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At least 415 records · Page 23

Blowing in the dark matter wind

Abstract Interactions between dark matter and ordinary matter will transfer momentum, and therefore give rise to a force on ordinary matter due to the dark matter ‘wind.’ We show that this force can be maximal in a realistic model of dark matter, meaning that an order-1 fraction of the dark matter momentum incident on a target of ordinary matter is reflected. The model consists of light (m ϕ ≲ eV) scalar dark matter with an effective interaction$$ {\phi}^2\overline{\psi}\psi $$ ϕ 2 ψ ¯ ψ , whereψis an electron or nucleon field. If the coupling is repulsive and sufficiently strong, the fieldϕis excluded from ordinary matter, analogous to the Meissner effect for photons in a superconductor. We show that there is a large region of parameter space that is compatible with existing constraints, where the force is large enough to be detected by existing force probes, such as satellite tests of the equivalence principle and torsion balance experiments. However, shielding of the dark matter by ordinary matter prevents existing experiments from being sensitive to the dark matter force. We show that precise measurements of spacecraft trajectories proposed to test long distance modifications of gravity are sensitive to this force for a wide range of parameters.

Physics↗

A Review of Scalable Hexagonal Boron Nitride ( h -BN) Synthesis for Present and Future Applications

Hexagonal boron nitride (h-BN) is a layered inorganic synthetic crystal exhibiting high temperature stability and high thermal conductivity. As a ceramic material it has been widely used for thermal management, heat shielding, lubrication, and as a filler material for structural composites. Recent scientific advances in isolating atomically thin monolayers from layered van der Waals crystals to study their unique properties has propelled research interest in mono/few layered h-BN as a wide bandgap insulating support for nanoscale electronics, tunnel barriers, communications, neutron detectors, optics, sensing, novel separations, quantum emission from defects, among others. Realizing these futuristic applications hinges on scalable cost-effective high-quality h-BN synthesis. Here, in this work, the authors review scalable approaches of high-quality mono/multilayer h-BN synthesis, discuss the challenges and opportunities for each method, and contextualize their relevance to emerging applications. Maintaining a stoichiometric balance B:N = 1 as the atoms incorporate into the growing layered crystal and maintaining stacking order between layers during multi-layer synthesis emerge as some of the main challenges for h-BN synthesis and the development of processes to address these aspects can inform and guide the synthesis of other layered materials with more than one constituent element. Finally, the authors contextualize h-BN synthesis efforts along with quality requirements for emerging applications via a technological roadmap.

2D materials↗

A boundary-based approach to the multiscale microstructural characterization of a W-Ni-Fe tungsten heavy alloy

Here, a combination electron backscattered diffraction and transmission electron microscopy based approach has been implemented to study the effects of purposefully introduced anisotropy in a tungsten heavy alloy (WHA) through hot-rolling. Particular attention has been paid to changes in number and proportion of various boundary types from a quantitative standpoint; incorporating qualitative behavioral observations from prior analyses to generate experimentally-validated bases for the examination and application of a microstructure which exhibits an optimal balance of strength and ductility. It is asserted that a combination of increased temperatures during rolling and additional isothermal hold time for the post-rolling annealing steps may lead to a reduction in unfavorable textural components due to rolling in the W-phase and a decrease in premature fracture due to W-W microcracking respectively. This is expected to further increase the proportion of interphase boundaries and improve the ductility of these rolled structures, producing a superior rolled WHA microstructure.

36 MATERIALS SCIENCE↗

Decoupling of peeling and ballooning thresholds for pedestal stability and reduction in ELM frequency via enhanced turbulence with edge electron cyclotron heating in DIII-D

Abstract The edge localized mode (ELM) frequency ( f ELM ) decreased by 63% when electron cyclotron heating (ECH) deposition location is shifted from ρ = 0.4 to ρ = 0.8 in DIII-D discharges where the power ratio between neutral beam injection (NBI) and ECH ( P NBI / P ECH ) is kept at ∼1. The performance of the pedestal in the ECH heated case is compared with a pure NBI reference discharge while keeping the total input power constant. All these discharges are performed at balanced input torque conditions. Furthermore, in the pure NBI discharge a strong decoupling of the peeling–ballooning (PB) thresholds is observed. The PB decoupling is preserved when the ECH is deposited at ρ = 0.8 and P NBI / P ECH ∼ 1, while the thresholds manifest a closed stability boundary when the ECH is deposited at ρ = 0.4. The inter-ELM pedestal recovery time is considerably larger for the ECH at ρ = 0.8 case. Increased pedestal turbulence is observed in beam emission spectroscopy (BES), Doppler backscattering and magnetic diagnostics for the ECH at the ρ = 0.8 case. Strong growth of a TEM-like mode is observed in BES and the mode growth is correlated with the decrease in f ELM . In view of these observations, the increased pedestal turbulence seems to be the plausible reason behind the delayed pedestal recovery following an ELM event in the ECH at ρ = 0.8 case, and the preservation of PB decoupling through temperature pedestal profile widening. TRANSP interpretative simulations show that the ECH at the ρ = 0.8 case is more susceptible to ITG/TEM turbulence.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Adsorption of Iodine on Metal Coupons in Humid and Dry Environments

In this study, five different metal coupons were evaluated for gaseous iodine [I2(g)] adsorption including two stainless steels (i.e., SS304 and SS316), two Inconel® alloys (i.e., 625 and 718) and pure Ni (i.e., Ni-200) within a dynamic flow-through system where temperature, iodine concentration, flow rate, atmosphere, and relative humidity were controlled. Humidity was shown to be critical to iodine adsorption on SS304 and SS316 and Ni-200 at ambient temperatures. The results presented herein suggest that a moisture mediated reaction is occurring. However, higher humidity levels decrease the adsorption, suggesting an ideal range of humidity for highest corrosion. A comparison of the five metal substrates showed the highest I2(g) adsorption in the following descending order Ni-200 > SS304 > SS316 >718>625.The 625 and 718 Inconel alloys were fairly inert to iodine adsorption under the conditions tested. Characterization by scanning electron microscopy, energy dispersive X-ray spectroscopy, and X-ray diffraction of the Ni-200 coupon indicates that NiI2 is formed and flakes off the surface as a black powder. The SS304 and SS316 coupons showed evidence of extensive reactions with I2(g) and formed a much more deliquescent corrosion product, which reacted with air when removed from the flow-through system for weighing on the analytical balance. These findings assist in predicting iodine adsorption behavior on a variety of metal surfaces under various conditions.

Beck, Chelsie L.↗

Supramolecular Assembly of U(IV) Clusters and Superatoms with Unconventional Countercations

Superatoms are nanometer-sized molecules or particles that form ordered lattices, mimicking their atomic counterparts. Hierarchical assembly of superatoms gives rise to emergent properties in lattices of quantum dots, p-block clusters, and fullerenes. In this report, we introduce a family of uranium-oxysulfate cluster anions whose hierarchical assembly in water is controlled by two parameters: acidity and the lanthanide or transition-metal countercation. In acid, larger Ln III (Ln = La–Ho) link hexamer (U 6 ) oxoclusters into body-centered cubic frameworks, while smaller Ln III (Ln = Er–Lu and Y) promote linking of 14 U 6 clusters into hollow superclusters (U 84 superatoms). U 84 assembles into superlattices including cubic-closest packed, body-centered cubic, and interpenetrating networks, bridged by interstitial countercations and U 6 clusters. Divalent transition metals (TM = Mn II and Zn II ) charge-balance and promote the fusion of 10 U 6 and 10 U monomers into a wheel-shaped cluster (U 70 ). Dissolution of U 70 in organic media shows (by small-angle X-ray scattering) that differing supramolecular assemblies are accessed, controlled by TM II -linking of U 70 clusters. Magnetic measurements of these assemblies reveal Curie–Weiss behavior at high temperatures, without pairing of the 5f 2 -electrons down to 2 K.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

QMMM 2023: A program for combined quantum mechanical and molecular mechanical modeling and simulations

Combined quantum mechanical and molecular mechanical (QM/MM) methods play an important role in multiscale modeling and simulations. QMMM 2023 is a general-purpose program for single-point calculations, geometry optimizations, transition-state optimizations, and molecular dynamics (MD) at the QM/MM level. It calls a QM package and an MM package to perform the required single-level calculations and combines them into a QM/MM energy by a variety of schemes. QMMM 2023 supports GAMESS-US, Gaussian, and ORCA as QM packages and Tinker as the MM package. Four types of treatments are available for embedding the QM subsystem in the MM environment: mechanical embedding with gas-phase calculations of the QM region, electronic embedding that allows polarization of the QM region by the MM environment, polarizable embedding for mutual polarization of the QM and MM regions, and flexible embedding for both mutual polarization and partial charge transfer between the QM and MM regions. Boundaries between QM and MM regions that pass through covalent bonds can be treated by several methods, including the redistributed charge (RC) scheme, redistributed charge and dipole (RCD) scheme, balanced-RC scheme, balanced-RCD scheme, screened charge scheme that takes account of charge penetration effects, and smeared charge scheme that delocalizes the MM charges near the QM–MM boundary. Geometry optimization can be done using the optimizer implemented in QMMM 2023 or the Berny optimizer in Gaussian through external calls to Gaussian. Molecular dynamics simulations can be performed at the pure-MM level, pure-QM level, fixed-partitioning QM/MM level, and adaptive-partitioning QM/MM level. As a result, the adaptive-partitioning treatments permit on-the-fly relocation of the QM–MM boundary by dynamically reclassifying atoms or groups into the QM or MM subsystems.

97 MATHEMATICS AND COMPUTING↗

Extreme tensile strain states in La 0.7 Ca 0.3 MnO 3 membranes

A defining feature of emergent phenomena in complex oxides is the competition and cooperation between ground states. In manganites, the balance between metallic and insulating phases can be tuned by the lattice; extending the range of lattice control would enhance the ability to access other phases. We stabilized uniform extreme tensile strain in nanoscale La 0.7 Ca 0.3 MnO 3 membranes, exceeding 8% uniaxially and 5% biaxially. Uniaxial and biaxial strain suppresses the ferromagnetic metal at distinctly different strain values, inducing an insulator that can be extinguished by a magnetic field. Electronic structure calculations indicate that the insulator consists of charge-ordered Mn 4+ and Mn 3+ with staggered strain-enhanced Jahn-Teller distortions within the plane. This highly tunable strained membrane approach provides a broad opportunity to design and manipulate correlated electron states.

36 MATERIALS SCIENCE↗

Vertical organic electrochemical transistors for complementary circuits

Abstract Organic electrochemical transistors (OECTs) and OECT-based circuitry offer great potential in bioelectronics, wearable electronics and artificial neuromorphic electronics because of their exceptionally low driving voltages (<1 V), low power consumption (<1 µW), high transconductances (>10 mS) and biocompatibility 1–5 . However, the successful realization of critical complementary logic OECTs is currently limited by temporal and/or operational instability, slow redox processes and/or switching, incompatibility with high-density monolithic integration and inferior n-type OECT performance 6–8 . Here we demonstrate p- and n-type vertical OECTs with balanced and ultra-high performance by blending redox-active semiconducting polymers with a redox-inactive photocurable and/or photopatternable polymer to form an ion-permeable semiconducting channel, implemented in a simple, scalable vertical architecture that has a dense, impermeable top contact. Footprint current densities exceeding 1 kA cm −2 at less than ±0.7 V, transconductances of 0.2–0.4 S, short transient times of less than 1 ms and ultra-stable switching (>50,000 cycles) are achieved in, to our knowledge, the first vertically stacked complementary vertical OECT logic circuits. This architecture opens many possibilities for fundamental studies of organic semiconductor redox chemistry and physics in nanoscopically confined spaces, without macroscopic electrolyte contact, as well as wearable and implantable device applications.

Science & Technology - Other Topics↗

An Anthradithiophene Donor Polymer for Organic Solar Cells with a Good Balance between Efficiency and Synthetic Accessibility

Over the past few years, the organic photovoltaics technology (OPV) has reached remarkable power conversion efficiencies (PCEs), mostly thanks to the advent of nonfullerene acceptors as well as to a high level of materials engineering. Yet, the complex materials syntheses behind these results ultimately limit technological readiness. The quest for scalable organic compounds offering high PCE and reasonably low synthetic complexity is a must to close the gap between laboratory R&D and commercial products. The synthesis and full characterization of a new conjugated polymer called PATTD is reported herein, based on a novel anthradithiophene as an electron–rich building block coupled with a commercially available dithienylbenzodithiophenedione as an electron–withdrawing comonomer. Its photovoltaic properties are studied in blends with IT–4F and IDIC as acceptors. PATTD:IT–4F–based photovoltaic devices exhibit a PCE approaching 10% and over 2300 h shelf–life stability. Finally, the PATTD scalability factor (SF), together with the PATTD–based photovoltaic performances, lead to a PCE/SF value equal to 0.297, placing such devices into the innermost circle of OPV materials, achieving one of the best compromises between efficiency and synthetic complexity and at the same time offering promising industrial perspectives.

14 SOLAR ENERGY↗

Highly Emissive Semi-Ladder-Type Copolymers, Aggregation State, and Solution-Processed Organic Light-Emitting Transistor

An organic light-emitting transistor (OLET) integrates the logic function of a field-effect transistor (FET) with electroluminescence of a light-emitting diode (LED) into a single device. This has the potential to play an important role in smart displays, electrically pumped organic laser, and other flexible electronic devices. For achieving high-performance solution-processed OLET, three semiladder copolymers—TPTI-CC, TPTI-C, and TPTI-F—were developed in this study. It was found that variation in the chemical structure lead to significant differences in energy level, emission color, and intermolecular aggregation. High photoluminescence quantum yields (PLQY) was obtained in these three polymers. Solution-processed trilayered OLET devices were fabricated, which exhibited strong electroluminescence, balanced charge mobility, and external quantum efficiency (EQE) of 2.8%.

36 MATERIALS SCIENCE↗

A Rhenium Bis -tetramethylphenanthroline Catalyst for CO 2 Reduction to Formate

Catalytic CO 2 reduction reactions featuring high selectivity toward formate are relatively rare. In some homogeneous molecular CO 2 -reducing electrocatalysis, using triethylamine (TEA) and isopropanol (IPA) as additives improves catalytic performance in producing formate. In this paper, we investigate whether the rhenium(I) bis-diimine dicarbonyl complexes, cis-[Re(N^N) 2 (CO) 2 ] + , where N^N is 2,2’-bipyridine ([1] + ) or 3,4,7,8-tetramethyl-1,10-phenanthroline ([2] + ), are capable of electrocatalytically reducing CO 2 to formate in acetonitrile containing TEA and IPA. Catalyst [1] + was ineffective at CO 2 reduction, yielding formate quantities comparable to those produced in experiments without the catalyst. Catalyst [2] + , however, is a promising electrocatalyst for the CO 2 reduction reaction in the presence of TEA and IPA, with formate being produced in millimolar concentrations (10.5 mM), as detected by 1 H NMR spectroscopy after 6 h electrolysis (formate Faradaic efficiency = 11%, with the major balance going to H 2 ). Upon more detailed examination, [2] + exhibited a turnover frequency (TOF) of 12 s –1 for formate, comparable to other leading molecular catalysts that competently execute this reduction. Combinations of spectroscopy, electrochemistry, and theory were used to better understand the mechanism of CO 2 reduction by [2] + . Fourier transform infrared spectroelectrochemical (FTIR-SEC) data provided no evidence for CO ligand dissociation or substitution upon one- and two-electron reduction of [2] + , suggesting that a mechanism distinct from one that is metal-hydride-based is operative in catalysis. Computational studies guide mechanistic investigations toward the proposed formation of a hydrophenanthroline-based intermediate responsible for hydride transfer to CO 2 and electrocatalytic formate production from [2] + .

Beverages↗

Dual Energy Electron Storage Ring Cooler Design for Relativistic Ion Beams

Collider experiments demand small beam emittances in order to achieve high luminosity. For light particles such as electrons, there exists a natural synchrotron radiation damping resulting in low emittance beams at equilibrium. In the case of heavy particle beams such as proton or ion beams, there is no significant synchrotron radiation damping effect and some cooling mechanism is needed to get to low emittance beams. A dual energy storage ring cooler is a novel concept proposed to cool hadron beams at higher energies. The design consists of two rings: a low energy ring and a high energy ring connected by the energy recovering linac (ERL) that provides the necessary energy difference. The low energy ring has an electron cooler where the cooling interaction takes place between the electron and hadron beams whereas electron beam going through the high energy ring undergoes synchrotron radiation damping. In this document, we present a possible design of a dual energy storage ring-based electron cooler for high energy proton beam cooling suitable for the Electron Ion Collider (EIC) to be built at Brookhaven National laboratory (BNL). A special feature of a dual energy storage ring cooler design is that the electron beam energy in the low energy section must be tuned to match the hadron beam velocity in the cooling section, and the electron beam energy in the high energy section is chosen to provide an adequate synchrotron radiation damping. In addition, the ring optics design is carried out considering chromaticity correction, dynamic aperture, momentum aperture, beam lifetime, radiation damping and the intrabeam scattering effect. Finally, the cooling performance is simulated for 275 GeV proton beams at the top energy of the EIC. In such a collider it is desirable to cool the hadron beams to balance the emittance growth rates due to intra-beam scattering (IBS) to maintain a high luminosity during the collision runs. In such a situation, a dual energy storage ring based cooler could be a practical approach to be used for hadron beam cooling.

Dhital, Bhawin↗

Theory of sigma bond resonance in flat boron materials

Abstract In chemistry, theory of aromaticity or π bond resonance plays a central role in intuitively understanding the stability and properties of organic molecules. Here we present an analogue theory for σ bond resonance in flat boron materials, which allows us to determine the distribution of two-center two-electron and three-center two-electron bonds without quantum calculations. Based on this theory, three rules are proposed to draw the Kekulé-like bonding configurations for flat boron materials and to explore their properties intuitively. As an application of the theory, a simple explanation of why neutral borophene with ~1/9 hole has the highest stability and the effect of charge doping on borophene’s optimal hole concentration is provided with the assumption of σ and π orbital occupation balance. Like the aromaticity theory for carbon materials, this theory greatly deepens our understanding on boron materials and paves the way for the rational design of various boron-based materials.

36 MATERIALS SCIENCE↗

Plastoquinone redox status influences carboxysome integrity via a RpaA ‐ and reactive oxygen species‐dependent regulatory network

SUMMARY Carboxysomes are bacterial microcompartments that encapsulate Rubisco and are a core component of the cyanobacterial carbon concentration mechanism (CCM). While carboxysome number, size, and spatial organization vary in different environmental conditions (CO 2 , light availability, redox state, temperature, and light quality), the molecular mechanisms underlying this potentially adaptive process remain elusive. Herein, we observe that mutants of the circadian rhythm/metabolism factor, Regulator of Phycobilisome Association A (RpaA), exhibit a striking breakdown of carboxysomes under certain environmental conditions. We find that conditions leading to overreduction of the plastoquinone (PQ) pool (mixotrophic growth, high irradiance, or chemical inhibition of electron transfer from PQ to the cytochromeb 6 fcomplex) are accompanied by an elevated generation of reactive oxygen species (ROS) and correlate with the loss of carboxysome integrity. Carboxysome breakdown is reversed by environmental conditions or chemical inhibitors that prevent PQ overreduction and accompanying ROS generation. Taken together, our data support a novel link between the redox status of the PQ pool and carboxysome integrity. Our results have implications for the fundamental understanding of cyanobacterial energy‐balancing pathways and may indicate new research directions for understanding how the carboxysome is remodeled in response to changing environments.

Plant Sciences↗

Advancing the mechanical integrity and fragmentation behavior of reactive projectiles

A multivariant statistical approach was used to identify treatment conditions that improve the survivability of structural reactive material (SRM) projectiles upon launch and enhance energy release upon impact. The study included both mechanical testing of projectiles as well as their reactive characterization. The projectiles were launched in a high-velocity impact-ignition testing system and impacted an anvil for vented chamber calorimetry. This study examined a link between ultimate compressive stress and combustion performance. Two treatments were applied to consolidated aluminum projectiles including annealing and addition of silica (SiO 2 ) inclusions. Results showed annealing at moderate temperatures resulted in intact SRM projectiles upon launch. Adding small concentrations (1–2 wt. %) of SiO 2 to the SRM promoted fragmentation and combustion performance upon impact. Compared to the untreated projectiles, annealing with SiO 2 inclusion processing treatments improved the energy conversion efficiency from 37–84% (for untreated projectiles) up to 54–98%. In conclusion, increasing interparticle dislocation recovery by annealing while balancing inclusions promoting fragmentation upon impact was the key to optimizing combustion performance for SRM ballistic impact applications.

42 ENGINEERING↗

Design and structural basis of selective 1,4-dihydropyridine inhibitors of the calcium-activated potassium channel K Ca 3.1

The 1,4-dihydropyridines, drugs with well-established bioavailability and toxicity profiles, have proven efficacy in treating human hypertension, peripheral vascular disorders, and coronary artery disease. Every 1,4-dihydropyridine in clinical use blocks L-type voltage-gated calcium channels. We now report our development, using selective optimization of a side activity (SOSA), of a class of 1,4-dihydropyridines that selectively and potently inhibit the intermediate-conductance calcium-activated K + channel K Ca 3.1, a validated therapeutic target for diseases affecting many organ systems. One of these 1,4-dihydropyridines, DHP-103, blocked K Ca 3.1 with an IC 50 of 6 nM and exhibited exquisite selectivity over calcium channels and a panel of >100 additional molecular targets. Using high-resolution structure determination by cryogenic electron microscopy together with mutagenesis and electrophysiology, we delineated the drug binding pocket for DHP-103 within the water-filled central cavity of the K Ca 3.1 channel pore, where bound drug directly impedes ion permeation. DHP-103 inhibited gain-of-function mutant K Ca 3.1 channels that cause hereditary xerocytosis, suggesting its potential use as a therapeutic for this hemolytic anemia. In a rat model of acute ischemic stroke, the second leading cause of death worldwide, DHP-103 administered 12 h postischemic insult in proof-of-concept studies reduced infarct volume, improved balance beam performance (measure of proprioception) and decreased numbers of activated microglia in infarcted areas. K Ca 3.1-selective 1,4-dihydropyridines hold promise for the many diseases for which K Ca 3.1 has been experimentally confirmed as a therapeutic target.

Ong, Seow Theng [Lee Kong Chian School of Medicine↗

Time-resolved in situ visualization of the structural response of zeolites during catalysis

Zeolites form an important class of materials that are widely used in various fields. Their unique properties come primarily from their size, shape, and connectivity of their sub-nm crystalline voids, the Si/Al ratio of the anionic framework, and the number and the nature of charge-balancing cations.The inhomogeneous distribution of the Si/Al ratio within crystals, and hence the cation density, the presence of organic residues, and their inhomogeneous distribution within crystals sensitively affect their performances because these factors influencethe intra-crystalline diffusion rates of the reactants and products. However, the information regarding these inhomogeneities in zeolite crystals cannot be obtained by conventional analytical tools because they only provide information regardingthe average properties of zeolite crystals. Here we employin situX-ray free electron laser-based time-resolved coherent X-ray diffraction imaging to investigate the internal deformations originating from the inhomogeneous Cu ion distributions in Cu-exchanged ZSM-5 zeolite crystals during the deoxygenation of nitrogen oxides with propene. We show that the interactions between the reactants and the active sites lead to an unusual strain distribution,which is confirmed by density functional theory simulations. Moreover, this elucidates the factors responsible for distinct active regions,which are essential to maximizing some applications with enhanced performances. These observations provide insights into the role of structural inhomogeneity in zeolites during a catalytic processand will assist the future design of zeolites for their applications.

36 MATERIALS SCIENCE↗