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At least 145 records · Page 8

Nucleation and growth of HNO3-3H2O particles in the polar stratosphere

Growth of nitric acid trihydrate (NAT) particles on background stratospheric aerosols is examined for an isolated air parcel cooled at a uniform rate. During the process of nucleation, the saturation ratio of HNO3 vapor reaches a maximum value between 2 and 15, corresponding to supercooling by 1-4 K. If cooling rates exceed 0.5-1 K/day, small particles of NAT are produced. A major fraction of the available condensation nuclei is activated and removal of HNO3 by gravitational settling is slow. If cooling rates are less than 0.5-1 K/day, the number of aerosols that nucleate is reduced, leading to differential growth of large NAT particles. Observations of 5 micron radius particles in clouds at temperatures above the water frost point may reflect condensation of NAT on ice particles that fall through a column of air as it is cooled. Rapid condensation of HNO3 on ice particles is promoted by the high supersaturation attained during nucleation and maintained during subsequent cooling. This process provides a mechanism for irreversible removal of HNO3.

Wofsy, Steven C.↗

Combinatorial gene inactivation of aldehyde dehydrogenases mitigates aldehyde oxidation catalyzed by E. coli resting cells

Aldehydes are attractive chemical targets both as end products in the flavors and fragrances industry and as synthetic intermediates due to their propensity for C–C bond formation. Here, in this study, we identify and address unexpected oxidation of a model collection of aromatic aldehydes, including many that originate from biomass degradation. When diverse aldehydes are supplemented to E. coli cells grown under aerobic conditions, as expected they are either reduced by the wild-type MG1655 strain or stabilized by a strain engineered for reduced aromatic aldehyde reduction (the E. coli RARE strain). Surprisingly, when these same aldehydes are supplemented to resting cell preparations of either E. coli strain, under many conditions we observe substantial oxidation. By performing combinatorial inactivation of six candidate aldehyde dehydrogenase genes in the E. coli genome using multiplexed automatable genome engineering (MAGE), we demonstrate that this oxidation can be substantially slowed, with greater than 50% retention of 6 out of 8 aldehydes when assayed 4 h after their addition. Given that our newly engineered strain exhibits reduced oxidation and reduction of aromatic aldehydes, we dubbed it the E. coli ROAR strain. We applied the new strain to resting cell biocatalysis for two kinds of reactions – the reduction of 2-furoic acid to furfural and the condensation of 3-hydroxybenzaldehyde and glycine to form a non-standard β-hydroxy-α-amino acid. In each case, we observed substantial improvements in product titer 20 h after reaction initiation (9-fold and 10-fold, respectively). Moving forward, the use of this strain to generate resting cells should allow aldehyde product isolation, further enzymatic conversion, or chemical reactivity under cellular contexts that better accommodate aldehyde toxicity.

59 BASIC BIOLOGICAL SCIENCES↗

Deconstructing the Local Intermolecular Ordering and Dynamics of Liquid Chloroform and Bromoform

Local intermolecular structure and dynamics of the polar molecular liquids chloroform and bromoform are studied by molecular dynamics simulation. Structural distribution functions, including 1- and 2-D pair correlations and dipole contour plots allow direct comparison and show agreement with recent analyses of diffraction experiments. Studies of the haloforms’ reorientational dynamics and longevity of structural features resulting from intermolecular interaction extend previous work toward deeper understanding of the factors controlling these features. Analyses of ensemble average structures and dynamical properties isolate mass, electrostatics, and steric packing as driving forces or contributing factors for the observed ordering and dynamics.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Dynamically Chiral Expanded Helicenes

Expanded helicenes are a class of chiral nanographenes with a screw-shaped skeleton and a larger diameter than their classical ortho-fused counterparts. The flexibility of this internal cavity results in helicenes that are often difficult to isolate as single enantiomers. Expanded helicenes are therefore an intriguing target for exploration of dynamic chirality, a phenomenon resulting from introduction of chiral auxiliaries to control structure in a racemic system. This contribution describes installation of chiral amine substituents into the cavity of a diformyl expanded [11]-helicene by mild, efficient, and reversible imine condensations. The resulting helicenes display strong molar circular dichroism up to |Δε| = 300 M -1 cm -1 and absorption dissymmetry factors of |g abs | = 0.010. The magnitude of circular dichroism can be varied by using different chiral amine substituents, which is correlated to the diastereomeric ratios of the helicenes. In conclusion, this is the first instance of dynamic chirality being used to observe a chiroptic response in expanded helicenes and is a significant synthetic improvement over methods which require conventional enantiomer resolution.

Rothenberger, August J. [University of California,↗

Electrochemical C–N Bond Formation within Boron Imidazolate Cages Featuring Single Copper Sites

Electrocatalysis expands the ability to generate industrially relevant chemicals locally and on-demand with intermittent renewable energy, thereby improving grid resiliency and reducing supply logistics. Herein, we report the feasibility of using molecular copper boron-imidazolate cages, BIF-29(Cu), to enable coupling between the electroreduction reaction of CO 2 (CO 2 RR) with NO 3 – reduction (NO 3 RR) to produce urea with high selectivity of 68.5% and activity of 424 μA cm –2 . Remarkably, BIF-29(Cu) is among the most selective systems for this multistep C–N coupling to-date, despite possessing isolated single-metal sites. The mechanism for C–N bond formation was probed with a combination of electrochemical analysis, in situ spectroscopy, and atomic-scale simulations. We found that NO 3 RR and CO 2 RR occur in tandem at separate copper sites with the most favorable C–N coupling pathway following the condensation between *CO and NH 2 OH to produce urea. In conclusion, this work highlights the utility of supramolecular metal–organic cages with atomically discrete active sites to enable highly efficient coupling reactions.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

Charge density fluctuations with enhanced superconductivity at the proposed quantum critical point of Sr0.77⁢Ba0.23⁢Ni2⁢As2

A quantum critical point (QCP) represents a continuous phase transition at absolute zero. In unconventional superconductors, enhanced superconducting transition temperature and magnetic fluctuation strength are often observed together, indicating magnetism-mediated superconductivity. This raises the question of whether quantum fluctuations in other degrees of freedom, such as charge, could similarly boost superconductivity. However, because charge is frequently intertwined with magnetism, isolating and understanding its specific role in Cooper pair formation pose a significant challenge. Here, we report persistent charge density fluctuations (CDFs) down to 15 K in the nonmagnetic superconductor Sr0.77⁢Ba0.23⁢Ni2⁢As2, which lie near a proposed nematic QCP associated with a sixfold enhancement of superconductivity. Our results show that the quasielastic CDFs do not condense into resolution-limited Bragg peaks but, rather, display nonsaturated strength. The phonons associated with CDFs completely soften at 25 K, with their critical behavior described by the same mathematical framework as the antiferromagnetic Fermi liquid model, yielding a fitted Curie-Weiss temperature of 𝜃≈0K. Additionally, we find that the nematic fluctuations are weakly coupled to the lattice, as evidenced by the absence of softening in nematic-coupled in-plane transverse acoustic phonons. Our discovery positions Sr𝑥⁢Ba1−𝑥⁢Ni2⁢As2 as a promising candidate for charge-fluctuation-driven superconductivity.

Aczel, Adam [ORNL] (ORCID:0000000319641943)↗

Lunar and Planetary Science XXXV: Dust: Theory and Experiments

The titles in this section include: 1) Experimental Study of the Radiation Pressure Forces on Isolated Micron-size Dust Particles; 2) Migration of Dust Particles and Their Collisions with the Terrestrial Planets; 3) Chemical In-Situ Analysis of Interplanetary and Interstellar Meteoroids; 4) Mass Spectrometer Calibration of Cassini Cosmic Dust Analyzer for Methane Ice via Laser Ablation; 5) Comparative Effects of 10.2 eV Photon and 200 keV Proton Irradiation on Condensed CO; 6) Experimental Studies on Heated and Unheated He-Irradiated Olivine Grains at Moderate He-Ion Fluences: Analogues to Radiation Damage in IDPs; 7) Impact Studies Using a One Stage Light Gas Gun; 8) Condensation Kinetics of Metallic Iron: An Experimental Study.

Source record↗

Disentangling High Harmonic Generation from Surface and Bulk States of a Topological Insulator

The discovery of topological phases has introduced a new dimension to materials science. Three-dimensional (3D) topological insulators (TIs) are a remarkable class of matter that is insulating in the bulk while hosting conductive topological surface states (TSSs) with unique charge and spin properties. High-order harmonic generation (HHG) has emerged as a powerful tool to probe condensed matter systems by providing insights into their electronic structure and dynamic behavior. Here, we investigate HHG in the prototype 3D-TI Bi$_2$Se$_3$. We demonstrate that the contributions of bulk and surface states to the harmonic emission can be controlled by tuning the thickness of thin film samples. An ultrathin (6 nm) film substantially enhances HHG from the surface states, while the bulk states dominate HHG in a thicker (50 nm) film. By applying a quasi-static terahertz perturbing field, we disentangle the bulk and surface responses and reveal the significant impact of the surface states' shift vector and Berry curvature on HHG. Our study provides effective methods for isolating the optical responses of TSSs from those of the bulk, which opens the door to resolving an ongoing debate regarding whether it is possible to reliably extract topological signatures in HHG.

Atomic Physics (physics.atom-ph)↗

Dicarboxylic acid anhydride condensation with compounds containing active methylene groups. 4: Some 4-nitrophthalic anhydride condensation reactions

By 4-nitrophthalic anhydride condensation with acetoacetate in acetic anhydride and triethylamine solution with subsequent breakdown of the intermediate condensation product, 5-nitroindanedione-1,3 was obtained. A 4-nitrophthalic anhydride with acetic anhydride, according to reaction conditions, may yield two products: in the presence of potassium acetate and at high temperatures 4-(or 5-)-nitro-2-acetylbenzoic acid is formed: in the presence of triethylamine and at room temperature 5-( or 6-)-nitrophthalic acetic acid is isolated. A 4-nitrophthalic anhydride and malonic acid in pyridine solution according to temperature yield either 5-( or 6-)-nitrophthalic acetic acid or 4-(or 5-)-nitro-2-acetylbenzoic acid.

Oskaja, V.↗

Microbial Characterization of Free Floating Condensate Aboard the Mir Space Station

Three samples of humidity condensate that had accumulated behind panels aboard the Russian space station Mir were collected and returned to earth for analysis. As these floating masses of liquid come into contact with the astronauts and the engineering systems, they have the potential to affect both crew health and systems performance. Using a combination of culturing techniques, a wide variety of organisms were isolated included Escherichia coli, Serratia marcescens, and a presumed Legionella species. In addition, microscopic analysis indicated the presence of protozoa, dust mites, and spirochetes. These findings suggest the need for more comprehensive microbial analysis of the environment through the use of new methodologies to allow a more thorough risk assessment of spacecraft. Copyright 2004 Springer-Verlag.

Spacecraft↗

NextSTEP Appendix A Modular ECLSS Effort Lessons Learned

NASA’s Artemis program provides the first steps for earth-independent exploration starting with crewed habitats in cislunar space and progressing toward crewed landings on the lunar surface that will prepare systems and crews for the exploration of Mars. The Next Space Technology for Exploration Partnerships (NextSTEP) is a public-private partnership model that facilitates commercial development of deep space exploration capabilities in support of more extensive human spaceflight missions in and beyond cislunar space. NASA issued the original NextSTEP Broad Agency Announcement (BAA) to U.S. industry in late 2014 and issued the second BAA (NextSTEP-2) in April 2016. The first appendix under NextSTEP-2, Appendix A, focused on developing deep space habitation concepts, engineering design and development, and risk reduction efforts leading to a habitation capability in cislunar space. NASA solicited concepts to develop and refine the evolvable, modular architecture, functional allocation options, standards, and common interfaces required to enable interoperability of the aggregate system to provide long duration deep space transit habitation, specifically enhancements and testing of deep space Environmental Control and Life Support Systems (ECLSS). Collins Aerospace, formerly UTC Aerospace Systems (UTAS), was awarded a Phase 1 and subsequent Phase 2 contract to “develop concepts that group ECLS systems into logical modules maximizing the use of common components and the development of unique methods and design concepts that support in-flight maintenance and repair for future exploration systems.” This paper summarizes the work accomplished under this effort, the lessons that can be applied to development of forthcoming habitation elements, and the gaps remaining to achieve a more resilient, maintainable, repairable and adaptable system capable of installation on a wide variety of habitat platforms. A primary accomplishment of this effort is the development and maturation of a modular palletization concept to enable standard rack interfaces, post-launch outfitting, and decoupling of structural supports that withstand launch environments from those needed for lower on-orbit loads in order to reduce installed mass and repurposing of panels within the habitat. In the course of the effort, Collins assessed numerous architecture trades, including the use of condensing and noncondensing heat exchangers, the ability of modular units to accommodate various habitat volumes and thermal loading, and the most appropriate order of and timing of delivery of regenerative ECLSS hardware to orbital habitats. In addition to the modularity of hardware elements, Collins developed software approaches for distributed/modular command, control, and communication systems and innovative Bayesian fault detection and isolation techniques. Finally, the effort explored advanced maintainability and supportability concepts including the definition of maintenance units (MUs) in place of the traditional Orbital Replacement Units (ORUs), increasing parts commonality to reduce the number and type of spare parts, the use of augmented reality to guide crews during maintenance and repair procedures, and how crews would prepare for and recover from long durations of habitat dormancy. Now that the NextSTEP Modular ECLSS effort has come to a close, it’s important to identify the lessons learned and where they can be leveraged to improve NASA’s broader program of ECLSS technology development and demonstration and ultimately how they can increase the performance of future surface and orbital habitats.

NextSTEP↗

NextSTEP Appendix A Modular ECLSS Effort Lessons Learned

NASA’s Artemis program provides the first steps for earth-independent exploration starting with crewed habitats in cislunar space and progressing toward crewed landings on the lunar surface that will prepare systems and crews for the exploration of Mars. The Next Space Technology for Exploration Partnerships (NextSTEP) is a public-private partnership model that facilitates commercial development of deep space exploration capabilities in support of more extensive human spaceflight missions in and beyond cislunar space. NASA issued the original NextSTEP Broad Agency Announcement (BAA) to U.S. industry in late 2014 and issued the second BAA (NextSTEP-2) in April 2016. The first appendix under NextSTEP-2, Appendix A, focused on developing deep space habitation concepts, engineering design and development, and risk reduction efforts leading to a habitation capability in cislunar space. NASA solicited concepts to develop and refine the evolvable, modular architecture, functional allocation options, standards, and common interfaces required to enable interoperability of the aggregate system to provide long duration deep space transit habitation, specifically enhancements and testing of deep space Environmental Control and Life Support Systems (ECLSS). Collins Aerospace, formerly UTC Aerospace Systems (UTAS), was awarded a Phase 1 and subsequent Phase 2 contract to “develop concepts that group ECLS systems into logical modules maximizing the use of common components and the development of unique methods and design concepts that support in-flight maintenance and repair for future exploration systems.” This paper summarizes the work accomplished under this effort, the lessons that can be applied to development of forthcoming habitation elements, and the gaps remaining to achieve a more resilient, maintainable, repairable and adaptable system capable of installation on a wide variety of habitat platforms. A primary accomplishment of this effort is the development and maturation of a modular palletization concept to enable standard rack interfaces, post-launch outfitting, and decoupling of structural supports that withstand launch environments from those needed for lower on-orbit loads in order to reduce installed mass and repurposing of panels within the habitat. In the course of the effort, Collins assessed numerous architecture trades, including the use of condensing and noncondensing heat exchangers, the ability of modular units to accommodate various habitat volumes and thermal loading, and the most appropriate order of and timing of delivery of regenerative ECLSS hardware to orbital habitats. In addition to the modularity of hardware elements, Collins developed software approaches for distributed/modular command, control, and communication systems and innovative Bayesian fault detection and isolation techniques. Finally, the effort explored advanced maintainability and supportability concepts including the definition of maintenance units (MUs) in place of the traditional Orbital Replacement Units (ORUs), increasing parts commonality to reduce the number and type of spare parts, the use of augmented reality to guide crews during maintenance and repair procedures, and how crews would prepare for and recover from long durations of habitat dormancy. Now that the NextSTEP Modular ECLSS effort has come to a close, it’s important to identify the lessons learned and where they can be leveraged to improve NASA’s broader program of ECLSS technology development and demonstration and ultimately how they can increase the performance of future surface and orbital habitats.

NextSTEP↗

Gravitational lensing of supernovae by dark matter candidates of mass M greater than about 0.001 solar masses

A review is presented concerning the gravitational lensing of supernovae by intervening condensed objects, including dark matter candidates such as dim stars and black holes. the expansion of the supernova beam within the lens produces characteristic time-dependent amplification and polarization which depend upon the mass of the lens. The effects of the shearing of the beam due to surrounding masses are considered, although the study of these effects is confined to isolated masses whose size is much less than that of the supernova (about 10 to the 15th cm). Equations for the effects of lensing and graphs comparing these effects in different classes of supernovae are compared. It is found that candidates for lensing would be those supernovae at least as bright as their parent galaxy, or above the range of luminosities expected for their spectral class.

Wagoner, Robert V.↗

Optimal coupling of Ho W 10 molecular magnets to superconducting circuits near spin clock transitions

A central goal in quantum technologies is to maximize GT 2 , where G stands for the coupling of a qubit to control and readout signals and T 2 is the qubit’s coherence time. Furthermore, this is challenging, as increasing G (e.g., by coupling the qubit more strongly to external stimuli) often leads to deleterious effects on T 2 . Here, we study the coupling of pure and magnetically diluted crystals of Ho W 10 magnetic clusters to microwave superconducting coplanar waveguides. Absorption lines give a broadband picture of the magnetic energy level scheme and, in particular, confirm the existence of level anticrossings at equidistant magnetic fields determined by the combination of crystal field and hyperfine interactions. Such “spin clock transitions” are known to shield the electronic spins against magnetic field fluctuations. The analysis of the microwave transmission shows that the spin-photon coupling also becomes maximum at these transitions. The results show that engineering spin-clock states of molecular systems offers a promising strategy to combine sizable spin-photon interactions with a sufficient isolation from unwanted magnetic noise sources.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Single-ion properties of the transverse-field Ising model material CoNb 2 O 6

We report CoNb 2 O 6 is one of the few materials that is known to approximate the one-dimensional transverse-field Ising model (1D-TFIM) near its quantum critical point. It has been inferred that Co 2+ acts as a pseudospin 1/2 with anisotropic exchange interactions that are largely Ising-like, enabling the realization of the TFIM. However, the behavior of CoNb 2 O 6 is known to diverge from the ideal TFIM under transverse magnetic fields that are far from the quantum critical point, requiring the consideration of additional anisotropic, bond-dependent (Kitaev-like) terms in the microscopic pseudospin-1/2 Hamiltonian. These terms are expected to be controlled in part by single-ion physics, namely the wave function for the pseudospin-1/2 angular momentum doublet. Here, we present the results of both inelastic neutron scattering measurements and electron paramagnetic resonance spectroscopy on CoNb 2 O 6 , which elucidate the single-ion physics of Co 2+ in CoNb 2 O 6 for the first time. We find that the system is well-described by an intermediate spin-orbit coupled Hamiltonian, and the ground state is a well-isolated Kramers doublet with an anisotropic g tensor. We provide the approximate wave functions for this doublet, which we expect will be useful in theoretical investigations of the anisotropic exchange interactions.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Nanomagnonic Cavities for Strong Spin-Magnon Coupling and Magnon-Mediated Spin-Spin Interactions

We present a theoretical approach to use ferromagnetic or ferrimagnetic nanoparticles as microwave nanomagnonic cavities to concentrate microwave magnetic fields into deeply subwavelength volumes ~ 10 –13 mm 3 . In this work, we show that the field in such nanocavities can efficiently couple to isolated spin emitters (spin qubits) positioned close to the nanoparticle surface reaching the single magnon-spin strong-coupling regime and mediate efficient long-range quantum state transfers between isolated spin emitters. Nanomagnonic cavities thus pave the way toward magnon-based quantum networks and magnon-mediated quantum gates.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Radiative tearing - Magnetic reconnection on a fast thermal-instability time scale

Two energy modification mechanisms which are known to occur in sheared magnetic fields are the tearing and thermal instabilities. These processes can be studied separately with formalisms incorporating just the effective driving mechanism of interest (finite resistivity for the tearing mode and unstable radiation for the thermal mode). A model which includes both effects, and a temperature-dependent resistivity, indicates that modified forms of these two instabilities may coexist for identical physical conditions. When they are isolated computationally, one can show that their limiting growth rates are approximately those of the uncoupled instabilities. The spatial structure and energy content of these two new hybrid processes are then individually examined and are found to differ considerably from those obtained from separate treatments of the driving mechanisms. The faster radiative instability, which has a hydromagnetically scaled growth rate like the condensation mode of the thermal instability, is shown to involve a substantial amount of magnetic field reconnection. This can be partially explained by a large temperature drop (or resistivity rise) at the X-point. The island width of the Coulomb-coupled radiative mode is 30 percent of that produced by a comparable level of the slower tearing instability. In addition, the perturbed magnetic energy in the radiative instability is 5 times that of the perturbed thermal energy, indicating an appreciable modification of the initial magnetic structure.

Steinolfson, R. S.↗

Electric-field control of the nucleation and motion of isolated three-fold polar vertices

Recently various topological polar structures have been discovered in oxide thin films. Despite the increasing evidence of their switchability under electrical and/or mechanical fields, the dynamic property of isolated ones, which is usually required for applications such as data storage, is still absent. Here, we show the controlled nucleation and motion of isolated three-fold vertices under an applied electric field. At the PbTiO 3 /SrRuO 3 interface, a two-unit-cell thick SrTiO 3 layer provides electrical boundary conditions for the formation of three-fold vertices. Utilizing the SrTiO 3 layer and in situ electrical testing system, we find that isolated three-fold vertices can move in a controllable and reversible manner with a velocity up to ~629 nm s -1 . Microstructural evolution of the nucleation and propagation of isolated three-fold vertices is further revealed by phase-field simulations. This work demonstrates the ability to electrically manipulate isolated three-fold vertices, shedding light on the dynamic property of isolated topological polar structures.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗