Bridging Thiolates in Metalloenzymes: From Model Complexes to Catalytic Small Molecule Activation

The discovery of cyano-iron carbonyls in the hydrogenases has inspired synthetic efforts to reproduce the active sites of these efficient H2-producing or H2-oxidation enzymes. Recent demonstration of the possibility of loading apo-HydA ([FeFe]-H2ase enzyme) and apo-HydF (maturase protein) with synthetic analogues of the active site provides evidence that small molecular models are indeed the essential catalyst. Interrogation by EPR spectroscopy of the biohybrids indicate a role for the cyanide in attaching the organometallic unit to a carrier protein; in fact, the cyanide has flipped from its origin in the synthetic diiron unit and inserts into the maturation protein, HydF, resulting in a 4Fe4S docking of the diiron model complex, but placing the cyanide nitrogen next to the 2Fe site. In order to probe the requirements for such cyanide isomerization, we have prepared cyanide-bridged constructs of 3-Fe systems with features related to the organoiron moiety within the loaded HydF protein. The orientation of the CN bridge is determined by the precursors; no cyanide flipping was observed. Density function theory computations find a high barrier accounts for the kinetically controlled products. In another study, complexes of formulation (µ-SCH2XCH2S)[Fe(CO)3]2, with X=CH2, CMe2, CEt2, NMe, NtBu, and NPh were determined to be photocatalysts for release of H2 gas from H3B←NHMe2. The thermal displacement of H3B←Net3 from photochemically generated (µ-SCH2XCH2S)[Fe(CO)3][Fe(CO)2(µ-H)(BH2-Net3)] by P(OEt)3 was monitored by time-resolved FTIR spectroscopy. Kinetic data reveals an associative mechanism for X=CH2 and dissociative mechanism for the alkylated and nitrogen bridgehead species. This allows us to rank the catalysts in terms of their B-H unit binding ability, a key step in the dehydrogenation process. The rate of H2 production from the initially formed (µ-SCH2XCH2S)[Fe(CO)3][Fe(CO)2(µ-H)(BH2-NHMe2)] complexes was inversely correlated with the lifetime of the analogous (μ-SCH2XCH2S)[Fe(CO)3][Fe(CO)2(µ-H)(BH2-Net3)] adducts. Finally, a new series of complexes featuring MN2S2 metallodithiolates bound to Mn/Re(CO)3X were synthesized and characterized as electrocatalysts for C)2 reduction. Butterfly type structures resulted from binding of the lone pairs of the sulfur atoms to the Re/Mn(CO)3X unit. Under a CO2 atmosphere, there was a current enhancement in the cyclic voltammogram which is indicative of CO2 reduction to CO. Detailed electrochemical experiments are presented along with an appropriate characterization of catalytic processes using cyclic voltammetry and bulk electrolysis. Two complexes will be used as a case study

Stray Light Artifacts in Imagery from the Landsat 8 Thermal Infrared Sensor

The Thermal Infrared Sensor (TIRS) has been collecting imagery of the Earth since its launch aboard Landsat 8 in early 2013. In many respects, TIRS has been exceeding its performance requirements on orbit, particularly in terms of noise and stability. However, several artifacts have been observed in the TIRS data which include banding and absolute calibration discrepancies that violate requirements in some scenes. Banding is undesired structure that appears within and between the focal plane array assemblies. In addition, in situ measurements have shown an error in the TIRS absolute radiometric calibration that appears to vary with season and location within the image. The source of these artifacts has been determined to be out-of-field radiance that scatters onto the detectors thereby adding a non-uniform signal across the field-of-view. The magnitude of this extra signal can be approximately 8% or higher (band 11) and is generally twice as large in band 11 as it is in band 10. A series of lunar scans were obtained to gather information on the source of this out-of-field radiance. Analyses of these scans have produced a preliminary map of stray light, or ghost, source locations in the TIRS out-of-field area. This dataset has been used to produce a synthetic TIRS scene that closely reproduces the banding effects seen in actual TIRS imagery. Now that the cause of the banding has been determined, a stray light optics model is in development that will pin-point the cause of the stray light source. Several methods are also being explored to correct for the banding and the absolute calibration error in TIRS imager

The Preflight Calibration of the Thermal Infrared Sensor (TIRS) on the Landsat Data Continuity Mission

The preflight calibration testing of TIRS evaluates the performance of the instrument at the component, subsystem and system level, The overall objective is to provide an instrument that is well calibrated and well characterized with specification compliant data that will ensure the data continuity of Landsat from the previous missions to the LDCM, The TIRS flight build unit and the flight instrument were assessed through a series of calibration tests at NASA Goddard Space Flight Center. Instrument-level requirements played a strong role in defining the test equipment and procedures used for the calibration in the thermal/vacuum chamber. The calibration ground support equipment (CGSE), manufactured by MEI and ATK Corporation, was used to measure the optical, radiometric and geometric characteristics of TIRS, The CGSE operates in three test configurations: GeoRad (geometric, radiometric and spatial), flood source and spectral, TIRS was evaluated though the following tests: bright target recovery, radiometry, spectral response, spatial shape, scatter, stray light, focus, and uniformity, Data were obtained for the instrument and various subsystems under conditions simulating those on orbit In the spectral configuration, a monochromator system with a blackbody source is used for in-band and out-of-band relative spectral response characterization, In the flood source configuration the entire focal plane array is illuminated simultaneously to investigate pixel-to-pixel uniformity and dead or inoperable pixels, The remaining tests were executed in the GeoRad configuration and use a NIST calibrated cavity blackbody source, The NIST calibration is transferred to the TIRS sensor and to the blackbody source on-board TIRS, The onboard calibrator will be the primary calibration source for the TIRS sensor on orbit

Landsat 9 Thermal Infrared Sensor 2 Subsystem-Level Spectral Test Results

Results from the Thermal Infrared Sensor 2 (TIRS-2) prelaunch spectral characterization at telescope and detector subsystem level are presented. The derived relative spectral response (RSR) shape is expected to be very similar to the instrument-level spectral response and provides an initial estimate of the RSR and its differences to the component-level RSR measurements. Such differences were observed at TIRS- 1 and are likely a result of angular dependence of the spectral response of the detector. The subsystem RSR measurements also provide an opportunity for a preliminary assessment of the spectral requirements. Final requirements verification will be performed at future thermal vacuum environmental testing with the fully assembled TIRS-2 instrument

The Operational Land Imager (OLI) and the Thermal Infrared Sensor (TIRS) on the Landsat Data Continuity Mission (LDCM)

The Landsat Data Continuity Mission (LDCM), a joint NASA and United States Geological Survey (USGS) mission, is scheduled for launch in December, 2012. The LDCM instrument payload will consist of the Operational Land Imager (OLI), provided by Ball Aerospace and Technology Corporation (BATC) under contract to NASA and the Thermal Infrared Sensor (TIRS), provided by NASA's Goddard Space Flight Center (GSFC). This paper will describe the design, capabilities and status of the OLI and TIRS instruments. The OLI will provide 8 channel multispectral images at a spatial resolution of 30 meters and panchromatic images at 15 meter spatial resolution. The TIRS is a 100 meter spatial resolution push-broom imager whose two spectral channels, centered at 10.8 and 12 microns, split the ETM+ thermal bands. The two channels allow the use of the "split-window" technique to aid in atmospheric correction. The TIRS focal plane consists of three Quantum Well Infrared Photodetector (QWIP) arrays to span the 185 km swath width. The OLI and TIRS instruments will be operated independently but in concert with each other. Data from both instruments will be merged into a single data stream at the (USGS)/Earth Resources Observation and Science (EROS) facility. The ground system, being developed by USGS, includes an Image Assessment System (lAS), similar to Landsat-7's, to operationally monitor, characterize and update the calibrations of the two sensors

Landsat 9 Thermal Infrared Sensor 2 Preliminary Stray Light Assessment

Although the Thermal Infrared Sensor 2 (TIRS-2) is a nearidentical copy of the Landsat 8/TIRS-1 instrument, an important design change to the optical system was designed to mitigate the stray light issue that plagued the TIRS-1 instrument [1, 2, 3]. This change involved the addition of several baffles strategically placed within the optical telescope to block the stray light paths that were present in the TIRS- 1 design. The specific optical changes were determined by first characterizing the TIRS-1 stray light paths on-orbit and then deriving a detailed optical model that was used to determine the locations and shapes of the mitigating baffles. The stray light design changes to the TIRS-2 instrument were confirmed through the initial thermal-vacuum characterization tests. Preliminary assessments of TIRS-2 indicate that the total stray light magnitude has been drastically reduced to a total magnitude of approximately 1% or less

LANDSAT 9 Thermal Infrared Sensor 2 Characterization Plan Overview

Landsat 9 will continue the Landsat data record into its fifth decade with a near-copy build of Landsat 8 with launch scheduled for December 2020. The two instruments on Landsat 9 are Thermal Infrared Sensor-2 (TIRS-2) and Operational Land Imager-2 (OLI-2). TIRS-2 is a two-channel pushbroom imager with a 15-degree field of view that will have a 16-day measurement cadence from its nominal 705-km orbit altitude. Its carefully developed instrument performance requirements and associated characterization plan will result in stable and well-understood science-quality imagery that will be used for environmental, economic and legal applications. This paper will present a summary of the plan for TIRS-2 prelaunch characterization at the component, subsystem, and instrument level

Extrasolar Planet Transits Observed at Kitt Peak National Observatory

We obtained J-, H- and JH-band photometry of known extrasolar planet transiting systems at the 2.1-m Kitt Peak National Observatory Telescope using the FLAMINGOS infrared camera between October 2008 and October 2011. From the derived lightcurves we have extracted the mid-transit times, transit depths and transit durations for these events. The precise mid-transit times obtained help improve the orbital periods and also constrain transit-time variations of the systems. For most cases the published system parameters successfully accounted for our observed lightcurves, but in some instances we derive improved planetary radii and orbital periods. We complemented our 2.1-m infrared observations using CCD z'-band and B-band photometry (plus two Hydrogen Alpha filter observations) obtained with the Kitt Peak Visitor's Center telescope, and with four H-band transits observed in October 2007 with the NSO's 1.6-m McMath-Pierce Solar Telescope. The principal highlights of our results are: 1) our ensemble of J-band planetary radii agree with optical radii, with the best-fit relation being: (Rp/R*)J = 0.0017 + 0.979 (Rp/R*)optical, 2) We observe star spot crossings during the transit of WASP-11/HAT-P-10, 3) we detect star spot crossings by HAT-P-11b (Kepler-3b), thus confirming that the magnetic evolution of the stellar active regions can be monitored even after the Kepler mission has ended, and 4) we confirm a grazing transit for HAT-P-27/WASP-40. In total we present 57 individual transits of 32 known exoplanet systems.Comment: 33 pages, 6 figures, accepted in Publications of the Astronomical Society of the Pacifi

Landsat 9 Thermal Infrared Sensor 2 Preliminary Stray Light Assessment

No abstract availabl

The Thermal Infrared Sensor on the Landsat Data Continuity Mission

The Landsat Data Continuity Mission (LDCM), a joint NASA and USGS mission, is scheduled for launch in December, 2012. The LDCM instrument payload will consist of the Operational Land Imager (OLI), provided by Ball Aerospace and Technology Corporation (BATC} under contract to NASA and the Thermal Infrared Sensor (TIRS), provided by NASA's Goddard Space Flight Center (GSFC). This paper outlines the design of the TIRS instrument and gives an example of its application to monitoring water consumption by measuring evapotranspiration