAS-DNP — and for the first time directly observe the dramatic dependence of polarization flow on temperature.The data are organized in subfolders. A PDF document in the root folder summarizes the list of all experiments in the dataset with precisions on experimental parameters and remarks (README.pdf). For each subfolder, the figures of the paper which were produced using the data is the subfolder is listed. Funding provided by: European Research CouncilCrossref Funder Registry ID: http://dx.doi.org/10.13039/501100000781Award Number: 714519: HP4allFunding provided by: H2020 Marie Skłodowska-Curie ActionsCrossref Funder Registry ID: http://dx.doi.org/10.13039/100010665Award Number: 766402: ZULFFunding provided by: NSF/DMR and the State of Florida*Crossref Funder Registry ID: Award Number: 1644779Funding provided by: NSF/DMR NIH*Crossref Funder Registry ID: Award Number: S10 OD018519Funding provided by: National Institutes of HealthCrossref Funder Registry ID: http://dx.doi.org/10.13039/100000002Award Number: P41 GM122698 01Funding provided by: National Science FoundationCrossref Funder Registry ID: http://dx.doi.org/10.13039/100000001Award Number: CHE 1229170Funding provided by: NSF/DMR and the State of FloridaCrossref Funder Registry ID: Award Number: 1644779Funding provided by: NSF/DMR NIHCrossref Funder Registry ID: Award Number: S10 OD018519All data consist of NMR spectra. Data were collected using high field NMR instruments by Bruker using the software Topspin 3.5.7 and Topspin 3.6.2. They were exported to CSV files

Pulse sequence and sample formulation optimization for dipolar order mediated 1H-13C cross-polarization

We have recently demonstrated the use of contactless radiofrequency pulse sequences under dissolution-dynamic nuclear polarization conditions as an attractive way of transferring polarization from sensitive 1H spins to insensitive 13C spins with low peak radiofrequency pulse powers and energies via a reservoir of dipolar order. However, many factors remain to be investigated and optimized to enable the full potential of this polarization transfer process. We demonstrate herein the optimization of several key factors by: (i) implementing more efficient shaped radiofrequency pulses; (ii) adapting 13C spin labelling; and (iii) avoiding methyl group relaxation sinks. Experimental demonstrations are presented for the case of [1-13C]sodium acetate and other relevant molecular candidates. By employing the range of approaches set out above, polarization transfer using the dipolar order mediated cross-polarization radiofrequency pulse sequence is improved by factors approaching ∼1.65 compared with previous results. Dipolar order mediated 1H→13C polarization transfer efficiencies reaching ∼76% were achieved using significantly reduced peak radiofrequency pulse powers relative to the performance of highly sophisticated state-of-the-art cross-polarization methods, indicating 13C nuclear spin polarization levels on the order of ∼32.1% after 10 minutes of 1H DNP. The approach does not require extensive pulse sequence optimization procedures and can easily accommodate high concentrations of 13C-labelled molecules

Gaia GraL: Gaia DR2 Gravitational Lens Systems. VII. XMM-Newton Observations of Lensed Quasars

© 2022. The Author(s). Published by the American Astronomical Society. This is the accepted manuscript version of an article which has been published in final form at https://doi.org/10.3847/1538-4357/ac4476We present XMM-Newton X-ray observations of nine confirmed lensed quasars at 1 ≲ z ≲ 3 identified by the Gaia Gravitational Lens program. Eight systems are strongly detected, with 0.3-8.0 keV fluxes F 0.3-8.0 ≳ 5 ×10-14 erg cm-2 s-1. Modeling the X-ray spectra with an absorbed power law, we derive power-law photon indices and 2-10 keV luminosities for the eight detected quasars. In addition to presenting sample properties for larger quasar population studies and for use in planning for future caustic-crossing events, we also identify three quasars of interest: a quasar that shows evidence of flux variability from previous ROSAT observations, the most closely separated individual lensed sources resolved by XMM-Newton, and one of the X-ray brightest quasars known at z > 3. These sources represent the tip of the discoveries that will be enabled by SRG/eROSITA.Peer reviewe

Gaia GraL: Gaia DR2 gravitational lens systems – VIII. A radio census of lensed systems

© 2024 The Author(s). Published by Oxford University Press on behalf of Royal Astronomical Society. This is an open access article distributed under the terms of the Creative Commons Attribution License (CC BY), https://creativecommons.org/licenses/by/4.0/We present radio observations of 24 confirmed and candidate strongly lensed quasars identified by the Gaia Gravitational Lenses working group. We detect radio emission from eight systems in 5.5 and 9 GHz observations with the Australia Telescope Compact Array (ATCA), and 12 systems in 6 GHz observations with the Karl G. Jansky Very Large Array (VLA). The resolution of our ATCA observations is insufficient to resolve the radio emission into multiple lensed images, but we do detect multiple images from 11 VLA targets. We have analysed these systems using our observations in conjunction with existing optical measurements, including measuring offsets between the radio and optical positions for each image and building updated lens models. These observations significantly expand the existing sample of lensed radio quasars, suggest that most lensed systems are detectable at radio wavelengths with targeted observations, and demonstrate the feasibility of population studies with high-resolution radio imaging.Peer reviewe

Gaia GraL: Gaia DR2 Gravitational Lens Systems. VIII. A radio census of lensed systems

We present radio observations of 24 confirmed and candidate strongly lensed quasars identified by the Gaia Gravitational Lenses (GraL) working group. We detect radio emission from 8 systems in 5.5 and 9 GHz observations with the Australia Telescope Compact Array (ATCA), and 12 systems in 6 GHz observations with the Karl G. Jansky Very Large Array (VLA). The resolution of our ATCA observations is insufficient to resolve the radio emission into multiple lensed images, but we do detect multiple images from 11 VLA targets. We have analysed these systems using our observations in conjunction with existing optical measurements, including measuring offsets between the radio and optical positions, for each image and building updated lens models. These observations significantly expand the existing sample of lensed radio quasars, suggest that most lensed systems are detectable at radio wavelengths with targeted observations, and demonstrate the feasibility of population studies with high resolution radio imaging

Removing Systemic Barriers to Equity, Diversity, and Inclusion: Report of the 2019 Plant Science Research Network Workshop “Inclusivity in the Plant Sciences”

A future in which scientific discoveries are valued and trusted by the general public cannot be achieved without greater inclusion and participation of diverse communities. To envision a path towards this future, in January 2019 a diverse group of researchers, educators, students, and administrators gathered to hear and share personal perspectives on equity, diversity, and inclusion (EDI) in the plant sciences. From these broad perspectives, the group developed strategies and identified tactics to facilitate and support EDI within and beyond the plant science community. The workshop leveraged scenario planning and the richness of its participants to develop recommendations aimed at promoting systemic change at the institutional level through the actions of scientific societies, universities, and individuals and through new funding models to support research and training. While these initiatives were formulated specifically for the plant science community, they can also serve as a model to advance EDI in other disciplines. The proposed actions are thematically broad, integrating into discovery, applied and translational science, requiring and embracing multidisciplinarity, and giving voice to previously unheard perspectives. We offer a vision of barrier-free access to participation in science, and a plant science community that reflects the diversity of our rapidly changing nation, and supports and invests in the training and well-being of all its members. The relevance and robustness of our recommendations has been tested by dramatic and global events since the workshop. The time to act upon them is now