Chemically Resolved Nuclear Magnetic Resonance Spectroscopy by Longitudinal Magnetization Detection with a Diamond Magnetometer
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Smits, Janis [University of New Mexico, Center for↗
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Correlating Protein Dynamics and Catalytic Activity of a Model Hydrogenase Using Paramagnetic and Biological Nuclear Magnetic Resonance Spectroscopy
Rational catalyst design remains a significant challenge, with electronic structure, steric, and electrostatic effects known to contribute to activity. Recently, dynamics has been recognized as another factor that impacts catalysis, though identifying and predicting these effects has remained out of reach. Nickel-substituted rubredoxin (NiRd), a protein-based mimic of a hydrogenase enzyme, serves as a model catalytic system in which dynamics can be systematically investigated with respect to activity. While over 30 secondary-sphere mutants of NiRd have been shown to be catalytically active, no significant correlation was observed between the rates and catalytic overpotential or electronic structure, prompting questions about the protein-derived factors that modulate activity. Here, in this work, NMR spectroscopy was used to investigate the roles of substrate accessibility, protein dynamics, and protein stability in controlling catalysis. Significant paramagnetic effects from the nickel center (S = 1) isolate the methylene proton resonances of the metal-coordinating cysteine residues. The sensitivity of resonance positions and linewidths to local environment offers an opportunity to study dynamical molecular changes around the metal center with high resolution. Machine learning algorithms were employed to identify correlations between the catalytic activity and the paramagnetic NMR spectra. These analyses revealed spectroscopic features of specific cysteine protons that report on catalytic overpotential and increased turnover rates, which are further supported by the results obtained using high-field NMR techniques. Collectively, these studies indicate the potential for multifrequency NMR techniques to resolve key contributors to catalytic activity and highlight the importance of local and outer-sphere dynamics.
Protein Engineering↗
In-beam spectroscopy reveals competing nuclear shapes in the rare isotope 62 Cr
In recent decades, rareisotope facilities have enabled the study of short-lived, neutron-rich nuclei. Their measured properties indicate that shell structure changes in the regime of unbalanced neutron-to-proton ratios compared to that of stable nuclei. In the so-called islands of inversion in the nuclear chart – around the neutron-rich nuclei 32 Mg, 42 Si and 64 Cr, for example – the textbook shell-model picture predicts the presence of spherical shapes due to the respective magic neutron numbers of 20, 28, and 40 of these nuclei. However, nuclei in these regions turn out to be deformed in their ground states. Another hallmark of these islands is shape coexistence, where a nucleus assumes different shapes with excitation energy. Furthermore, we present evidence for this phenomenon from the observation of an excited 0 + state in 62 Cr, two neutrons away from the heart of the island of inversion around neutron number N = 40. We use large-scale shell-model calculations to interpret the results and report extrapolations for the doubly-magic nucleus 60 Ca.
73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
Deciphering spin-parity assignments of nuclear levels
Spin-parity assignments of nuclear levels are critical for understanding nuclear structure and reactions. However, inconsistent notation conventions and ambiguous reporting in research papers often lead to confusion and misinterpretations. Here, this paper examines the policies of the Evaluated Nuclear Structure Data File (ENSDF) and the evaluations by Endt and collaborators, highlighting key differences in their approaches to spin-parity notation. Sources of confusion are identified, including ambiguous use of strong and weak arguments and the conflation of new experimental results with prior constraints. Recommendations are provided to improve clarity and consistency in reporting spin-parity assignments, emphasizing the need for explicit notation conventions, clear differentiation of argument strengths, community education, and separate reporting of new findings. These steps aim to enhance the accuracy and utility of nuclear data for both researchers and evaluators.
Experimental Nuclear Physics↗
Optimized High-Sensitivity Nanoscale Nuclear Quadrupolar Resonance Spectroscopy of 11B in hBN through NV ensembles in Diamond.
Abstract not provided.
Henshaw, Jacob↗
Progress Towards Microcalorimeter Gamma Spectroscopy Analysis for Nuclear Fuel Separations
The High Efficiency and Resolution Microcalorimeter Spectrometer, 400 pixels (HERMES-400) is an ultra-high resolution gamma-ray spectrometer at Idaho National Laboratory’s Materials and Fuels Complex. HERMES-400 is intended to enable precise nondestructive analysis of advanced fuel cycle materials. Key upgrades and repairs of the instrument were performed this year to improve performance. First, the fourth and final microcalorimeter detector module was installed, meeting the milestone for its integration into the system. Operation with all four modules enables higher detector efficiency than any previous microcalorimeter gamma-ray system. Second, a thinner magnetic shield was installed. This shields the sensitive microcalorimeter pixels from stray magnetic fields while allowing transmission of lower-energy gamma rays, which are important to isotopic analysis. Finally, the cryostat, which provides cooling of the modules to their operating temperature, was found to have a helium coolant leak, which was repaired. HERMES-400 is in a stable state to perform repeated, long-term gamma-ray measurements with good detector efficiency and energy resolution. In FY25, irradiated TRISO fuel and salts from advanced electrochemical recycling techniques are candidates for microcalorimeter measurements. A final upgrade of the magnetic shielding and vibration damping of the system is also planned to maximize the system performance.
46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗
Analytical development work on bis- /phenoxyphenyl/ ethers, mix 4P3E
Gas chromatography and infrared and nuclear magnetic resonance spectroscopy procedures for characterizing bis phenoxyphenyl ethers
INFRARED SPECTROSCOPY↗
Resolving Chemical and Spatial Heterogeneities at Complex Electrochemical Interfaces in Li-Ion Batteries
The high specific capacities of Ni-rich transition metal oxides have garnered immense interest for improving the energy density of Li-ion batteries (LIBs). Despite the potential of these materials, Ni-rich cathodes suffer from interfacial instabilities that lead to crystallographic rearrangement of the active material surface as well as the formation of a cathode electrolyte interphase (CEI) layer on the composite during electrochemical cycling. While changes in crystallographic structure can be detected with diffraction-based methods, probing the chemistry of the disordered, heterogeneous CEI layer is challenging. In this work, we use a combination of ex situ solid-state nuclear magnetic resonance (SSNMR) spectroscopy and X-ray photoemission electron microscopy (XPEEM) to provide chemical and spatial information, on the nanometer length scale, on the CEI deposited on LiNi 0.8 Mn 0.1 Co 0.1 O 2 (NMC811) composite cathode films. XPEEM elemental maps offer insight into the lateral arrangement of the electrolyte decomposition products that comprise the CEI and paramagnetic interactions (assessed with electron paramagnetic resonance (EPR) and relaxation measurements) in 13 C SSNMR provide information on the radial arrangement of the CEI from the NMC811 particles outward. Using this approach, here we find that LiF, Li 2 CO 3 , and carboxy-containing structures are directly appended to NMC811 active particles, whereas soluble species detected during in situ 1 H and 19 F solution NMR experiments (e.g., alkyl carbonates, HF, and vinyl compounds) are randomly deposited on the composite surface. We show that the combined approach of ex situ SSNMR and XPEEM, in conjunction with in situ solution NMR, allows spatially-resolved, molecular-level characterization of paramagnetic surfaces and new insights into electrolyte oxidation mechanisms in porous electrode films.
36 MATERIALS SCIENCE↗
A novel method for quantifying irradiation damage in nuclear graphite using Raman spectroscopy
Raman spectroscopy has long been used in studying irradiation damage in carbon/graphite materials. It is however unclear if the measurements from different types of materials are directly comparable. Further, decoupling the contribution from irradiation temperature and fluence to the total damage in nuclear graphite possessing irradiation damage gradient is currently not readily feasible as it requires a complete set of test reactor irradiation experiments over the relevant temperature and fluence range. A novel methodology has therefore been proposed and developed to quantify total irradiation damage evolution at crystal level based on graphite Raman G-band position shift. Specifically, G-band positions derived from a large number of spectra collected from the fractured surface of microfine-grained POCO ZXF-5Q graphite possessing proton irradiation damage gradient were plotted with open literature Raman data on HOPG, BEPO (AXGP graphite), PCEA and IG-110 graphite as a function of dpa. The total damage level within 2σ beam radius in this POCO graphite was estimated to be equivalent to ~2–5 dpa at ~350–370 °C. Derived G-band positions were then mapped to the three-stage amorphization trajectory model indicating beam centre area has entered the second stage, i.e., transitioning from nanocrystalline graphite into amorphous carbon. G-band position relative shift (ΔG) curve with a ‘turn-around’ peak as a function of total damage can be used for in-service lifetime prediction. Importantly, the developed methodology has the potential to ‘unify’ total damage levels across different grades of nuclear graphite caused by ion, neutron and proton irradiation at different temperatures.
46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗
Gamma-ray Spectroscopy in Low-Power Nuclear Research Reactors
Gamma-ray spectroscopy is an effective technique for radioactive material characterization, routine inventory verification, nuclear safeguards, health physics, and source search scenarios. Gamma-ray spectrometers typically cannot be operated in the immediate vicinity of nuclear reactors due to their high flux fields and their resulting inability to resolve individual pulses. Low-power reactor facilities offer the possibility to study reactor gamma-ray fields, a domain of experiments hitherto poorly explored. In this work, we present gamma-ray spectroscopy experiments performed with various detectors in two reactors: The EPFL zero-power research reactor CROCUS, and the neutron beam facility at the Ohio State University Research Reactor (OSURR). We employed inorganic scintillators (CeBr3), organic scintillators (trans-stilbene and organic glass), and high-purity germanium semiconductors (HPGe) to cover a range of typical—and new—instruments used in gamma-ray spectroscopy. The aim of this study is to provide a guideline for reactor users regarding detector performance, observed responses, and therefore available information in the reactor photon fields up to 2 MeV. The results indicate several future prospects, such as the online (at criticality) monitoring of fission products (like Xe, I, and La), dual-particle sensitive experiments, and code validation opportunities.
Pakari, Oskari V. (ORCID:0000000337048190)↗
CHICOX, a heavy-ion detection system for GRETA
The CHICOX detection system is an array of position sensitive parallel plate avalanche counters used for heavy ion detection in in-beam particle-gamma coincidence experiments. CHICOX, an upgrade of the CHICO2 array, is geometrically compatible with the GRETINA and GRETA gamma-ray arrays and provides an angular resolution sufficient to utilize the excellent position resolution of GRETINA/GRETA. CHICOX was successfully commissioned and fielded as an auxiliary detector to GRETINA in a campaign of stable-beam Coulomb excitation experiments at the ATLAS facility of Argonne National Laboratory. We report here on the design and in-beam performance of the CHICOX array.
46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗
A new metric to control nucleation and grain size distribution in hybrid organic–inorganic perovskites by tuning the dielectric constant of the antisolvent
In perovskite research, there is a widely exploited but poorly explained phenomenon in which the addition of “antisolvents (ATS)” to precursor solutions results in higher-quality films. We explain the mechanism and driving force underlying an antisolvent-driven solvent extraction process. Density functional theory calculations uncover the defining effects of antisolvent choice on the extent of complexation between a lead salt and a methylammonium cation in solution. We experimentally validate the computational results using ultraviolet-visible spectroscopy and 207 Pb nuclear magnetic spectroscopy of methylammonium lead iodide solutions, containing both a processing solvent and an antisolvent. Furthermore, we uncover, and subsequently identify, the appearance of new species in solution as a result of the addition of the antisolvent. Furthermore, we observe that the choice of antisolvent has a substantial effect on the nature of the complexation of the methylammonium lead iodide (MAPbI 3 ) precursor species, whose origin we explain at an atomic level; specifically, the lower the dielectric of the antisolvent, the stronger the intermolecular binding energy between methylammonium cation (MA + ) cation and PbI 3 - plumbate, independent of the solvent or antisolvent interaction with the lead salt. Thin films were characterized using scanning electron microscopy; images of the films show how the addition of an antisolvent influences and, importantly, can be used to alter thin-film grain size. Grain size and distribution in thin films is reflected by the choice of antisolvent, promoting slower nucleation rates, a lower nucleation density, and hence larger final grain size.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Laser Excitation of the Th-229 Nucleus
The 8.4 eV nuclear isomer state in Th-229 is resonantly excited in Th-doped CaF 2 crystals using a tabletop tunable laser system. A resonance fluorescence signal is observed in two crystals with different Th-229 dopant concentrations, while it is absent in a control experiment using Th-232. The nuclear resonance for the Th 4 + ions in Th: CaF 2 is measured at the wavelength 148.3821(5) nm, frequency 2020.409(7) THz, and the fluorescence lifetime in the crystal is 630(15) s, corresponding to an isomer half-life of 1740(50) s for a nucleus isolated in vacuum. These results pave the way toward Th-229 nuclear laser spectroscopy and realizing optical nuclear clocks. Published by the American Physical Society 2024
Physics↗
Half-life determination of heavy ions in a storage ring considering feeding and depleting background processes
Heavy-ion storage rings have relatively large momentum acceptance which allows for multiple ion species to circulate at the same time. This needs to be considered in radioactive decay measurements of highly charged ions, where atomic charge exchange reactions can significantly alter the intensities of parent and daughter ions. In this study, we investigate this effect using the decay curves of ion numbers in the recent 205 Tl 81+ bound-state beta decay experiment conducted using the Experimental Storage Ring at GSI Darmstadt. To understand the intricate dynamics of ion numbers, we present a set of differential equations that account for various atomic and nuclear reaction processes—bound state beta decay, atomic electron recombination and capture, and electron ionization. By incorporating appropriate boundary conditions, we develop a set of differential equations that accurately simulate the decay curves of various simultaneously stored ions in the storage ring: 205 Tl 81+ , 205 Pb 81+ , 205 Pb 82+ , 200 Hg 79+ , and 200 Hg 80+ . Through a quantitative comparison between simulations and experimental data, we provide insights into the detailed reaction mechanisms governing stored heavy ions within the storage ring. Our approach effectively models charge-changing processes, reduces the complexity of the experimental setup, and provides a simpler method for measuring the decay half-lives of highly charged ions in storage rings.
73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
Structural and spectroscopic characterization of an einsteinium complex
The transplutonium elements (atomic numbers 95–103) are a group of metals that lie at the edge of the periodic table. As a result, the patterns and trends used to predict and control the physics and chemistry for transition metals, main-group elements and lanthanides are less applicable to transplutonium elements. Furthermore, understanding the properties of these heavy elements has been restricted by their scarcity and radioactivity. This is especially true for einsteinium (Es), the heaviest element on the periodic table that can currently be generated in quantities sufficient to enable classical macroscale studies. Here we characterize a coordination complex of einsteinium, using less than 200 nanograms of 254 Es (with half-life of 275.7(5) days), with an organic hydroxypyridinone-based chelating ligand. X-ray absorption spectroscopic and structural studies are used to determine the energy of the L 3 -edge and a bond distance of einsteinium. Photophysical measurements show antenna sensitization of EsIII luminescence; they also reveal a hypsochromic shift on metal complexation, which had not previously been observed in lower-atomic-number actinide elements. Here, these findings are indicative of an intermediate spin–orbit coupling scheme in which j–j coupling (whereby single-electron orbital angular momentum and spin are first coupled to form a total angular momentum, j) prevails over Russell–Saunders coupling. Together with previous actinide complexation studies, our results highlight the need to continue studying the unusual behaviour of the actinide elements, especially those that are scarce and short-lived.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Phosphate‐functionalized Zirconium Metal–Organic Frameworks for Enhancing Lithium–Sulfur Battery Cycling
Abstract Lithium–sulfur batteries are promising candidates for next‐generation energy storage devices due to their outstanding theoretical energy density. However, they suffer from low sulfur utilization and poor cyclability, greatly limiting their practical implementation. Herein, we adopted a phosphate‐functionalized zirconium metal–organic framework (Zr‐MOF) as a sulfur host. With their porous structure, remarkable electrochemical stability, and synthetic versatility, Zr‐MOFs present great potential in preventing soluble polysulfides from leaching. Phosphate groups were introduced to the framework post‐synthetically since they have shown a strong affinity towards lithium polysulfides and an ability to facilitate Li ion transport. The successful incorporation of phosphate in MOF‐808 was demonstrated by a series of techniques including infrared spectroscopy, solid‐state nuclear magnetic resonance spectroscopy, and X‐ray pair distribution function analysis. When employed in batteries, phosphate‐functionalized Zr‐MOF (MOF‐808‐PO4) exhibits significantly enhanced sulfur utilization and ion diffusion compared to the parent framework, leading to higher capacity and rate capability. The improved capacity retention and inhibited self‐discharge rate also demonstrate effective polysulfide encapsulation utilizing MOF‐808‐PO4. Furthermore, we explored their potential towards high‐density batteries by examining the cycling performance at various sulfur loadings. Our approach to correlate structure with function using hybrid inorganic–organic materials offers new chemical design strategies for advancing battery materials.
Liu, Bingqian↗
Ionic Pairs-Engineered Fluorinated Covalent Organic Frameworks Toward Direct Air Capture of CO 2
The covalent organic frameworks (COFs) possessing high crystallinity and capability to capture low-concentration CO 2 (400 ppm) from air are still underdeveloped. The challenge lies in simultaneously incorporating high-density active sites for CO 2 insertion and maintaining the ordered structure. Herein, a structure engineering approach is developed to afford an ionic pair-functionalized crystalline and stable fluorinated COF (F-COF) skeleton. The ordered structure of the F-COF is well maintained after the integration of abundant basic fluorinated alcoholate anions, as revealed by synchrotron X-ray scattering experiments. The breakthrough test demonstrates its attractive performance in capturing (400 ppm) CO 2 from gas mixtures via O$-$C bond formation, as indicated by the in situ spectroscopy and operando nuclear magnetic resonance spectroscopy using 13 C-labeled CO 2 sources. Both theoretical and experimental thermodynamic studies reveal the reaction enthalpy of ≈-40 kJ mol -1 between CO 2 and the COF scaffolds. This implies weaker interaction strength compared with state-of-the-art amine-derived sorbents, thus allowing complete CO 2 release with less energy input. The structure evolution study from synchrotron X-ray scattering and small-angle neutron scattering confirms the well-maintained crystalline patterns after CO 2 insertion. In conclusion, the as-developed proof-of-concept approach provides guidance on anchoring binding sites for direct air capture (DAC) of CO 2 in crystalline scaffolds.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Localized and Collective Dynamics in Liquid-like Polyethylenimine-Based Nanoparticle Organic Hybrid Materials
In this work, broadband dielectric spectroscopy, rheology, and nuclear magnetic resonance spectroscopy are employed to study molecular dynamics in a nanoparticle organic hybrid materials(NOHMs)system comprising 20 wt% silica nanoparticles ionically-bonded to a polyethylenimine canopy. By comparing the neat polymer (used as a canopy) to the derivative NOHMs, we find that timescales characterizing segmental dynamics in the NOHM are identical to those for the neat polymer. Detailed analysis of the carbon-spin lattice relaxation times yields mechanistic insights into localized and collective dynamics, in quantitative agreement with dielectric results. Interestingly, the NOHMs retain liquid-like characteristics unlike conventional polymer nanocomposites but exhibit higher viscosity due to additional contributions from tethered polymer chains, and mesoscopic structuring. These findings demonstrate the potential of achieving unique and desired material properties via NOHMs by an informed choice of the canopy material.
36 MATERIALS SCIENCE↗