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At least 739 records · Page 41

Quantifying accessible sites and reactivity on titania–silica (photo)catalysts: Refining TOF calculations

It can be difficult to determine the number of active atoms accessible to the fluid phase in mixed oxide catalysts, as required for obtaining true turnover frequencies (TOF). Here, we utilize the selective titration of surface Ti atoms with phenylphosphonic acid (PPA) on TiO 2 –SiO 2 materials to estimate the number of reactant-accessible sites. TiO 2 –SiO 2 composites were synthesized over a range of Ti loadings from grafting of titanocene dichloride (Cp 2 TiCl 2 ) or tetraethoxy orthotitanate (TEOT) on SiO 2 and sol–gel co-hydrolysis of Si and Ti alkoxides. The materials were characterized by DRUV–vis, XRD, BET, and XANES. Despite the significant morphological and electronic differences, materials prepared by Cp 2 TiCl 2 and TEOT yielded a near-constant TOF of 0.14 h -1 (±0.04) across Ti loadings, for benzyl alcohol photooxidation, when normalizing rates by sites titrated by PPA. The fraction of Ti atoms titrated by PPA was strongly dependent on synthesis method and surface density. PPA titration and benzyl alcohol photooxidation may be useful measures of surface accessibility in other supported oxides.

Eaton, Todd R.↗

Deciphering Distinct Overpotential-Dependent Pathways for Electrochemical CO 2 Reduction Catalyzed by an Iron–Terpyridine Complex

[Fe(tpyPY2Me)] 2+ ([Fe] 2+ ) is a homogeneous electrocatalyst for converting CO 2 into CO featuring low overpotentials of <100 mV, near-unity selectivity, and high activity with turnover frequencies faster than 100 000 s -1 . To identify the origins of its exceptional performance and inform future catalyst design, we report a combined computational and experimental study that establishes two distinct mechanistic pathways for electrochemical CO 2 reduction catalyzed by [Fe] 2+ as a function of applied overpotential. Electrochemical data shows the formation of two catalytic regimes at low (η TOF/2 of 160 mV) and high (η TOF/2 of 590 mV) overpotential plateaus. We propose that at low overpotentials [Fe] 2+ undergoes a two-electron reduction, two-proton-transfer mechanism (electrochemical-electrochemical-chemical-chemical, EECC), where turnover occurs through the dicationic iron complex, [Fe] 2+ . Computational analysis supports the importance of the singlet ground-state electronic structure for CO 2 binding and that the rate-limiting step is the second protonation in this low-overpotential regime. When more negative potentials are applied, an additional electron-transfer event occurs through either a stepwise or proton-coupled electron-transfer (PCET) pathway, enabling catalytic turnover from the monocationic iron complex ([Fe] + ) via an electrochemical-chemical-electrochemical-chemical (ECEC) mechanism. Comparison of experimental kinetic data obtained from variable controlled potential electrolysis (CPE) experiments with direct product detection with calculated rates obtained from the energetic span model supports the PCET pathway as the most likely mechanism. Moreover, we build upon this mechanistic understanding to propose the design of an improved ligand framework that is predicted to stabilize the key transition states identified in our study and explore their electronic structures using an energy decomposition analysis. Finally, taken together, this work highlights the value of synergistic computational/experimental approaches to decipher mechanisms of new electrocatalysts and direct the rational design of improved platforms.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Inhomogeneity of Cellulose Microfibril Assembly in Plant Cell Walls Revealed with Sum Frequency Generation Microscopy

Sum frequency generation (SFG) vibrational spectroscopy can selectively detect and analyze noncentrosymmetric components interspersed in amorphous matrices; this principle has been used for studies of nanoscale structure and mesoscale assembly of cellulose in plant cell walls. However, the spectral information averaged over a large area or volume cannot provide regiospecific or tissue-specific information of different cells in plants. Here, we demonstrate spatially resolved SFG analysis and imaging by combining a broad-band SFG spectroscopy system with an optical microscope. The system was designed to irradiate both narrow-band 800 nm and broad-band tunable IR beams through a single reflective objective lens, but from opposite sides of the surface normal direction of the sample. The developed technique was used to reveal inhomogeneous distributions of cellulose microfibrils within single cell walls, such as cotton fibers and onion epidermis as well as among different tissues in Arabidopsis inflorescence stems and bamboo culms. SFG microscopy can be used for vibrational spectroscopic imaging of other biological systems in complement to conventional Fourier transform infrared spectroscopy and confocal Raman microscopy.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Laser-pulse compression in a collisional plasma under weak-relativistic ponderomotive nonlinearity

We present theory and numerical analysis which demonstrate laser-pulse compression in a collisional plasma under the weak-relativistic ponderomotive nonlinearity. Plasma equilibrium density is modified due to the ohmic heating of electrons, the collisions, and the weak relativistic-ponderomotive force during the interaction of a laser pulse with plasmas. First, within one-dimensional analysis, the longitudinal self-compression mechanism is discussed. Three-dimensional analysis (spatiotemporal) of laser pulse propagation is also investigated by coupling the self-compression with the self-focusing. In the regime in which the laser becomes self-focused due to the weak relativistic-ponderomotive nonlinearity, we provide results for enhanced pulse compression. The results show that the matched interplay between self-focusing and self-compression can improve significantly the temporal profile of the compressed pulse. Enhanced pulse compression can be achieved by optimizing and selecting the parameters such as collision frequency, ion-temperature, and laser intensity.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

The possibility of anesthesia stimulated by a train of current pulses

This study considers a simple theoretical model of blocking the passage of signals (action potentials) from sensory neurons, thereby affecting anesthesia without the use of anesthetics as a result of a sequence of unipolar current pulses generated by an external source. The proposed model allows the selection of parameters and the required frequency of the repetition of current pulses for the possible implementation of anesthesia, depending on the electrical characteristics of the skin and the conductivity of the saline solution in which the myelinated nerve fibers are located.

59 BASIC BIOLOGICAL SCIENCES↗

MIGHTEE: total intensity radio continuum imaging and the COSMOS/XMM-LSS Early Science fields

ABSTRACT MIGHTEE is a galaxy evolution survey using simultaneous radio continuum, spectropolarimetry, and spectral line observations from the South African MeerKAT telescope. When complete, the survey will image ∼20 deg2 over the COSMOS, E-CDFS, ELAIS-S1, and XMM-Newton Large Scale Structure field (XMM-LSS) extragalactic deep fields with a central frequency of 1284 MHz. These were selected based on the extensive multiwavelength data sets from numerous existing and forthcoming observational campaigns. Here, we describe and validate the data processing strategy for the total intensity continuum aspect of MIGHTEE, using a single deep pointing in COSMOS (1.6 deg2) and a three-pointing mosaic in XMM-LSS (3.5 deg2). The processing includes the correction of direction-dependent effects, and results in thermal noise levels below 2 $\mathrm{\mu }$Jy beam−1 in both fields, limited in the central regions by classical confusion at ∼8 arcsec angular resolution, and meeting the survey specifications. We also produce images at ∼5 arcsec resolution that are ∼3 times shallower. The resulting image products form the basis of the Early Science continuum data release for MIGHTEE. From these images we extract catalogues containing 9896 and 20 274 radio components in COSMOS and XMM-LSS, respectively. We also process a close-packed mosaic of 14 additional pointings in COSMOS and use these in conjunction with the Early Science pointing to investigate methods for primary beam correction of broad-band radio images, an analysis that is of relevance to all full-band MeerKAT continuum observations, and wide-field interferometric imaging in general. A public release of the MIGHTEE Early Science continuum data products accompanies this article.

Heywood, I. (ORCID:0000000168645057)↗

Search for continuous gravitational wave signals from luminous dark photon superradiance clouds with LVK O3 observations

Superradiance clouds of kinetically mixed dark photons around spinning black holes can produce observable multimessenger electromagnetic and gravitational wave signals. The cloud generates electric fields of up to a teravolt-per-meter, which leads to a cascade production of charged particles, yielding a turbulent quasiequilibrium plasma around the black hole, and resulting in electromagnetic fluxes ranging from supernova to pulsar-like luminosities. For stellar mass black holes, such systems resemble millisecond pulsars and are expected to emit pulsating radio waves and continuous gravitational waves (CWs) within the LIGO-Virgo-KAGRA (LVK) sensitivity band. We select 44 sources with approximately coincident frequencies or positive frequency drifts from existing pulsar catalogs as potential candidates of long-lasting superradiance clouds around old Galactic black holes. For a subset of 34 sources that are well measured and have not been previously targeted, we perform the first search for CW emission in LVK data from the third observing run. We find no evidence of a CW signal and place 95% confidence level upper limits on the emitted strain amplitude. We interpret these results, together with limits from previous searches, in terms of the underlying dark photon theory by performing an analysis of the expected signals from superradiance clouds from Galactic black holes. Finally, we find that, even for moderately spinning black holes, the absence of an observed CW signal disfavors a discrete set of dark photon masses between about 10 −13 and 10 −12 eV/c 2 and kinetic mixing couplings in the range of 10 −9 –10 −7 , subject to assumptions about the properties of the black hole population and the cloud’s electromagnetic emission.

astronomical black holes↗

Electronic and Vibrational Dynamics of Hollow Au Nanocages Embedded in Cu 2 O Shells

Abstract We have synthesized hollow Au nanocages embedded within thick porous shells of cuprous oxide (Cu 2 O). The shell causes a significant redshift of the localized surface plasmon resonance of Au into the near‐ IR . Electron–phonon coupling in the Au nanocage is 3–6 times faster in the core–shell structure due to the higher thermal conductivity of Cu 2 O compared to water. Coherent phonon oscillations within the Au lattice are characterized by a breathing mode of the entire structure for both bare and core–shell nanocages, an assignment made through the use of structural mechanics simulations. The experimental frequencies are obtained through simulations by selectively applying a force to the shell of the core–shell structure. We interpret this as rapid thermal expansion of the gold leading to a mechanical force that acts on the shell.

Szymanski, Paul↗

Electric power processing, distribution and control for advanced aerospace vehicles.

The results of a current study program to develop a rational basis for selection of power processing, distribution, and control configurations for future aerospace vehicles including the Space Station, Space Shuttle, and high-performance aircraft are presented. Within the constraints imposed by the characteristics of power generation subsystems and the load utilization equipment requirements, the power processing, distribution and control subsystem can be optimized by selection of the proper distribution voltage, frequency, and overload/fault protection method. It is shown that, for large space vehicles which rely on static energy conversion to provide electric power, high-voltage dc distribution (above 100 V dc) is preferable to conventional 28 V dc and 115 V ac distribution per MIL-STD-704A. High-voltage dc also has advantages over conventional constant frequency ac systems in many aircraft applications due to the elimination of speed control, wave shaping, and synchronization equipment.

Krausz, A.↗

On the theory of compliant wall drag reduction in turbulent boundary layers

A theoretical model has been developed which can explain how the motion of a compliant wall reduces turbulent skin friction drag. Available experimental evidence at low speeds has been used to infer that a compliant surface selectively removes energy from the upper frequency range of the energy containing eddies and through resulting surface motions can produce locally negative Reynolds stresses at the wall. The theory establishes a preliminary amplitude and frequency criterion as the basis for designing effective drag reducing compliant surfaces.

Ash, R. L.↗

A spaceborne receiver for measuring electromagnetic field intensity

Description of a very accurately controlled receiver for monitoring the electromagnetic radiations in both existing and projected space communication bands. Based on analysis of the existing and projected space communication bands, 108 to 174 MHz, 240 to 478 MHz, and 1535 to 1665 MHz were covered. The receiver achieves accurate control via a digitally tuned synthesizer and a wide range of digital control including frequency band coverage and gain control selection. Digital memory was provided to store 16 separate digital command instructions which can be programmed via a command data link. The receiver provides for transmission to the ground of both a predetection signal and signals in digital format, which in turn, were provided by sampling and analog-to-digital conversions.

Reich, B. W.↗

Size and modal analyses of fines and ultrafines from some Apollo 17 samples

Scanning electron and optical microscopy techniques have been used to determine the grain-size frequency distributions and morphology-based modal analyses of fine and ultrafine fractions of some Apollo 17 regolith samples. There are significant and large differences between the grain-size frequency distributions of the less than 10-micron size fraction of Apollo 17 samples, but there are no clear relations to the local geologic setting from which individual samples have been collected. This may be due to effective lateral mixing of regolith particles in this size range by micrometeoroid impacts. None of the properties of the frequency distributions support the idea of selective transport of any fine grain-size fraction, as has been proposed by other workers. All of the particle types found in the coarser size fractions also occur in the less than 10-micron particles. In the size range from 105 to 10 microns there is a strong tendency for the percentage of regularly shaped glass to increase as the graphic mean grain size of the less than 1-mm size fraction decreases, both probably being controlled by exposure age.

Greene, G. M.↗

A long-range and long-life telemetry data-acquisition system for heart rate and multiple body temperatures from free-ranging animals

The system includes an implantable transmitter, external receiver-retransmitter collar, and a microprocessor-controlled demodulator. The size of the implant is suitable for animals with body weights of a few kilograms or more; further size reduction of the implant is possible. The ECG is sensed by electrodes designed for internal telemetry and to reduce movement artifacts. The R-wave characteristics are then specifically selected to trigger a short radio frequency pulse. Temperatures are sensed at desired locations by thermistors and then, based on a heartbeat counter, transmitted intermittently via pulse interval modulation. This modulation scheme includes first and last calibration intervals for a reference by ratios with the temperature intervals to achieve good accuracy even over long periods. Pulse duration and pulse sequencing are used to discriminate between heart rate and temperature pulses as well as RF interference.

Lund, G. F.↗

Application of a ground based minicomputer system for real time, closed loop control of remotely piloted aircraft models used in stall/spin research

The paper describes a minicomputer-based, real-time closed loop remote control system at NASA Langley outdoor facility which is used to determine the stall/departure/spin characteristics of high-performance aircraft. The experiments are conducted with 15% dynamically scaled, unpowered models that are dropped from 3000 m and ground controlled. The effects of time delays and sampling rates on the stability of the control system and the selection of digital algorithms to meet frequency response and real time constraints are examined. Also described is the implementation of the modular software for the flexible programming of multi-axis control laws.

Montoya, R. J.↗

Acoustic measurements of the X-wing rotor

Noise measurements of a stoppable X-wing rotor system model, tested in the Ames 40- by 80-foot wind tunnel, are summarized. Performance, control system stability, and noise of the model were investigated at various forward speeds, tip speeds, collective blade angles, jet blowing velocities, and model attack angles. The model was tested in the rotating wing helicopter configuration, in the fixed wing configuration, and in wing configurations between the two. Noise data obtained in the helicopter configuration at the two highest tip speeds (Mach 0.44 and 0.47) and at wind tunnel speeds below 140 knots are reported. Test configuration and performance information are included. General acoustic measurements (dB, dBA, and PNdB) at six microphone locations are presented for all conditions under which the background noise was below the model noise. More specific measurements (1/3-octave and blade passage frequency harmonic levels) are presented for selected conditions. Graphs of dBA and 1/3-octave spectra, which show the noise trends as functions of operating condition, are included. The noise depends mainly on the jet blowing velocity. The noise levels were highest at moderate jet blowing velocities, less at the highest velocity, and lowest with no blowing at all.

Mosher, M.↗

Space structure vibration modes: How many exist? Which ones are important?

This report attempts to shed some light on the two issues raised in the title, namely, how many vibration modes does a real structure have, and which of these modes are important? The surprise-free answers to these two questions are, respectively, an infinite number and the first several modes. The author argues that the absurd subspace (all but the first billion modes) is not a strength of continuum modeling, but, in fact, a weakness. Partial differential equations are not real structures, only mathematical models. This note also explains (1) that the PDE model and the finite element model are, in fact, the same model, the latter being a numerical method for dealing with the former, (2) that modes may be selected on dynamical grounds other than frequency alone, and (3) that long slender rods are useful as primitive cases but dangerous to extrapolate from.

Hughes, P. C.↗

A Battery Charger and State of Charge Indicator

A battery charger which has a full wave rectifier in series with a transformer isolated 20 kHz dc-dc converter with high frequency switches, which are programmed to actively shape the input dc line current to be a mirror image of the ac line voltage is discussed. The power circuit operates at 2 kW peak and 1 kW average power. The BC/SCI has two major subsystems: (1) the battery charger power electronics with its controls; and (2) a microcomputer subsystem which is used to acquire battery terminal data and exercise the state of charge software programs. The state of charge definition employed is the energy remaining in the battery when extracted at a 10 kW rate divided by the energy capacity of a fully charged new battery. The battery charger circuit is an isolated boost converter operating at an internal frequency of 20 kHz. The switches selected for the battery charger are the single most important item in determining its efficiency. The combination of voltage and current requirements dictate the use of high power NPN Darlington switching transistors. The power circuit topology is a three switch design which utilizes a power FET on the center tap of the isolation transformer and the power Darlingtons on each of the two ends. An analog control system is employed to accomplish active input current waveshaping as well as the necessary regulation.

Latos, T. S.↗