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At least 505 records · Page 28

Dinuclear Gold(I) Complexes Bearing Alkyl-Bridged Bis(N-heterocyclic carbene) Ligands as Catalysts for Carboxylative Cyclization of Propargylamine: Synthesis, Structure, and Kinetic and Mechanistic Comparison to the Mononuclear Complex [Au(IPr)Cl]

Eight new dinuclear gold(I) complexes, [Au 2 (L)X 2 ] (1–8), were synthesized using a straightforward synthetic procedure under very mild conditions. The complexes have been characterized by NMR spectroscopy, elemental analysis, and single-crystal X-ray structure analysis. Their catalytic activity was investigated in the carboxylative cyclization of propargylamine (PPA). A superior performance in comparison to [Au(IPr)Cl] (9) was obtained for complexes 1 and 2 having an eight-methylene bridge connecting two NHCs with an arene bearing an isopropyl substituent for X = Cl, Br. This prompted more detailed kinetic and mechanistic studies by FTIR comparing dinuclear complex 2 of X = Cl to complex 9. Fortuitously the FTIR studies allowed monitoring of the formation of the products carbamic acid (CA) and carbamate salt (CS), as well as a key cyclized intermediate first discovered by Ikariya. These data allow additional insight into the mechanism as well as the central role which may be played by Au(I) carbamate formation as a higher energy resting state present in the catalytic cycle. In conclusion, the crystal structures of four of the new complexes and a detailed computational study relevant to the role of carbamic acid (CA) and carbamates in the catalytic cycle are also reported.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Direct Observation of Morphological and Chemical Changes during the Oxidation of Model Inorganic Ligand-Capped Particles

Functionalization and volatilization are competing reactions during the oxidation of carbonaceous materials and are important processes in many different areas of science and technology. Here, we present a combined ambient pressure X-ray photoelectron spectroscopy (APXPS) and grazing incidence X-ray scattering (GIXS) investigation of the oxidation of oleic acid ligands surrounding NaYF 4 nanoparticles (NPs) deposited onto SiO x /Si substrates. While APXPS monitors the evolution of the oxidation products, GIXS provides insight into the morphology of the ligands and particles before and after the oxidation. Our investigation shows that the oxidation of the oleic acid ligands proceeds at O 2 partial pressures of below 1 mbar in the presence of X-rays, with the oxidation eventually reaching a steady state in which mainly CH x and –COOH functional groups are observed. The scattering data reveal that the oxidation and volatilization reaction proceeds preferentially on the side of the particle facing the gas phase, leading to the formation of a chemically and morphologically asymmetric ligand layer. This comprehensive picture of the oxidation process could be obtained only by combining the X-ray scattering and APXPS data. The investigation presented here lays the foundation for further studies of the stability of NP layers in the presence of reactive trace gases and ionizing radiation and for other nanoscale systems where chemical and morphological changes happen simultaneously and cannot be understood in isolation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Measurements of fusion reaction history in inertially confined burning plasmas

Direct evidence of inertially confined fusion ignition appears in the abrupt temperature increase and consequent rapid increase in the thermonuclear burn rate as seen in the reaction history. The Gamma Reaction History (GRH) and Gas Cherenkov Detector (GCD) diagnostics are γ-based Cherenkov detectors that provide high quality measurements of deuterium–tritium fusion γ ray production and are, thus, capable of monitoring the thermonuclear burn rate. Temporal shifts in both peak burn time and burn width have been observed during recent high-yield shots (yields greater than 1017 neutrons) and are essential diagnostic signatures of the ignition process. While the current GRH and GCD detectors are fast enough to sense the changes of reaction history due to alpha heating, they do not have enough dynamic range to capture the onset of alpha heating. The next generation of instrumentation, GRH-15m, is proposed to increase the yield-rate coverage to measure the onset of alpha-heating.

42 ENGINEERING↗

UV-Fluorescence Imaging of Silicon PV Modules After Outdoor Aging and Accelerated Stress Testing

Fast, non-destructive, outdoor-compatible methods for photovoltaic module characterization are essential for monitoring module quality without disrupting energy production. UV-fluorescence (UVF) imaging of the encapsulant layer can be used for crack detection in the field. We show that UVF patterns vary widely between modules and types of applied stress. We propose that combining accelerated stress testing (e.g. thermal cycling and damp heat) with field investigations can help build understanding of different types of UVF, which are formed and subsequently quenched at varying rates. Ultimately, such understanding could enable estimating when cracks were formed.

41 EE - Solar Energy Technologies Office (EE-4S)↗

Climate Dynamics Preceding Summer Forest Fires in California and the Extreme Case of 2018

Recent record-breaking wildfire seasons in California prompt an investigation into the climate patterns that typically precede anomalous summer burned forest area. Using burned-area data from the U.S. Forest Service’s Monitoring Trends in Burn Severity (MTBS) product and climate data from the fifth major global reanalysis produced by the European Centre for Medium-Range Weather Forecasts (ERA5) over 1984–2018, relationships between the interannual variability of antecedent climate anomalies and July California burned area are spatially and temporally characterized. Lag correlations show that antecedent high vapor pressure deficit (VPD), high temperatures, frequent extreme high temperature days, low precipitation, high subsidence, high geopotential height, low soil moisture, and low snowpack and snowmelt anomalies all correlate significantly with July California burned area as far back as the January before the fire season. Seasonal regression maps indicate that a global midlatitude atmospheric wave train in late winter is associated with anomalous July California burned area. July 2018, a year with especially high burned area, was to some extent consistent with the general patterns revealed by the regressions: low winter precipitation and high spring VPD preceded the extreme burned area. However, geopotential height anomaly patterns were distinct from those in the regressions. Extreme July heat likely contributed to the extent of the fires ignited that month, even though extreme July temperatures do not historically significantly correlate with July burned area. While the 2018 antecedent climate conditions were typical of a high-burned-area year, they were not extreme, demonstrating the likely limits of statistical prediction of extreme fire seasons and the need for individual case studies of extreme years.

54 ENVIRONMENTAL SCIENCES↗

Laboratory Investigation of Gas Transport Through Variably Saturated Rock [Slides]

Project Overview: Noble gas fission products, such as xenon (Xe), are monitored to detect nuclear tests. For well-contained subsurface tests, transport to the surface will impact detected isotopic ratios, complicating event identification. Role of water saturation in subsurface transport is not well understood. Historic tests have taken place near or below the water table. To accurately predict breakthrough times and fractionation, gas transport must be characterized through intact rock with variable saturation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

A double peak in the seasonality of California's photosynthesis as observed from space

Solar-induced chlorophyll fluorescence (SIF) has been shown to be a powerful proxy for photosynthesis and gross primary productivity (GPP). The recently launched TROPOspheric Monitoring Instrument (TROPOMI) features the required spectral resolution and signal-to-noise ratio to retrieve SIF from space. Here, we present a downscaling method to obtain 500 m spatial resolution SIF over California. We report daily values based on a 14 d window. TROPOMI SIF data show a strong correspondence with daily GPP estimates at AmeriFlux sites across multiple ecosystems in California. We find a linear relationship between SIF and GPP that is largely invariant across ecosystems with an intercept that is not significantly different from zero. Measurements of SIF from TROPOMI agree with MODerate Resolution Imaging Spectroradiometer (MODIS) vegetation indices – the normalized difference vegetation index (NDVI), enhanced vegetation index (EVI), and near-infrared reflectance of vegetation index (NIR$_v$) – at annual timescales but indicate different temporal dynamics at monthly and daily timescales. TROPOMI SIF data show a double peak in the seasonality of photosynthesis, a feature that is not present in the MODIS vegetation indices. The different seasonality in the vegetation indices may be due to a clear-sky bias in the vegetation indices, whereas previous work has shown SIF to have a low sensitivity to clouds and to detect the downregulation of photosynthesis even when plants appear green. We further decompose the spatiotemporal patterns in the SIF data based on land cover. The double peak in the seasonality of California's photosynthesis is due to two processes that are out of phase: grasses, chaparral, and oak savanna ecosystems show an April maximum, while evergreen forests peak in June. An empirical orthogonal function (EOF) analysis corroborates the phase offset and spatial patterns driving the double peak. The EOF analysis further indicates that two spatiotemporal patterns explain 84 % of the variability in the SIF data. Results shown here are promising for obtaining global GPP at sub-kilometer spatial scales and identifying the processes driving carbon uptake.

54 ENVIRONMENTAL SCIENCES↗

On particle track detectors

Aqueous sodium hydroxide is widely used to develop charged particle tracks in polycarbonate film, particularly Lexan. The chemical nature of the etching process for this system has been determined. A method employing ultra-violet absorbance was developed for monitoring the concentration of the etch products in solution. Using this method it was possible to study the formation of the etching solution saturated in etch products. It was found that the system super-saturates to a significant extent before precipitation occurs. It was also learned that the system approaches its equilibrium state rather slowly. It is felt that both these phenomena may be due to the presence of surfactant in the solution. In light of these findings, suggestions are given regarding the preparation and maintenance of the saturated etch solution. Two additional research projects, involving automated techniques for particle track analysis and particle identification using AgCl crystals, are briefly summarized.

Benton, E. V.↗

Software engineering project management - A state-of-the-art report

The management of software engineering projects in the aerospace industry was investigated. The survey assessed such features as contract type, specification preparation techniques, software documentation required by customers, planning and cost-estimating, quality control, the use of advanced program practices, software tools and test procedures, the education levels of project managers, programmers and analysts, work assignment, automatic software monitoring capabilities, design and coding reviews, production times, success rates, and organizational structure of the projects.

Thayer, R. H.↗

Market analysis of seismic security systems

This report provides information on the commercialization potential of the NASA Activity Monitor. Data on current commercially available products, market size, and growth are combined with information on the NASA technology and the projected impact of this technology on the market.

Taglio, S.↗

Reflectance Measurements, Part 2

Improving the productivity of spectroreflectometer readings taken to monitor induced contamination of lenses, mirrors, and coatings in the space environment are described. More sophisticated modelling techniques were applied to the laboratory data collected last summer in order to produce a more accurate model of the nonlinearities and noise sources of the instrumentation. This would ultimately allow for correction of known anomalies by the digital computer, yielding an anticipated order to magnitude improvement in the accuracy of the reflectance measurements, while reducing the total measuring time. The construction of and programming for a modernized version of the electronics used in Beckman DK-2 spectroreflectometers suffered because of a schedule lag in fabrication of a modified form of the carrier frequency pickoff. Separate development of the electronics and the computer programming was partially accomplished.

Brown, R. A.↗

Recent advances in multispectral sensing of ocean surface temperature from space

Visual and infrared measurements from the five channel AVHRR on the NOAA-7 satellite are used operationally to derive sea surface temperatures. The multichannel data perform daytime and nighttime cloud detection tests, and the several atmospheric window channels in the thermal infrared correct for atmospheric attenuation. Monitoring of the sea surface temperature product with buoy data indicates stability in mean bias and rms difference with little variation by season or geographic area. Global mapping enables the derivation of monthly mean isotherms, monthly and annual changes, and anomaly patterns relative to climatology. Problems are associated with noise in the 3.7 micro m window channel, and with the injection of substantial volcanic aerosol into the stratosphere by the El Chichon eruption. Multichannel sea surface temperature charts are used to study phenomena such as equatorial long waves and the recent El Nino episode.

Mcclain, E. P.↗

A prototype gas exchange monitor for exercise stress testing aboard NASA Space Station

This paper describes an easy-to-use monitor developed to track the weightlessness deconditioning aboard the NASA Space Station, together with the results of testing of a prototype instrument. The monitor measures the O2 uptake and CO2 production, and calculates the maximum O2 uptake and anaerobic threshold during an exercise stress test. The system uses two flowmeters in series to achieve a completely automatic calibration, and uses breath-by-breath compensation for sample line-transport delay. The monitor was evaluated using two laboratory methods and was shown to be accurate. The system's block diagram and the bench test setup diagram are included.

Orr, Joseph A.↗

Nonlocal thermodynamic equilibrium effects of vibrationally excited NO

Results are presented of a laboratory investigation of the vibrational distribution of NO produced in the reaction between O(3P) and NO2(X 2A1). To minimize vibrational quenching, the experiments were performed in a fast-flow system. The production of NO(X) radicals was monitored with laser-induced fluorescence. It was found that the NO vibrational population ratio measured correlates well with the earlier observation of high vibrational excitation in O2.

Moralejo, C.↗

Mars Mobile Lander Systems for 2005 and 2007 Launch Opportunities

A series of Mars missions are proposed for the August 2005 launch opportunity on a medium class Evolved Expendable Launch Vehicle (EELV) with a injected mass capability of 2600 to 2750 kg. Known as the Ranger class, the primary objective of these Mars mission concepts are: (1) Deliver a mobile platform to Mars surface with large payload capability of 150 to 450 kg (depending on launch opportunity of 2005 or 2007); (2) Develop a robust, safe, and reliable workhorse entry, descent, and landing (EDL) capability for landed mass exceeding 750 kg; (3) Provide feed forward capability for the 2007 opportunity and beyond; and (4) Provide an option for a long life telecom relay orbiter. A number of future Mars mission concepts desire landers with large payload capability. Among these concepts are Mars sample return (MSR) which requires 300 to 450 kg landed payload capability to accommodate sampling, sample transfer equipment and a Mars ascent vehicle (MAV). In addition to MSR, large in situ payloads of 150 kg provide a significant step up from the Mars Pathfinder (MPF) and Mars Polar Lander (MPL) class payloads of 20 to 30 kg. This capability enables numerous and physically large science instruments as well as human exploration development payloads. The payload may consist of drills, scoops, rock corers, imagers, spectrometers, and in situ propellant production experiment, and dust and environmental monitoring.

Sabahi, D.↗

Limits on the UV Photodecomposition of Carbonates on Mars

The effect of UV (ultraviolet) light on the stability of calcium carbonate in a simulated martian atmosphere was experimentally investigated. Sample cells containing C-13 labeled calcite were irradiated with a Xe arc lamp in 10 mbar of simulated martian atmosphere and a quadrupole mass spectrometer was used to monitor the headspace gases for the production of (13)CO2. We found no experimental evidence of the UV photodecomposition of calcium carbonate in a simulated martian atmosphere. Extrapolating the lower limit of detection of our experimental system to an upper limit of carbonate decomposition on Mars yields a quantum efficiency of 3.5 x 10(exp -8) molecules/photon over the wavelength interval of 190-390 nm and a maximum UV photodecomposition rate of 1.2 x 10(exp -13) kg m(exp -2) s(exp -1) from a calcite surface. The maximum loss of bulk calcite due to this process would be 2.5 nm yr(exp -1). However, calcite is expected to be thermodynamically stable on the surface of Mars and potential UV photodecomposition reaction mechanisms indicate that while calcium carbonate may decompose under vacuum, it would be stable in a CO2 atmosphere. Given the expected stability of carbonate on Mars and our inability to detect carbonate decomposition, we conclude that it is unlikely that the apparent absence of carbonate on the martian surface is due to UV photo decomposition of calcite in the current environment.

Quinn, Richard↗

Oceanographic Research

The PNF-300 Natural Fluorometer is an optical instrument for oceanographic research developed under NASA contract by Biospherical Instruments, Inc. An important innovation for oceanographers, it measures photosynthetic productivity and estimates phytoplankton production less expensively, is non-intrusive and can be used on site - an improved way of estimating ocean productivity. Applications include environmental impact studies, monitoring plankton concentrations in a reservoir, and other research uses.

Source record↗

BOUSSOLE: A Joint CNRS-INSU, ESA, CNES, and NASA Ocean Color Calibration and Validation Activity

This report presents the Bouee pour l'acquisition de Series Optiques a Long Terme (BOUSSOLE) project, the primary objectives of which are to provide a long-term time series of optical properties in support of a) calibration and validation activities associated with satellite ocean color missions, and b) bio-optical research in oceanic waters. The following are included in the report: 1) an introduction to the rationale for establishing the project; 2) a definition of vicarious calibration and the specific requirements attached to it; 3) the organization of the project and the characteristics of the measurement site--in the northwestern Mediterranean Sea; 4) a qualitative overview of the collected data; 5) details about the buoy that was specifically designed and built for this project; 6) data collection protocols and data processing techniques; 7) a quantitative summary of the collected data, and a discussion of some sample results, including match-up analyses for the currently operational ocean color sensors, namely MERIS, SeaWiFS, and MODIS; and 8) preliminary results of the vicarious radiometric calibration of MERIS, including a tentative uncertainty budget. The results of this match-up analysis allow performance comparisons of various ocean color sensors to be performed, demonstrating the ability of the BOUSSOLE activity, i.e., combining a dedicated platform and commercial-off-the-shelf instrumentation, to provide data qualified to monitor the quality of ocean color products on the long term.

Antoine, David↗