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At least 1,585 records · Page 88

Increased localization of Majorana modes in antiferromagnetic chains on superconductors

Magnet-superconductor hybrid (MSH) systems are a key platform for custom-designed topological superconductors. Ideally, the ends of a one-dimensional MSH structure will host Majorana zero-modes (MZMs), the fundamental unit of topological quantum computing. However, some experiments with ferromagnetic (FM) chains show a more complicated picture. Due to tiny gap sizes and hence long coherence lengths, MZMs might hybridize and lose their topological protection. Recent experiments on a niobium surface have shown that both FM and antiferromagnetic (AFM) chains may be engineered, with the magnetic order depending on the crystallographic direction of the chain. While FM chains are well understood, AFM chains are less so. Here, we study two models inspired by the niobium surface: A minimal model to elucidate the general topological properties of AFM chains and an extended model to more closely simulate a real system by mimicking the proximity effect. Here, we find that, in general, for AFM chains, the topological gap is larger than for FM ones, and thus, coherence lengths are shorter for AFM chains, yielding more pronounced localization of MZMs in these chains. While for some parameters AFM chains may be topologically trivial, we find in these cases that adding an adjacent chain can result in a nontrivial system, with a single MZM at each chain end.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Elucidating the Morphological Instability Mechanisms During Electrodeposition of Active Metals

The primary aim of this investigation is to elucidate the mechanisms by which a group of metals pertinent to battery technology exhibit unstable growth morphology during electrodeposition, which are crucial for the operational efficacy of batteries. The metals under consideration include alkali metals alongside zinc, all of which are characterized by high atomic mobility and reactivity with the electrolytes employed in battery systems. These materials represent promising electrode candidates for next-generation rechargeable batteries that are anticipated to deliver significantly enhanced energy density at a reduced cost. Nevertheless, the widespread occurrence of distinctly non-uniform morphologies, exemplified by the emergence of filamentous and moss-like structures, constitutes a significant impediment to their effective utilization, as it leads to accelerated capacity degradation and potential internal short circuits. This study addresses a critical question that has thus far garnered limited attention: Does the residual stress induced by the plating process play an instrumental role in inducing the morphological instability? Utilizing zinc as the primary model system, this project will be executed through three interconnected tasks: (1) the quantification of the relationship between plating stress and electroplating morphologies, (2) the three-dimensional imaging of the microstructure of the mossy structure at the nanoscale, and (3) the development of a mesoscale electroplating model to interpret empirical findings and generate additional predictive insights.

25 ENERGY STORAGE↗

An extended motif in the SARS-CoV-2 spike modulates binding and release of host coatomer in retrograde trafficking

β-Coronaviruses such as SARS-CoV-2 hijack coatomer protein-I (COPI) for spike protein retrograde trafficking to the progeny assembly site in endoplasmic reticulum-Golgi intermediate compartment (ERGIC). However, limited residue-level details are available into how the spike interacts with COPI. Here we identify an extended COPI binding motif in the spike that encompasses the canonical K-x-H dibasic sequence. This motif demonstrates selectivity for αCOPI subunit. Guided by an in silico analysis of dibasic motifs in the human proteome, we employ mutagenesis and binding assays to show that the spike motif terminal residues are critical modulators of complex dissociation, which is essential for spike release in ERGIC. αCOPI residues critical for spike motif binding are elucidated by mutagenesis and crystallography and found to be conserved in the zoonotic reservoirs, bats, pangolins, camels, and in humans. Collectively, our investigation on the spike motif identifies key COPI binding determinants with implications for retrograde trafficking.

59 BASIC BIOLOGICAL SCIENCES↗

Unraveling the Nature of Excellent Potassium Storage in Small-Molecule Se@Peapod-Like N-Doped Carbon Nanofibers

The potassium-selenium (K-Se) battery is considered as an alternative solution for stationary energy storage because of abundant resource of K. However, the detailed mechanism of the energy storage process is yet to be unraveled. In this work, the findings in probing the working mechanism of the K-ion storage in Se cathode are reported using both experimental and computational approaches. A flexible K-Se battery is prepared by employing the small-molecule Se embedded in freestanding N -doped porous carbon nanofibers thin film (Se@NPCFs) as cathode. The reaction mechanisms are elucidated by identifying the existence of short-chain molecular Se encapsulated inside the microporous host, which transforms to K 2 Se by a two-step conversion reaction via an "all-solid-state" electrochemical process in the carbonate electrolyte system. Through the whole reaction, the generation of polyselenides (K 2 Se n , 3 ≤ n ≤ 8) is effectively suppressed by electrochemical reaction dominated by Se-2 molecules, thus significantly enhancing the utilization of Se and effecting the voltage platform of the K-Se battery. This work offers a practical pathway to optimize the K-Se battery performance through structure engineering and manipulation of selenium chemistry for the formation of selective species and reveal its internal reaction mechanism in the carbonate electrolyte.

25 ENERGY STORAGE↗

Theoretical Modeling of Electrochemical Proton-Coupled Electron Transfer

Proton-coupled electron transfer (PCET) plays an essential role in a wide range of electrocatalytic processes. Here, a vast array of theoretical and computational methods have been developed to study electrochemical PCET. These methods can be used to calculate redox potentials and pKa values for molecular electrocatalysts, proton-coupled redox potentials and bond dissociation free energies for PCET at metal and semiconductor interfaces, and reorganization energies associated with electrochemical PCET. Periodic density functional theory can also be used to compute PCET activation energies and perform molecular dynamics simulations of electrochemical interfaces. Various approaches for maintaining a constant electrode potential in electronic structure calculations and modeling complex interactions in the electric double layer (EDL) have been developed. Theoretical formulations for both homogeneous and heterogeneous electrochemical PCET spanning the adiabatic, nonadiabatic, and solvent-controlled regimes have been developed and provide analytical expressions for the rate constants and current densities as functions of applied potential. The quantum mechanical treatment of the proton and inclusion of excited vibronic states have been shown to be critical for describing experimental data, such as Tafel slopes and potential dependent kinetic isotope effects. The calculated rate constants can be used as input to microkinetic models and voltammogram simulations to elucidate complex electrocatalytic processes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Metal–Metal Bonding in Actinide Dimers: U 2 and U 2 –

Understanding direct metal–metal bonding between actinide atoms has been an elusive goal in chemistry for years. Here we report for the first time the anion photoelectron spectrum of U 2 – . The threshold of the lowest electron binding energy (EBE) spectral band occurs at 1.0 eV, which corresponds to the electron affinity (EA) of U 2 , whereas the vertical detachment energy of U 2 – is found at EBE ~ 1.2 eV. Electronic structure calculations on U 2 and U 2 – were carried out with state-of-the-art theoretical methods. The computed values of EA(U 2 ) and EA(U) and the difference between the computed dissociation energies of U 2 and U 2 – are found to be internally consistent and consistent with experiment. Analysis of the bonds in U 2 and U 2 – shows that while U 2 has a formal quintuple bond, U 2 – has a quadruple bond, even if the effective bond orders differ only by 0.5 unit instead of one unit. Furthermore, the resulting experimental-computational synergy elucidates the nature of metal–metal bonding in U 2 and U 2 – .

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Meterwave observations of a coronal hole

Meter-wave maps are presented showing a coronal hole at 30.9, 50.0, and 73.8 MHz using the Clark Lake Radioheliograph in October 1984. The coronal hole seen against the disk at all three frequencies shows interesting similarities to, and significant differences from its optical signatures in HeI lambda10830 spectroheliograms. The 73.8 MHz coronal hole, when seen near disk center, appears to coincide with the HeI footprint of the hole. At the lower frequencies, the emission comes from higher levels of the corona, and the hole appears to be displaced, probably due to the non-radial structure of the coronal hole. The contrast of the hole relative to the quiet Sun is much greater than reported previously for a coronal hole observed at 80 MHz. The higher contrast is certainly real, due to the superior dynamic range, sensitivity, and calibration of the Clark Lake instrument. Using a coronal hole model, the electron density is derived from radio observations of the brightness temperature. A very large discrepancy is found between the derived density and that determined from Skylab EUV observations of coronal holes. This discrepancy suggests that much of the physics of coronal holes has yet to be elucidated.

Wang, Z.↗

The formation and evolution of Alpha and Tellus tesserae on Venus

Although tesserae comprise at approximately 10 percent of the surface of Venus, the nature of their formation and evolution is not well understood. One important clue to elucidate this problem is tessera boundaries which are of two types: type 1 are generally embayed by plains; type 2 boundaries are characterized by being linear at the hundred kilometer scale and often associated with steep scarps or tectonic features. Previous study of a distinctive type 2 boundary at Alpha Regio was pursued in order to characterize and assess the implications for this style in general. A model of gravitational relaxation of the tessera block was presented to explain the specific style of type 2 feature seen at western Alpha; however, this model cannot account for the full range of interior structures of Alpha, namely widespread compressional features overprinted by extensional features and volcanism. In order to explain the features of Alpha, we have considered a three-stage model involving (1) mantle downwelling and compression of the lithosphere, (2) delamination of the thickened tessera root, and (3) gravitational relaxation and extension of the tessera plateau. We compare this to the characteristics of Tellus Regio in order to test its broader application.

Gilmore, M. S.↗

Promoting Atomically Dispersed MnN 4 Sites via Sulfur Doping for Oxygen Reduction: Unveiling Intrinsic Activity and Degradation in Fuel Cells

Carbon supported and nitrogen coordinated single Mn site catalysts (Mn-N-C) catalysts are the most desirable platinum group metal (PGM)-free cathode catalysts for proton exchange membrane fuel cells (PEMFCs) due to their insignificant Fenton reactions (vs. Fe), earth abundances (vs. Co) and encouraging activity and stability. However, current Mn-N-C catalysts suffer from high over-potential due to low intrinsic activity and less dense MnN 4 sites. Herein, we present sulfur-doped Mn-N-C catalyst (Mn-N-C-S) synthesized through an effective adsorption-pyrolysis process. Using electron microscopy and X-ray absorption spectroscopy (XAS) techniques, we verify the uniform dispersion of MnN 4 sites and confirm the effect of S doping on the Mn-N coordination. The Mn-N-C-S catalyst exhibits a favorable oxygen reduction reaction (ORR) activity in acidic media relative to the S-free Mn-N-C catalyst. The corresponding membrane electrode assembly (MEA) generated a remarkable performance with a peak power density of 500 mW cm -2 under a realistic H 2 /air environment. The constant voltage tests of fuel cells confirm the much-enhanced stability of the Mn-N-C-S catalyst compared to the Fe-N-C and Fe-N-C-S catalysts. The electron microscopy and Fourier transform XAS analysis provide insights into catalyst degradation associated with Mn oxidation and agglomeration. The theoretical calculation elucidates that the promoted ORR activity is mainly attributed to the spatial effect stemmed from the repulsive interaction between the ORR intermediates and adjacent S do-pants.

25 ENERGY STORAGE↗

Neurochemical background and approaches in the understanding of motion sickness

The problems and nature of space motion sickness were defined. The neurochemical and neurophysiological bases of vestibular system function and of the expression of motion sickness wre reviewed. Emphasis was given to the elucidation of the neuropharmacological mechanisms underlying the effects of scopolamine and amphetamine on motion sickness. Characterization of the ascending reticular activating system and the limbic system provided clues to the etiology of the side effects of scopolamine. The interrelationship between central cholinergic pathways and the peripheral (autonomic) expression of motion sickness was described. A correlation between the stress of excessive motion and a variety of hormonal responses to that stress was also detailed. The cholinergic system is involved in the efferent modulation of the vestibular hair cells, as an afferent modulator of the vestibular nuclei, in the activation of cortical and limbic structures, in the expression of motion sickness symptoms and most likely underscores a number of the hormonal changes that occur in stressful motion environments. The role of lecithin in the regulation of the levels of neurotransmitters was characterized as a possible means by which cholinergic neurochemistry can be modulated.

Kohl, R. L.↗

Role of Intradomain Heterogeneity on Ion and Polymer Dynamics in Block Polymer Electrolytes: Investigating Interfacial Mobility and Ion-Specific Dynamics and Transport

Block polymers show promise as solid-state battery electrolytes due to the optimization of conductive and mechanical properties enabled via tuning of block chemistry and length. We investigate a polystyrene-block-poly(oligo-oxyethylene methacrylate) (PS-b-POEM) electrolyte doped with various lithium salts to investigate the role of molecular structure on ion transport properties and on local ion dynamics and associations. Anion charge becomes more delocalized with increasing size, reducing the coupling between salt ions while increasing coupling between ion and polymer chain motions and creating a more mobile overall environment. We observe support for this ion-polymer coupling via 1 H, 7 Li and 19 F NMR spectroscopy, from which we obtain ion-specific mobility transition temperatures that differ from the polymer glass transition temperature. We also note faster transport and weaker local energetic interactions with anion size using temperature-dependent NMR diffusometry. 1 H NMR spectroscopy further elucidates polymer chain dynamics and enables quantification of the temperature-dependent fraction of the conducting block that is immobile near the PS-POEM domain interface. As a result, NMR thus represents a species-specific and timescale-specific platform to quantify phase and interface behavior, and to correlate ion-specific transport with polymer chain dynamics.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Aspartate Residues in a Forisome-Forming SEO Protein Are Critical for Protein Body Assembly and Ca 2+ Responsiveness

Forisomes are protein bodies known exclusively from sieve elements of legumes. Forisomes contribute to the regulation of phloem transport due to their unique Ca 2+ -controlled, reversible swelling. The assembly of forisomes from sieve element occlusion (SEO) protein monomers in developing sieve elements and the mechanism(s) of Ca 2+ -dependent forisome contractility are poorly understood because the amino acid sequences of SEO proteins lack conventional protein–protein interaction and Ca 2+ -binding motifs. Here we selected amino acids potentially responsible for forisome-specific functions by analyzing SEO protein sequences in comparison to those of the widely distributed SEO-related (SEOR), or SEOR proteins. SEOR proteins resemble SEO proteins closely but lack any Ca 2+ responsiveness. We exchanged identified candidate residues by directed mutagenesis of the Medicago truncatula SEO1 gene, expressed the mutated genes in yeast ( Saccharomyces cerevisiae ) and studied the structural and functional phenotypes of the forisome-like bodies that formed in the transgenic cells. We identified three aspartate residues critical for Ca 2+ responsiveness and two more that were required for forisome-like bodies to assemble. The phenotypes observed further suggested that Ca 2+ -controlled and pH-inducible swelling effects in forisome-like bodies proceeded by different yet interacting mechanisms. Finally, we observed a previously unknown surface striation in native forisomes and in recombinant forisome-like bodies that could serve as an indicator of successful forisome assembly. To conclude, this study defines a promising path to the elucidation of the so-far elusive molecular mechanisms of forisome assembly and Ca 2+ -dependent contractility.

59 BASIC BIOLOGICAL SCIENCES↗

Understanding the Deactivation of Ag–ZrO 2 /SiO 2 Catalysts for the Single-step Conversion of Ethanol to Butenes

Ag–ZrO 2 /SBA-16 has recently been found to be efficient for catalyzing the single-step conversion of ethanol to butene (1- and 2-butene mixtures) in the presence of H 2 . The reaction proceeds via a cascading sequence of reactions over mixed metal and Lewis sites, with the catalyst composition tuned to selectively favor butene formation. However, the catalyst slowly deactivates when evaluated over long reaction times. Here, we evaluated the lifetime of the Ag–ZrO 2 /SBA-16 catalyst system for ethanol-to-butene conversion at 325 °C for up to 800 hours on stream. Several characterization techniques were used to elucidate the mechanism(s) by which catalyst deactivation occurs. Coke deposition, Ag particle sintering, and Ag 0 -to-Ag + oxidation state change were identified to be the major causes of catalyst deactivation. Coke deposits cover primarily Lewis acid sites which are responsible for aldol condensation, Meerwein-Ponndorf-Verley (MPV) reduction, and dehydration reactions. Ag particle sintering and Ag oxidation state change leads to a reduction in the number of metallic Ag sites responsible for the dehydrogenation/hydrogenation steps. The fresh catalyst likely experiences hydrothermal sintering in the early stage of reaction and permanently loses some active Lewis acid sites before reaching a new structural steady state. The deactivation of Lewis acid sites leads to a decrease in overall ethanol conversion, whereas the deactivation of the metallic Ag sites decreases the butene selectivity. For catalyst regeneration, oxidative calcination (at 500 °C) followed by reduction (at 325 °C) successfully removes all the coke species on the catalyst surface and restores the metallic Ag particles of the 4Ag–4ZrO 2 /SBA-16 catalysts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Fe-single atom catalysts facilitate fast electron transfer with MoS 2 /SnS 2 cathodes in lithium–sulfur batteries

Lithium–sulfur batteries (LSBs) emerge as promising next-generation energy storage systems offering cost-effectiveness, environmental friendliness, and high theoretical energy density. The practical implementation of LSBs faces significant hindrances due to the shuttle effect and sluggish redox reactions. To address these challenges, single-atom catalyst (SAC) based combination materials from d-block elements can offer increased active catalytic sites, rapid charge transfer, accelerated electron migration, and fast sulfur redox conversion kinetics of lithium polysulfides (LiPSs). In this study, we fabricated three different LSB cathodes: pure S, S@MoS 2 /SnS 2 , and S@Fe–MoS 2 /SnS 2 . These cathodes were then used to explore the cycle life, capacity, rate capability, and redox kinetic reactions of LiPSs while assessing the influence of Fe-SACs on their performance. As a result, LSBs with S@Fe–MoS 2 /SnS 2 cathodes demonstrate an extended cycle life of 1000 cycles at a C-rate of 0.2C, maintaining a capacity close to 500 mA h g −1 , the highest initial discharge capacity of 1622 mA h g −1 and 1066 mA h g −1 at 0.05C and 0.2C, and excellent rate capabilities of 708 mA h g −1 and 558 mA h g −1 at 1C and 2C, respectively. The synergistic effect of the Fe-SAC-based combination cathode (S@Fe–MoS 2 /SnS 2 ) creates plentiful adsorptive and highly active catalytic sites, resulting in substantially enhanced capacity for adsorbing soluble long-chain LiPSs. This facilitates ultra-fast redox kinetics, surpassing the performance of the S@MoS 2 /SnS 2 and pure S cathodes. In the ex situ analysis, results from powder X-ray diffraction (XRD) to observe the new phase, soft X-ray absorption spectroscopy (XAS) to investigate the electronic structure, and hard X-ray photoelectron microscopy (HAXPES) with different energies (900 eV, 2000 eV, and 6000 eV) to track the chemical-state evolution of Fe-SACs in MoS 2 /SnS 2 cathodes displayed notable electrochemical reversibility involving S 8 ⇄ LiPSs ⇄ Li 2 S conversion even after 1000 cycles. Additionally, in situ, operando Raman analysis can unveil a novel catalytic mechanism of Fe-SACs in MoS 2 /SnS 2 “facilitating rapid electron transfer” during the discharge and charge processes of LSBs involving the conversion of S 8 ⇄ long-chain LiPSs ⇄ Li 2 S 2 /Li 2 S. This study elucidates the working mechanism of Fe-SAC cathodes, offering insights into overcoming the shuttle effect and facilitating sulfur redox kinetics to advance commercial LSBs.

36 MATERIALS SCIENCE↗

Absence of μ SR evidence for magnetic order in the pseudogap phase of Bi 2 + x Sr 2 - x CaCu 2 O 8 + δ

We present an extended zero-field muon spin relaxation (ZF-$µSR$) study of overdoped $Bi_{2+x}Sr_{2-x}\,CaCu_2O_{8+δ}$ (Bi2212) single crystals, intended to elucidate the origin of weak quasistatic magnetism previously detected by $µSR$ in the superconducting and normal states of optimallydoped and overdoped samples. New results on heavily-overdoped single crystals show a similar monotonically decreasing ZF-$µSR$ relaxation rate with increasing temperature that persists above the pseudogap (PG) temperature $T^*$ and does not evolve with hole doping ($p$). Additional measurements using an ultra-low background apparatus confirm that this behavior is an intrinsic property of Bi2212, which cannot be due to magnetic order associated with the PG phase. Instead we show that the temperature-dependent relaxation rate is most likely caused by structural changes that modify the contribution of the nuclear dipole fields to the ZF-$µSR$ signal. Finally, our results for Bi2212 emphasize the importance of not assuming the nuclear-dipole field contribution is independent of temperature in ZF-$µSR$ studies of high-temperature (high-$T_c$) cuprate superconductors, and do not support a recent $µSR$ study of $YBa_2Cu_3O_{6+x}$ that claims to detect magnetic order in the PG phase.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Phonon spectrum of $\mathrm{Pr_2Zr_2O_7}$ and $\mathrm{Pr_2Ir_2O_7}$ as evidence of coupling of the lattice with electronic and magnetic degrees of freedom

Magnetic materials with pyrochlore crystal structure form exotic magnetic states due to the high lattice frustration. Here in this work we follow the effects of coupling of the lattice and electronic and magnetic degrees of freedom in two praseodymium-based pyrochlores $\mathrm{Pr_2Zr_2O_7}$ and $\mathrm{Pr_2Ir_2O_7}$. In either of these materials, the presence of magnetic interactions does not lead to magnetically ordered low temperature states; however, their electronic properties are different. A comparison of Raman phonon spectra of $\mathrm{Pr_2Zr_2O_7}$ and $\mathrm{Pr_2Ir_2O_7}$ allows us to identify magnetoelastic coupling in $\mathrm{Pr_2Zr_2O_7}$ that elucidates its magnetic properties at intermediate temperatures and allows us to characterize phonon-electron scattering in the semimetallic $\mathrm{Pr_2Ir_2O_7}$. We also show that the effects of random disorder on the Raman phonon spectra is small.

36 MATERIALS SCIENCE↗

Tuning Active Site Flexibility by Defect Engineering of Graphene Ribbon Edge‐hosted Fe−N 3 Sites

Abstract Nitrogen‐doped, carbon‐supported transition metal catalysts are excellent for several reactions. Structural engineering of M−N x sites to boost catalytic activity is rarely studied. Here, we demonstrate that the structural flexibility of Fe−N 3 site is vital for tuning the electronic structure of Fe atoms and regulating the catalytic transfer hydrogenation (CTH) activity. By introducing carbon defects, we construct Fe−N 3 sites with varying Fe−N bond lengths distinguishable by X‐ray absorption spectroscopy. We investigate the CTH activity by density‐functional theory and microkinetic calculations and reveal that the vertical displacement of the Fe atom out of the plane of the support, induced by the Fe−N 3 distortion, raises the Fe orbital and strengthens binding. We propose that the activity is controlled by the relaxation of the reconstructed site, which is further affected by Fe−N bond length, an excellent activity descriptor. We elucidate the origin of the CTH activity and principles for high‐performing Fe−N−C catalysts by defect engineering.

Yang, Piaoping↗

A Low-Voltage Layered Na 2 TiGeO 5 Anode for Lithium-Ion Battery

Titanium-based anode materials have achieved much progress with the wide studies in lithium-ion batteries. However, these known materials usually possess high discharge voltage platforms and limited energy densities. In this work, a titanium-based oxide of Na 2 TiGeO 5 with layered structure, two-dimensional lamellar frame and exposed highly active (001) facet, exhibiting good electrochemical performance in terms of high capacity (410 mAh g –1 with a current density of 50 mA g –1 ), excellent rate capability and cycling stability with no obvious capacity attenuation after 4000 cycles, is reported. The appropriate discharge voltage plateau at around 0.2 V endows the Na 2 TiGeO 5 anode material high security compared with graphite and high energy density compared with spinel Li 4 Ti 5 O 12 . Combining the electrochemical tests and the density functional theory calculations, the Li + storage mechanism of Na 2 TiGeO 5 is elucidated and the conversion reaction process is revealed. More importantly, this study provides a way to develop low-voltage and high-capacity titanium-based anode materials for efficient energy storage.

25 ENERGY STORAGE↗