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At least 127 records · Page 7

Tuning Uranium Redox Chemistry in Asymmetric Polyoxometalate Complexes: Access to U(IV), U(V), and Transient U(VI)

We report the synthesis and characterization of asymmetric sandwich-type complexes [TpU IV EW 11 O 39 ] x– (E = P; x = 4, E = Si; x = 5, Tp = trispyrazolylborate). These complexes represent rare examples of the selective formation of asymmetric actinide-polyoxometalate (An-POM) complexes. Oxidation studies show that the U V analogues are stable and accessible, with both complexes isolated. Attempts to access U VI with this framework yield mixed results. Attempts to produce [TpU VI PW 11 O 39 ] 2– only led to decomposition, while electrochemical oxidation experiments gave evidence of transient formation of [TpU VI SiW 11 O 39 ] 3– in solution. Rapid decomposition of [TpU VI SiW 11 O 39 ] 3– inhibits full characterization. These studies indicate that the redox properties and stability of An-POM complexes containing actinides in higher valencies are dependent on the anionic charge of the assembly.

Actinides↗

Mechanisms of Asymmetric Membrane Formation in Nonsolvent-Induced Phase Separation

We report the first simulations of nonsolvent-induced phase separation (NIPS) that predict membrane microstructures with graded asymmetric pore size distribution. In NIPS, a polymer solution film is immersed in a nonsolvent bath, enriching the film in nonsolvent, and leading to phase separation that forms a solid polymer-rich membrane matrix and polymer-poor membrane pores. We demonstrate how mass-transfer-induced spinodal decomposition, thermal fluctuations, and glass-transition dynamics implemented with mobility contrast between the polymer-rich and polymer-poor phases are essential to the formation of asymmetric membrane microstructures. Specifically, we show that the competition between the propagation of the phase-separation and glass-transition fronts determines the degree of pore-size asymmetry. In conclusion, we also explore the sensitivity of these microstructures to the initial film composition, and compare their formation in 2D and 3D.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Enhanced Emission from Bright Excitons in Asymmetrically Strained Colloidal CdSe/Cd x Zn 1– x Se Quantum Dots

Colloidal CdSe quantum dots (QDs) designed with a high degree of asymmetric internal strain have recently been shown to host a number of desirable optical properties including subthermal room-temperature line widths, suppressed spectral diffusion, and high photoluminescence (PL) quantum yields. It remains an open question, however, whether they are well-suited for applications requiring emission of identical single photons. Here we measure the low-temperature PL dynamics and the polarization-resolved fluorescence line narrowing spectra from ensembles of these strained QDs. Our spectroscopy reveals the radiative recombination rates of bright and dark excitons, the relaxation rate between the two, and the energy spectra of the quantized acoustic phonons in the QDs that can contribute to relaxation processes. In comparison to conventional colloidal CdSe/ZnS core/shell QDs, we find that in asymmetrically strained CdSe QDs over six times more light is emitted directly by the bright exciton. Furthermore, these results are therefore encouraging for the prospects of chemically synthesized colloidal QDs as emitters of single indistinguishable photons.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Energizing Robust Sulfur/Lithium Electrochemistry via Nanoscale-Asymmetric-Size Synergism

Sluggish redox kinetics and dendrite growth perplex the fulfillment of efficient electrochemistry in lithium–sulfur (Li–S) batteries. The complicated sulfur phase transformation and sulfur/lithium diversity kinetics necessitate an all-inclusive approach in catalyst design. Herein, a compatible mediator with nanoscale-asymmetric-size configuration by integrating Co single atoms and defective CoTe 2–x (Co SA -CoTe 2–x @NHCF) is elaborately developed for regulating sulfur/lithium electrochemistry synchronously. Substantial electrochemistry and theoretical analyses reveal that CoTe 2–x exhibits higher catalytic activity in long-chain polysulfide transformation and Li 2 S decomposition, while monodispersed Co sites are more effective in boosting sulfur reduction kinetics to regulate Li 2 S deposition. Such cascade catalysis endows Co SA -CoTe 2–x @NHCF with the all-around service of “trapping-conversion-recuperation” for sulfur species during the whole redox reaction. Furthermore, it is demonstrated by in situ transmission electron microscopy that initially formed electronic-conductive Co and ionic-conductive Li 2 Te provide sufficient lithiophilic sites to regulate homogeneous Li plating and stripping with markedly suppressed dendrite growth. Consequently, by coupling the Co SA -CoTe 2–x @NHCF interlayer and Li@Co SA -CoTe 2–x @NHCF anode, the constructed Li–S full batteries deliver superior cycling stability and rate performance, and the flexible pouch cell exhibits stable cycling performance at 0.3 C. In conclusion, the gained insights into the synergistic effect of asymmetric-size structures pave the way for the integrated catalyst design in advanced Li–S systems.

36 MATERIALS SCIENCE↗

Coherent control of asymmetric spintronic terahertz emission from two-dimensional hybrid metal halides

Abstract Next-generation terahertz (THz) sources demand lightweight, low-cost, defect-tolerant, and robust components with synergistic, tunable capabilities. However, a paucity of materials systems simultaneously possessing these desirable attributes and functionalities has made device realization difficult. Here we report the observation of asymmetric spintronic-THz radiation in Two-Dimensional Hybrid Metal Halides (2D-HMH) interfaced with a ferromagnetic metal, produced by ultrafast spin current under femtosecond laser excitation. The generated THz radiation exhibits an asymmetric intensity toward forward and backward emission direction whose directionality can be mutually controlled by the direction of applied magnetic field and linear polarization of the laser pulse. Our work demonstrates the capability for the coherent control of THz emission from 2D-HMHs, enabling their promising applications on the ultrafast timescale as solution-processed material candidates for future THz emitters.

36 MATERIALS SCIENCE↗

Symmetry-breaking in patch formation on triangular gold nanoparticles by asymmetric polymer grafting

Synthesizing patchy particles with predictive control over patch size, shape, placement and number has been highly sought-after for nanoparticle assembly research, but is fraught with challenges. Here we show that polymers can be designed to selectively adsorb onto nanoparticle surfaces already partially coated by other chains to drive the formation of patchy nanoparticles with broken symmetry. In our model system of triangular gold nanoparticles and polystyrene-b-polyacrylic acid patch, single- and double-patch nanoparticles are produced at high yield. These asymmetric single-patch nanoparticles are shown to assemble into self-limited patch-patch connected bowties exhibiting intriguing plasmonic properties. To unveil the mechanism of symmetry-breaking patch formation, we develop a theory that accurately predicts our experimental observations at all scales—from patch patterning on nanoparticles, to the size/shape of the patches, to the particle assemblies driven by patch-patch interactions. Both the experimental strategy and theoretical prediction extend to nanoparticles of other shapes such as octahedra and bipyramids. Our work provides an approach to leverage polymer interactions with nanoscale curved surfaces for asymmetric grafting in nanomaterials engineering.

42 ENGINEERING↗

Symmetric and asymmetric DNA N6-adenine methylation regulates different biological responses in Mucorales

DNA N6-adenine methylation (6mA) has recently gained importance as an epigenetic modification in eukaryotes. Its function in lineages with high levels, such as early-diverging fungi (EDF), is of particular interest. Here, we investigated the biological significance and evolutionary implications of 6mA in EDF, which exhibit divergent evolutionary patterns in 6mA usage. The analysis of two Mucorales species displaying extreme 6mA usage reveals that species with high 6mA levels show symmetric methylation enriched in highly expressed genes. In contrast, species with low 6mA levels show mostly asymmetric 6mA. Interestingly, transcriptomic regulation throughout development and in response to environmental cues is associated with changes in the 6mA landscape. Furthermore, we identify an EDF-specific methyltransferase, likely originated from endosymbiotic bacteria, as responsible for asymmetric methylation, while an MTA-70 methylation complex performs symmetric methylation. The distinct phenotypes observed in the corresponding mutants reinforced the critical role of both types of 6mA in EDF.

59 BASIC BIOLOGICAL SCIENCES↗

Asymmetric magnetic proximity interactions in MoSe 2 /CrBr 3 van der Waals heterostructures

Magnetic proximity interactions between atomically thin semiconductors and two-dimensional magnets provide a means to manipulate spin and valley degrees of freedom in non-magnetic monolayers, without using applied magnetic fields. In such van der Waals heterostructures, magnetic proximity interactions originate in the nanometre-scale coupling between spin-dependent electronic wavefunctions in the two materials, and typically their overall effect is regarded as an effective magnetic field acting on the semiconductor monolayer. Here we demonstrate that magnetic proximity interactions in van der Waals heterostructures can in fact be markedly asymmetric. Valley-resolved reflection spectroscopy of MoSe2/CrBr3 van der Waals structures reveals strikingly different energy shifts in the K and K' valleys of the MoSe2 due to ferromagnetism in the CrBr3 layer. Density functional calculations indicate that valley-asymmetric magnetic proximity interactions depend sensitively on the spin-dependent hybridization of overlapping bands and as such are likely a general feature of hybrid van der Waals structures. Here, these studies suggest routes to control specific spin and valley states in monolayer semiconductors.

36 MATERIALS SCIENCE↗

Asymmetric electrode ionomer for low relative humidity operation of anion exchange membrane fuel cells

The operation of fuel cells under low relative humidity (RH) conditions gives substantial cost and performance benefits. Nonetheless, it is not currently feasible to operate anion exchange membrane fuel cells (AEMFCs) at low RH conditions because current materials for membrane electrode assembly cannot provide sufficient water for the oxygen reduction reaction. In this work, we synthesized polyfluorene ionomers with different ammonium concentrations for anode and cathode to control water management. We designed several asymmetric electrodes that enable high performance under low RH conditions via not only conventional backward water diffusion (anode to cathode) but also forward diffusion (cathode to anode). The AEMFCs using optimized asymmetric electrodes exhibited high H 2 /CO 2 -free air performance (rated power density of circa 540 mW cm -2 at 90 °C under 75% (anode) and 50% RH (cathode) conditions), which is comparable to those of state-of-the-art AEMFCs under nearly water-saturated conditions. The durability of the AEMFCs is excellent, generating 0.6 A cm -2 for >900 h at 80 °C under 50% RH (cathode) conditions. This study demonstrates that high-performance and durable AEMFCs under low RH and high current generating conditions are possible.

25 ENERGY STORAGE↗

Reduction of asymmetric wall force in JET and ITER disruptions including runaway electrons

It was shown that asymmetric vertical displacement event (AVDE) disruptions in JET and ITER do not produce a large asymmetric force on conducting structures surrounding the plasma, provided that the current quench (CQ) time is less than the resistive wall penetration time. This is verified with JET data. In ITER the CQ is expected to be comparable to the resistive wall penetration time, which gives a small wall force. It is shown that runaway electrons (REs) in JET do not produce a large wall force, and this is verified with JET data. This occurs if the RE current is about half of the initial plasma current. In ITER, the RE current might be comparable to the initial current, and REs might lengthen the CQ time sufficiently to produce a large wall force.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Spin–orbit torques in structures with asymmetric dusting layers

Current-induced spin–orbit torques (SOTs) in heavy metal/ferromagnet heterostructures have emerged as an efficient method for magnetization switching with applications in nonvolatile magnetic memory and logic devices. However, experimental realization of SOT switching of perpendicular magnetization requires an additional inversion symmetry breaking, calling for modifications of the conventional SOT heterostructures. In this work, we study SOTs and deterministic switching of perpendicular magnetization by inserting different asymmetric dusting layers at the heavy metal/ferromagnet interface. Similar to the previous works with lateral structural asymmetry, we study the emergence of current-induced perpendicular effective magnetic fields (H z eff ). By examining three different material combinations of heavy metal/dusting layers (W/IrMn, Pt/IrMn, and W/Ta), we shed light on the origins of H z eff ; we show that H z eff is generically created in all the studied asymmetric structures, has a close correlation with the interfacial magnetic anisotropy, and is independent of the signs of spin Hall angles of the materials. Furthermore, we show that the induction of H z eff enables field-free deterministic SOT switching of perpendicular magnetization. Our results can be used in designing SOT heterostructures for practical applications in nonvolatile technologies.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗

Whistler waves generated by nongyrotropic and gyrotropic electron beams during asymmetric guide field reconnection

Using a two-dimensional particle-in-cell simulation of asymmetric reconnection with a guide field whose strength is 0.3 times the reconnecting magnetic field, we study electron distribution functions and wave intensities in the diffusion region, focusing on the electron diffusion region (EDR). Wave activities with frequencies below the electron cyclotron frequency are observed, and these are whistler waves propagating almost anti-parallel to the magnetic field. The waves are concentrated near the magnetospheric separatrix away from the X line, but the wave activity also spreads through the EDR near the X line. The reconnection outflows are asymmetric in the outflow direction in the magnetospheric side, and the wave intensity is stronger in the side of the faster electron outflow. We study the whistler waves using the fast Fourier transform, analyses of electron velocity distribution functions, and the dispersion solver calculation. Along the magnetospheric separatrix in the stronger outflow side, highly anisotropic electron beams exist with super-Alfvénic drift speeds. The dispersion analysis shows that there are two modes: a temperature anisotropy mode and a beam mode. Outside the EDR, the whistler wave intensity is highest near the separatrix, but the wave intensity decreases if we move away from the separatrix toward the magnetic neutral line because of the increase in the electron population near zero parallel velocity. In the EDR, in the velocity plane perpendicular to the magnetic field, ring/crescent electron distribution functions are observed. Near the X-line, the wave power is enhanced where nongyrotropic electrons contribute to increase the perpendicular temperature anisotropy.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Features of correlation measurements of the parameters of pulsed hyperspectral optical fields using an asymmetric interferometer

Differences in correlation measurements of the parameters of pulsed hyperspectral optical fields using symmetric and asymmetric interferometers are considered. It is shown analytically that the resulting cross-correlation function is sensitive to phase perturbations in the original wave field. The considered setup, which contains a telescopic reflective 4f system of parabolic mirrors in one arm, demonstrates that in the case of an asymmetric interferometer, the presence of aberrations leads to degradation of the reconstructed image, whereas in the case of symmetric interferometers these aberrations do not affect the result. (paper)

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗

Interfacial electroneutrality controls transport of asymmetric salts through charge-patterned mosaic membranes

Membranes that selectively enhance target solute permeation while rejecting competing species are essential for precision separations. This study introduces charge-patterned mosaic membranes (CMMs) that selectively transport divalent asymmetric salts by leveraging a net-neutral membrane–solution interface. This mechanism, dictated by the charge ratio of positive and negative domains on the membrane surface and the balance of cations and anions in the salt, is supported by analytical, numerical, and experimental results. Analytical solutions identified cationic domain coverages (f + ) of 33%, 50%, and 66% as optimal for the selective transport of +2:−1 salts, +1:−1 salts, and +1:−2 salts, respectively, under conditions where the pattern size (L) is significantly larger than the Debye length. Numerical simulations and experiments using CMMs with alternating charged-stripes inkjet-printed onto nanostructure copolymer substrates confirmed these findings. By varying stripe widths to control f + , pressure-driven filtration experiments demonstrated selective enrichment of MgCl 2 and K 2 SO 4 at the predicted f + values, with deviations from these values leading to salt rejection. These results highlight the pivotal role of a net-neutral interface in enabling asymmetric salt enrichment. This study positions CMMs as a versatile platform for tuning ion selectivity, addressing challenges in resource recovery, water treatment, and precision separations.

additive manufacturing↗

Asymmetric drift in MaNGA: mass and radially dependent stratification rates in galaxy discs

ABSTRACT We measure the age–velocity relationship from the lag between ionized gas and stellar tangential speeds in ∼500 nearby disc galaxies from MaNGA in Sloan Digital Sky Survey IV (SDSS-IV). Selected galaxies are kinematically axisymmetric. Velocity lags are asymmetric drift, seen in the Milky Way’s (MW) solar neighbourhood and other Local Group galaxies; their amplitude correlates with stellar population age. The trend is qualitatively consistent in rate ($\dot{\sigma }$) with a simple power-law model where σ ∝ tb that explains the dynamical phase-space stratification in the solar neighbourhood. The model is generalized based on disc dynamical times to other radii and other galaxies. We find in-plane radial stratification parameters σ0,r (dispersion of the youngest populations) in the range of 10–40 km s−1 and 0.2 < br < 0.5 for MaNGA galaxies. Overall, brincreases with galaxy mass, decreases with radius for galaxies above 10.4 dex (M⊙) in stellar mass, but is ∼constant with radius at lower mass. The measurement scatter indicates the stratification model is too simple to capture the complexity seen in the data, unsurprising given the many possible astrophysical processes that may lead to stellar population dynamical stratification. None the less, the data show dynamical stratification is broadly present in the galaxy population, with systematic trends in mass and density. The amplitude of the asymmetric drift signal is larger for the MaNGA sample than the MW, and better represented in the mean by what is observed in the discs of M31 and M33. Either typical discs have higher surface-density or, more likely, are dynamically hotter (hence thicker) than the MW.

Bershady, Matthew A. (ORCID:0000000231314374)↗

From capture to collapse: Revisiting black hole formation by fermionic asymmetric dark matter in neutron stars

Fermionic asymmetric dark matter (ADM) can be captured in neutron stars (NSs) via scatterings with the star constituents. The absence of dark matter annihilation due to its asymmetric nature leads to ADM accumulation in the NS core, potentially reaching densities sufficient to exceed the Chandrasekhar limit and trigger its gravitational collapse into a black hole (BH), eventually consuming the NS from within. Therefore, the existence and observation of old neutron stars provide a means to constrain the properties of ADM. We revisit previous constraints on the mass and scattering cross section off neutrons of fermionic ADM across a class of models. We critically examine common simplifying approximations used in the literature to derive these limits. Our analysis includes improved treatments of dark matter capture, thermalization, BH formation, accretion, and evaporation. We find that previous results can be relaxed by a few orders of magnitude once these effects are properly accounted for.

79 ASTRONOMY AND ASTROPHYSICS↗

Asymmetric ferroelectricity by design in atomic-layer superlattices with broken inversion symmetry

In atomic-layer superlattices constructed using three constituent phases, CaTiO 3 , SrTiO 3 , and BaTiO 3 , the stacking sequence of the atomic layers is found to control the symmetry of the high-temperature dielectric response. In such a superlattice when a nanostructured asymmetric strain is programmed into the lattice via the stacking order, the natural symmetry at high temperatures is removed and a polarized sample is obtained in which the polarization increases as the temperature is lowered. Here, in contrast to a ferroelectric characterized by a bistable ground state with two equal and opposite electronic polarizations, our experiments show evidence of asymmetric ferroelectric correlations that set in when such a sample becomes hysteretic below a temperature T x , with two unequal polarization states. We further show that both the magnitude and direction of this ferroelectric asymmetry can be controlled by the engineered atomic-layer stacking order and periodicity of the superlattice.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Energy dependence of $\textit{p}$ + 232 Th fission mass distributions: Mass-asymmetric standard I and standard II modes, and multichance fission

Background: The predominant mass-asymmetric fission of actinide nuclides occurs mainly through the so-called standard I and standard II modes. Though understood to be caused by shape-dependent shell structures encountered between the fission barrier deformation and scission, the most relevant shell gaps are still not firmly established. The standard I mode had been associated with the spherical doubly magic 132 Sn, and thus the $\textit{Z}$ = 50 proton shell, but recently it has been proposed that standard I and standard II are associated with quadrupole and octupole deformed gaps at $\textit{Z}$ = 52 and 56, respectively. Purpose: In this work, we investigate how the relative probabilities of the standard I and standard II modes vary with excitation energy near threshold, probing where the two modes bifurcate. Methods: The Australian National University Heavy Ion Accelerator Facility and CUBE fission spectrometer have been used to measure fission mass distributions for the $\textit{p}$ + 232 Th reaction (forming 233 Pa) at closely spaced bombarding energy intervals from 6.5 to 28 MeV. Results: A model-independent analysis of the energy dependence of the shape of the mass-asymmetric peak shows a strong dependence of the standard I and standard II relative probability on excitation energy near threshold. Conclusions: The results are consistent with the standard II mode having a lower fission barrier than standard I in 233 Pa, with the latter increasing continually in relative probability above its barrier energy. It is concluded that multichance fission, in particular last chance fission, plays a strong role in determining the observed energy dependence of all fission modes.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗