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At least 847 records · Page 47

Modification of the Coordination Environment of Active Sites on MoC for High-Efficiency CH 4 Production

Modulating the coordination environment of active sites on catalyst surfaces is crucial to developing effective catalysts and controlling catalysis, but it is highly challenging. Guided by our first-principles calculations, we experimentally accomplish the modification of the coordination environment of active sites on MoC nanoparticle surfaces by anchoring pyridinic N atom rings of holey graphene on Mo atoms. The rings produce electrostatic forces that enable the tuning of the Mo sites' affinity to reaction intermediates, which passivates Mo hollow sites, activates Mo top sites and reduces the over-adsorption of OH on the Mo active sites, as predicted by the calculations. The atomic-level modification is well confirmed by atomic-resolution imaging, high-resolution electron tomography, synchrotron soft X-ray spectroscopy and operando electrochemical infrared spectroscopy. Consequently, the Faradaic efficiency for CO 2 reduction to CH 4 is enhanced from 16% to 89%, a record high efficiency so far, in aqueous electrolyte. Meantime, it also exhibits a negligible activity loss over 50 h.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Copoly(Imide Siloxane) Abhesive Materials with Varied Siloxane Oligomer Length

Incorporation of PDMS moieties into a polyimide matrix lowered the surface energy resulting in enhanced adhesive interactions. Polyimide siloxane materials were generated using amine-terminated PDMS oligomers of different lengths to study changes in surface migration behavior, phase segregation, mechanical, thermal, and optical properties. These materials were characterized using contact angle goniometry, tensile testing, and differential scanning calorimetry. The surface migration behavior of the PDMS component depended upon the siloxane molecular weight as indicated by distinct relationships between PDMS chain length and advancing water contact angles. Similar correlations were observed for percent elongation values obtained from tensile testing, while the addition of PDMS reduced the modulus. High fidelity topographical modification via laser ablation patterning further reduced the polyimide siloxane surface energy. Initial particulate adhesion testing experiments demonstrated that polyimide siloxane materials exhibited greater abhesive interactions relative to their respective homopolyimides.

Wohl, Christopher J.↗

Effect of surface roughness on the microwave emission from soils

The effect of surface roughness on the brightness temperature of a moist terrain was studied through the modification of Fresnel reflection coefficient and using the radiative transfer equation. The modification involves introduction of a single parameter to characterize the roughness. It is shown that this parameter depends on both the surface height variance and the horizontal scale of the roughness. Model calculations are in good quantitative agreement with the observed dependence of the brightness temperature on the moisture content in the surface layer. Data from truck mounted and airborne radiometers are presented for comparison. The results indicate that the roughness effects are greatest for wet soils where the difference between smooth and rough surfaces can be as great as 50K.

Choudhury, B. J.↗

Estimation of ground temperature from GFCR radiometric signal

A procedure was developed which demonstrates the feasibility of estimating actual surface temperature from the effective brightness temperature which can be conveniently measured by a radiometer from remote sensing platforms. Atmospheric corrections to the effective brightness temperature are computed corresponding to the 'base model' atmosphere and several modifications of this caused by deviations of the various atmospheric or surface parameters from their base model values. Simple analytical relations were established between the deviations of these parameters and the additional temperature corrections required to compensate for them. Effects of simultaneous variation of several parameters also were examined. Use of these analytical relations, instead of radiative transfer calculations, results in tremendous savings in data reduction costs.

Gupia, S. K.↗

Control of the boundary layer separation about an airfoil by active surface heating

Application of active control to separated flow on the RC(6)-08 airfoil at high angle of attack by localized surface heating is numerically simulated by integrating the compressible two-dimensional nonlinear Navier-Stokes equations solver. Active control is simulated by local modification of the temperature boundary condition over a narrow strip on the upper surface of the airfoil. Both mean and perturbed profiles are favorably altered when excited with the same natural frequency of the shear layer by moderate surface heating for both laminar and turbulent separation. The shear layer is found to be very sensitive to localized surface heating in the vicinity of the separation point. The excitation field at the surface sufficiently altered both the local as well as the global circulation to cause a significant increase in lift and reduction in drag.

Maestrello, Lucio↗

Improved Hydrology over Peatlands in a Global Land Modeling System

Peatlands of the Northern Hemisphere represent an important carbon pool that mainly accumulated since the last ice age under permanently wet conditions in specific geological and climatic settings. The carbon balance of peatlands is closely coupled to water table dynamics. Consequently, the future carbon balance over peatlands is strongly dependent on how hydrology in peatlands will react to changing boundary conditions, e.g. due to climate change or regional water level drawdown of connected aquifers or streams. Global land surface modeling over organic-rich regions can provide valuable global-scale insights on where and how peatlands are in transition due to changing boundary conditions. However, the current global land surface models are not able to reproduce typical hydrological dynamics in peatlands well. We implemented specific structural and parametric changes to account for key hydrological characteristics of peatlands into NASA's GEOS-5 Catchment Land Surface Model (CLSM, Koster et al. 2000). The main modifications pertain to the modeling of partial inundation, and the definition of peatland-specific runoff and evapotranspiration schemes. We ran a set of simulations on a high performance cluster using different CLSM configurations and validated the results with a newly compiled global in-situ dataset of water table depths in peatlands. The results demonstrate that an update of soil hydraulic properties for peat soils alone does not improve the performance of CLSM over peatlands. However, structural model changes for peatlands are able to improve the skill metrics for water table depth. The validation results for the water table depth indicate a reduction of the bias from 2.5 to 0.2 m, and an improvement of the temporal correlation coefficient from 0.5 to 0.65, and from 0.4 to 0.55 for the anomalies. Our validation data set includes both bogs (rain-fed) and fens (ground and/or surface water influence) and reveals that the metrics improved less for fens. In addition, a comparison of evapotranspiration and soil moisture estimates over peatlands will be presented, albeit only with limited ground-based validation data. We will discuss strengths and weaknesses of the new model by focusing on time series of specific validation sites.

Bechtold, M.↗

Estimation of surface temperature in remote pollution measurement experiments

A simple algorithm has been developed for estimating the actual surface temperature by applying corrections to the effective brightness temperature measured by radiometers mounted on remote sensing platforms. Corrections to effective brightness temperature are computed using an accurate radiative transfer model for the 'basic atmosphere' and several modifications of this caused by deviations of the various atmospheric and surface parameters from their base model values. Model calculations are employed to establish simple analytical relations between the deviations of these parameters and the additional temperature corrections required to compensate for them. Effects of simultaneous variation of two parameters are also examined. Use of these analytical relations instead of detailed radiative transfer calculations for routine data analysis results in a severalfold reduction in computation costs.

Gupta, S. K.↗

Comparisons between Geosat and Seasat tracking over non-ocean surfaces

The differences in both the quantity and quality of the nonocean measurements of the Geosat and Seasat altimeters due to the tracker modifications and satellite and antenna design changes are presented. The Geosat tracker exhibits more agility over the rougher surfaces and therefore is able to maintain lock better than Seasat. Large off-nadir attitude excursions created differences in Geosat tracking between cycles. The Geosat altimeter was at times able to track over surfaces Seasat could not, but sometimes the acquisition problem was worse. It is observed that Geosat yields denser coverage, but over land Seasat measurements yield a better overall picture of the general topography. It is concluded that the Geosat elevation data set over land can best be utilized to augment the information obtained from the Seasat data and is most useful when investigating topography at scales less than 100 km.

Brenner, A. C.↗

Space Shuttle separate-surface control-system study

A control system concept is presented that produces proportional control of yaw moment for the space shuttle from early entry to Mach 2 with only software modifications of the vehicle. It uses separate deflections of the inboard and outboard elevon surfaces and is evaluated, by determining the maximum static yawing moment available by considering the deflection limits of the elevon surfaces. A proportional moment slightly in excess of that produced by the most effective reaction control system (RCS) jet for yaw control can be obtained. In addition to the static moment study, a control law is designed which is intended to produce desired flying qualities.

Brown, L. W.↗

Influence of Ply Waviness on Fatigue Life of Tapered Composite Flexbeam Laminates

Nonlinear tapered flexbeam laminates, with significant ply waviness, were cut from a full-size composite rotor hub flexbeam. The specimens were tested under combined axial tension and cyclic bending loads. All of the specimens had wavy plies through the center and near the surfaces (termed marcelled areas), although for some of the specimens the surface marcels were very obvious, and for others they were much smaller. The specimens failed by first developing cracks through the marcels at the surfaces, and then delaminations grew from those cracks, in both directions. Delamination failure occurred in these specimens at significantly shorter fatigue lives than similar specimens without waviness, tested in ref. 2. A 2D finite element model was developed which closely approximated the flexbeam geometry, boundary conditions, and loading. In addition, the FE model duplicated the waviness observed in one of the test specimens. The model was analyzed using a geometrically nonlinear FE code. Modifications were made to the original model to reduce the amplitude of the marcels near the surfaces. The analysis was repeated for each modification. Comparisons of the interlaminar normal stresses, sigma(sub n), in the various models showed that under combined axial-tension and cyclic-bending loading, for marcels of the same aspect ratio, sigma(sub n) stresses increased as the distance along the taper, from thick to thin end, increased. For marcels of the same aspect ratio and at the same X-location along the taper, sigma(sub n) stresses decreased as the distance from the surface into the flexbeam interior increased. A technique was presented for determining the smallest acceptable marcel aspect ratio at various locations in the flexbeam.

Murri, Gretchen B.↗

Effect of surface roughness on the microwave emission from soils

The effect of surface roughness on the brightness temperature of a moist terrain has been studied through the modification of Fresnel reflection coefficient and using the radiative transfer equation. The modification involves introduction of a single parameter to characterize the roughness. It is shown that this parameter depends on both the surface height variance and the horizontal scale of the roughness. Model calculations are in good quantitative agreement with the observed dependence of the brightness temperature on the moisture content in the surface layer. Data from truck mounted and airborne radiometers are presented for comparison. The results indicate that the roughness effects are great for wet soils where the difference between smooth and rough surfaces can be as great as 50 K.

Choudhury, B. J.↗

30S subunit recognition and G1405 modification by the aminoglycoside-resistance 16S ribosomal RNA methyltransferase RmtC

Acquired ribosomal RNA (rRNA) methylation has emerged as a significant mechanism of aminoglycoside resistance in pathogenic bacterial infections. Modification of a single nucleotide in the ribosome decoding center by the aminoglycoside-resistance 16S rRNA (m 7 G1405) methyltransferases effectively blocks the action of all 4,6-deoxystreptamine ring-containing aminoglycosides, including the latest generation of drugs. To define the molecular basis of 30S subunit recognition and G1405 modification by these enzymes, we used a S-adenosyl-L-methionine analog to trap the complex in a postcatalytic state to enable determination of a global 3.0 Å cryo-electron microscopy structure of the m 7 G1405 methyltransferase RmtC bound to the mature Escherichia coli 30S ribosomal subunit. This structure, together with functional analyses of RmtC variants, identifies the RmtC N-terminal domain as critical for recognition and docking of the enzyme on a conserved 16S rRNA tertiary surface adjacent to G1405 in 16S rRNA helix 44 (h44). To access the G1405 N7 position for modification, a collection of residues across one surface of RmtC, including a loop that undergoes a disorder-to order transition upon 30S subunit binding, induces significant distortion of h44. This distortion flips G1405 into the enzyme active site where it is positioned for modification by two almost universally conserved RmtC residues. Further, these studies expand our understanding of ribosome recognition by rRNA modification enzymes and present a more complete structural basis for future development of strategies to inhibit m 7 G1405 modification to resensitize bacterial pathogens to aminoglycosides.

59 BASIC BIOLOGICAL SCIENCES↗

Crater formation and modification on the icy satellites of Uranus and Saturn - Depth/diameter and central peak occurrence

Fresh crater shapes, in particular crater depth/diameter ratios d/D, have been measured for craters on nine of the icy satellites. Crater depths were determined from photoclinometry plus some shallow measurements. Interior morphology, including rimwall slope, was also examined from photoclinometry profiles. Central peak statistics and the characteristic break in slope of d/D curves were determined in order to estimate the transition diameter from simple to complex craters. Crater morphology and transition diameters on the icy satellites were then compared with crater morphology on the terrestrial rocky planets in order to separate or evaluate the relative importance and similarity of surface gravity and target characteristics in controlling crater formation and modification in icy and rocky targets. Estimates of effective rheologies of the target materials were also obtained based on morphologic changes.

Schenk, Paul M.↗

Root gravitropism in maize and Arabidopsis

Research during the period 1 March 1992 to 30 November 1993 focused on improvements in a video digitizer system designed to automate the recording of surface extension in plants responding to gravistimulation. The improvements included modification of software to allow detailed analysis of localized extension patterns in roots of Arabidopsis. We used the system to analyze the role of the postmitotic isodiametric growth zone (a region between the meristem and the elongation zone) in the response of maize roots to auxin, calcium, touch and gravity. We also used the system to analyze short-term auxin and gravitropic responses in mutants of Arabidopsis with reduced auxin sensitivity. In a related project, we studied the relationship between growth rate and surface electrical currents in roots by examining the effects of gravity and thigmostimulation on surface potentials in maize roots.

Evans, Michael L.↗

Mechanisms of Oxide Formation in the Self-Reacting Friction Stir Weld Process

The initial objective of this study was to evaluate the effect of an extended delay time between preweld cleaning and the completion of a self-reacting friction stir welding (SRFSW) process on the resulting quality of various thickness panels of AA2219-T87. The current NASA standard specifies no more than a 48 hour delay between preweld cleaning and actual welding. The concern is whether increasing the cleaning delay time results in development of the residual oxide defect (ROD) in SRFSW. This concern emanates from the possibility of increased time correlating with increased oxide layer thickness on the faying surfaces. Oxide content on the faying surfaces has been reported to correlate with the occurrence of the ROD which reduces mechanical properties. When the SRFSW process was first adopted by the NASA Marshall Space Flight Center (MSFC), unexpected low tensile values that resulted were attributed to oxides within the weld that appeared to follow the former faying surface contours. Mitigation of the ROD was achieved through a combination of modifications to the processing parameters, tool designs, and incorporation of a weld seam offset. Two operations are involved in preweld cleaning: the first is removal of oil and grease, and the second is removal of surface oxides. In arc welding, improper cleaning of the faying surfaces of aluminum welded joints can increase the sensitivity toward development of defects. As the aluminum is locally melted, these contaminants contribute toward the development of porosity, inclusions, entrapped oxides, and other discontinuities which can degrade the strength of the weld joint. For weldment of large structures, the weld joint is typically cleaned, fit-up, and tack welded prior to the final full penetration welding pass. Because of the stringent joint fit-up requirements for mismatch and peaking for launch vehicle structures, the joint fit-up can sometimes contribute to lengthy delays between cleaning and tack welding, especially for circumferential weld joints on large diameter components. When the conventional friction stir welding (CFSW) process was introduced at the NASA MSFC, there was no procedure for cleaning prior to the solid-state joining process. As the process expanded to include SRFSW, preparation of the faying, crown, and root surfaces were implemented to overcome the ROD. Although the solid-state process is not expected to reach temperatures high enough for dissociation of the native oxide layer, concern remained regarding the redeposition of the native oxide layer within the stir zone. NASA has previously established the allowable time at 48 hours between preweld cleaning and a SRFSW process. The effect of potential 2 contamination resulting from an extended delay to 188 hours was subsequently evaluated for SRFSWs using tensile testing and metallographic imaging. Tensile specimens were tested at room temperature (RT), and at cryogenic conditions of liquid nitrogen (LN2) and liquid hydrogen. No detrimental effect on weld quality, as determined by weld strength, was reported for cleaning delays of 48, 120, 168, 240 or 288 hours. While no trends were established in this study, which extended the delay from 48 to 188 hours, there were a few outliers in terms of ultimate tensile strength (UTS). According to M. Fisher's 2014 Boeing Company Memo no. EYBF-MAF-14-029, all outliers were above the minimum acceptance criteria, but out of family with respect to the average values. As the robustness and reliability of any process ultimately depends on the average values as well as the outliers, an understanding of the cause of these outliers will ultimately improve the process. This report examines those outliers and their possible causes.

Schneider, J. A.↗

Solution-Deposited and Patternable Conductive Polymer Thin-Film Electrodes for Microbial Bioelectronics

Microbial bioelectronic devices integrate naturally occurring or synthetically engineered electroactive microbes with microelectronics. These devices have a broad range of potential applications, but engineering the biotic–abiotic interface for biocompatibility, adhesion, electron transfer, and maximum surface area remains a challenge. Prior approaches to interface modification lack simple processability, the ability to pattern the materials, and/or a significant enhancement in currents. We report a novel conductive polymer coating that significantly enhances current densities relative to unmodified electrodes in microbial bioelectronics is reported. The coating is based on a blend of poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonate) (PEDOT:PSS) crosslinked with poly(2-hydroxyethylacrylate) (PHEA) along with a thin polydopamine (PDA) layer for adhesion to an underlying indium tin oxide (ITO) electrode. When used as an interface layer with the current-producing bacterium Shewanella oneidensis MR-1, this material produces a 178-fold increase in the current density compared to unmodified electrodes, a current gain that is higher than previously reported thin-film 2D coatings and 3D conductive polymer coatings. The chemistry, morphology, and electronic properties of the coatings are characterized and the implementation of these coated electrodes for use in microbial fuel cells, multiplexed bioelectronic devices, and organic electrochemical transistor based microbial sensors are demonstrated. It is envisioned that this simple coating will advance the development of microbial bioelectronic devices.

patterned bioelectronics↗

Cross-Sections of Nanocellulose from Wood Analyzed by Quantized Polydispersity of Elementary Microfibrils

Bio-based nanocellulose has been shown to possess impressive mechanical properties and simplicity for chemical modifications. The chemical properties are largely influenced by the surface area and functionality of the nanoscale materials. However, finding the typical cross-sections of nanocellulose, such as cellulose nanofibers (CNFs), has been a long-standing puzzle, where subtle changes in extraction methods seem to yield different shapes and dimensions. Here, we extracted CNFs from wood with two different oxidation methods and variations in degree of oxidation and high-pressure homogenization. Additionally, the cross-sections of CNFs were characterized by small-angle X-ray scattering and wide-angle X-ray diffraction in dispersed and freeze-dried states, respectively, where the results were analyzed by assuming that the cross-sectional distribution was quantized with an 18-chain elementary microfibril, the building block of the cell wall. We find that the results agree well with a pseudosquare unit having a size of about 2.4 nm regardless of sample, while the aggregate level strongly depends on the extraction conditions. Furthermore, we find that aggregates have a preferred cohesion of phase boundaries parallel to the (110)-plane of the cellulose fibril, leading to a ribbon shape on average.

36 MATERIALS SCIENCE↗