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At least 1,423 records · Page 79

Long-Term Changes in Light Scattering in Chesapeake Bay Inferred from Secchi Depth, Light Attenuation, and Remote Sensing Measurements

The relationship between the Secchi depth (Z(sub SD)) and the diffuse attenuation coefficient for photosynthetically active radiation (K(sub d)(PAR)), and in particular the product of the two, Z(sub SD) X K(sub d)(PAR), is governed primarily by the ratio of light scattering to absorption. We analyzed measurements of Z(sub SD) and K(sub d)(PAR) at main stem stations in Chesapeake Bay and found that the Z(sub SD) X K(sub d)(PAR) product has declined at rates varying from 0.020 to 0.033 /yr over the 17 to 25 years of measurement, implying that there has been a long -term increase in the scattering-to-absorption ratio. Remote sensing reflectance at the green wavelength most relevant to Z(sub SD) and K(sub d)(PAR) in these waters, R(sub rs)(555), did not exhibit an increasing trend over the 10 years of available measurements. To reconcile the observations we constructed a bio-optical model to calculate Z(sub SD), K(sub d)(PAR), Z(sub SD) X K(sub d)(PAR), and R(sub rs)(555) as a function of light attenuating substances and their mass-specific absorption and scattering coefficients. When simulations were based exclusively on changes in concentrations of light attenuating substances, a declining trend in Z(sub SD) E K(sub d) entailed an increasing trend in R(sub rs)(555), contrary to observations. To simulate both decreasing Z(sub SD) X K(sub d)(PAR) and stationary R(sub rs)(555), it was necessary to allow for a declining trend in the ratio of backscattering to total scattering. Within our simulations, this was accomplished by increasing the relative proportion of organic detritus with high mass-specific scattering and low backscattering ratio. An alternative explanation not explicitly modeled is an increasing tendency for the particulate matter to occur in large aggregates. Data to discriminate between these alternatives are not available.

Gallegos, Charles L.↗

Pore space partition of metal-organic frameworks for gas storage and separation

Pore space partition (PSP) concept is a synthetic design concept and can also serve as a structure analysis method useful for next-step synthetic planning and execution. PSP provides an integrated chemistry-topology-focused tool to design new materials platforms. While PSP is no less effective for making large-pore materials, the growing importance of small-molecule gas storage and separation for green-energy applications provides impetus for developing small-pore materials for which the PSP strategy is uniquely suited. Currently, the best embodiment of the PSP concept is the partitioned-acs (pacs) platform in which both fine or coarse adjustments to the building blocks have sparked a transformation of a prototype framework into a huge and continuously expanding family of chemically robust materials with controllable pore metrics and functionalities suitable for tailored applications. The pacs compositional diversity results from the platform’s intrinsic multi-module nature, geometric flexibility and tolerance towards individual module variations, and mutual structure-directing effects among various modules, all of which combine to enable the molecular-level uniform co-assemblies of chemical components rarely seen together elsewhere. Here, in this contribution, we present an overview of different pore space engineering methods and how different MOF materials have contributed to important advances in chemical stability, industrial gas storage and gas separation. In particular, we will focus on synthetic assembly of the pacs system, highlighting the differences of pacs materials from other MOF platforms and advantages of pacs materials in enhancing various MOF properties.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Fast Organic Vapor Phase Deposition of Thin Films in Light-Emitting Diodes

Fast deposition of thin films is essential for achieving low-cost, high throughput phosphorescent organic light emitting diode (PHOLED) production. In this work, we demonstrate rapid and uniform growth of semiconductor thin films by organic vapor phase deposition (OVPD). A green PHOLED comprising an emission layer (EML) grown at 50 Å/s with bis[2-(2-pyridinyl-N)phenyl-C](acetylacetonato)iridium(III) (Ir(ppy)2(acac)) doped into 4,4 bis(N-carbazolyl)-1,1zolylld (CBP) exhibits a maximum external quantum efficiency of 20 ± 1%. The morphology, charge transport properties, and radiative efficiency under optical and electrical excitation of the PHOLED EML are investigated as functions of the deposition rate via both experimental and theoretical approaches. The EML shows no evidence for gas phase nucleation of the organic molecules at deposition rates as high as 50 Å/s. However, the roll-off in quantum efficiency at high current progressively increases with deposition rate due to enhanced triplet-polaron annihilation. The roll-off results from accumulation of stress within the PHOLED EML that generates a high density of defect states. Here, the defects, in turn, act as recombination sites for triplets and hole polarons, leading to enhanced triplet-polaron annihilation at high current. We introduce a void nucleation model to describe the film morphology evolution that is observed using electron microscopy.

42 ENGINEERING↗

Chlamydomonas CHT7 is involved in repressing DNA replication and mitotic genes during synchronous growth

In the green alga Chlamydomonas reinhardtii, regulation of the cell cycle in response to external cues is critical for survival in a changing environment. The loss of the nuclear COMPROMISED HYDROLYSIS OF TRIACYLGLYCEROLS 7 (CHT7) protein affects the expression of many genes especially in response to nitrogen availability. Cells lacking CHT7 exhibit abnormal cell morphology following nitrogen deprivation and fail to resume normal cell division after N resupply. To investigate the function of CHT7 in the regulation of cell cycle-related pathways, cells were synchronized, and RNA-seq analysis was performed during various stages of the cell cycle. In the cht7 mutant following nitrogen deprivation, the cells were not dividing, but a subset of cell cycle genes involved in DNA replication and mitosis were found to be derepressed, suggesting that the CHT7 protein plays a role in cell cycle regulation that is opposite to that of the mitotic cyclin-dependent kinases. Furthermore, genes for cell wall synthesis and remodeling were found to be abnormally induced in nondividing cht7 cells; this misregulation may deplete cellular resources and thus contribute to cell death following nitrogen deprivation. Lastly, 43 minimally characterized kinases were found to be highly misregulated in cht7. Further analysis suggested that some of these CHT7-regulated kinases may be related to the MAP3K and Aurora-like kinases, while others are unique. Together, these results suggest a role of CHT7 in transcriptional regulation of the cell cycle and reveal several pathways and genes whose expression appears to be subject to a CHT7-mediated regulatory network.

59 BASIC BIOLOGICAL SCIENCES↗

Solid State Television Camera (CID)

The design, development and test are described of a charge injection device (CID) camera using a 244x248 element array. A number of video signal processing functions are included which maximize the output video dynamic range while retaining the inherently good resolution response of the CID. Some of the unique features of the camera are: low light level performance, high S/N ratio, antiblooming, geometric distortion, sequential scanning and AGC.

Steele, D. W.↗

Evidence of erosive burning in shuttle solid rocket motor

Known models of Shuttle Solid Rocket Motor (SRM) performance have failed to produce pressure-time traces which accurately matched actual motor performance, especially during the first 5 seconds after ignition and during the last quarter of web burn time. Efforts to compensate for these differences in model reconstruction and actual performance resulted in resorting to the use of a Burning Anomaly Rate Function (BARF). It was suspected that propellant erosive burning was primarily responsible for the variation of model from actual results. The three dimensional Hercules Grain Design and Internal Ballistics Evaluation Program was made operational and slightly modified and an extensive trial and error effort was begun to test the hypothesis of erosive burning as an explanation of the burning anomaly. It was found that introduction of erosive burning (using Green's erosive burning equation) over portions of the aft segment grain and above a threshold gas Mach number did, in fact, give excellent agreement with the actual motor trace.

Martin, C. L.↗

Collisional excitation of interstellar methyl cyanide

Theoretical calculations are used to determine the collisional excitation rates of methyl cyanide under interstellar molecular cloud conditions. The required Q(L,M) as a function of kinetic temperature were determined by averaging fixed energy IOS (infinite order sudden) results over appropriate Boltzmann distributions of collision energies. At a kinetic temperature of 40 K, rates within a K ladder were found to be accurate to generally better than about 30 percent.

Green, Sheldon↗

Latent-failure risk estimates for computer control

It is shown that critical computer controls employing unmonitored safety circuits are unsafe. Analysis supporting this result leads to two additional, important conclusions: (1) annual maintenance checks of safety circuit function do not, as widely believed, eliminate latent failure risk; (2) safety risk remains even if multiple, series-connected protection circuits are employed. Finally, it is shown analytically that latent failure risk is eliminated when continuous monitoring is employed.

Dunn, William R.↗

Phosphate Limitation Responses in Marine Green Algae Are Linked to Reprogramming of the tRNA Epitranscriptome and Codon Usage Bias

Marine algae are central to global carbon fixation, and their productivity is dictated largely by resource availability. Reduced nutrient availability is predicted for vast oceanic regions as an outcome of climate change; however, there is much to learn regarding response mechanisms of the tiny picoplankton that thrive in these environments, especially eukaryotic phytoplankton. Here, we investigate responses of the picoeukaryote Micromonas commoda, a green alga found throughout subtropical and tropical oceans. Under shifting phosphate availability scenarios, transcriptomic analyses revealed altered expression of transfer RNA modification enzymes and biased codon usage of transcripts more abundant during phosphate-limiting versus phosphate-replete conditions, consistent with the role of transfer RNA modifications in regulating codon recognition. To associate the observed shift in the expression of the transfer RNA modification enzyme complement with the transfer RNAs encoded by M. commoda, we also determined the transfer RNA repertoire of this alga revealing potential targets of the modification enzymes. Codon usage bias was particularly pronounced in transcripts encoding proteins with direct roles in managing phosphate limitation and photosystem-associated proteins that have ill-characterized putative functions in “light stress.” The observed codon usage bias corresponds to a proposed stress response mechanism in which the interplay between stress-induced changes in transfer RNA modifications and skewed codon usage in certain essential response genes drives preferential translation of the encoded proteins. Collectively, we expose a potential underlying mechanism for achieving growth under enhanced nutrient limitation that extends beyond the catalog of up- or downregulated protein-encoding genes to the cell biological controls that underpin acclimation to changing environmental conditions.

59 BASIC BIOLOGICAL SCIENCES↗

Oblique-incidence secondary emission from charged dielectrics

Secondary electron emission coefficients were measured on FEP-Teflon for normal and oblique incidence in the presence of a normal electric field. Such measurements require knowledge of the electrostatic environment surrounding the specimen, and they require calculation of particle trajectories such that particle impact parameters can be known. A simulation using a conformal mapping, a Green's integral, and a trajectory generator provides the necessary mathematical support for the measurements, which were made with normal fields of 1.5 and 2.7 kV/mm. When incidence is normal and energy exceeds the critical energy, the coefficient is given by (V sub 0/V) to the .58 power, and for oblique incidence this expression may be divided by the cosine of the angle. The parameter V sub 0 is a function of normal field.

Robinson, J. W.↗

Minimum High Fire Temperatures Detected in AVIRIS Spectral Measurements from Brazil in 1995

In August and September of 1995 the Airborne Visible/Infrared Imaging Spectrometer (AVIRIS) was deployed to Brazil as part of the NASA Smoke Cloud Aerosol and Radiation experiment in Brazil (SCAR-B). AVIRIS measures spectra from 400 to 2500 nm at 10-nm intervals. These spectra are acquired as images with dimensions of 11 by up to 800 km with 20-m spatial resolution. Spectral images measured by AVIRIS are spectrally, radiometrically, and spatially calibrated. During the SCAR-B deployment, AVIRIS measured more than 300 million spectra of regions of Brazil. A portion of these spectra were acquired over areas of actively burning fires. Actively burning fires emit radiance in the AVIRIS spectral range as a function of temperature. This emitted radiance is expressed from the 2500-nm end of the AVIRIS spectrum to shorter wavelengths as a function of intensity and modeled by the Planck function. The objective of this research and analysis was to use spectroscopic methods to determine the minimum high temperature of the most intense fires measured in the SCAR-B AVIRIS data set. Spectra measured by AVIRIS with hot sources have been previously examined for volcanic lava.

Green, Robert O.↗

Broadband Wavefront Sensing for JWST Fine Phasing

An application of broadband image-based wavefront sensing is considered for JWST fine phasing. The wavefront sensing error is derived as a function of filter bandpass and then applied to determine the appropriate filter specifications for observatory fine-phasing. These specifications are defined by considering an optimization in the trade space consisting of detector integration time vs. filter bandpass subject to wavefront sensing error budget constraints.

Dean, Bruce↗

Bandgap Engineering of Ga 2 O 3 by MOCVD Through Alloying with Indium

Ga 2 O 3 and In 2 O 3 are vital semiconductors with current and future electronic device applications. Here, we study the alloying of In 2 O 3 and Ga 2 O 3 (IGO) and the associated changes in structure, morphology, band gap, and electrical transport properties. Undoped films of IGO were deposited on sapphire substrates with varying indium (In) percentage from zero to 100% by metal-organic chemical vapor deposition (MOCVD). Some films were annealed in H 2 to induce electrical conductivity. The measurements showed the optical band gap decreased by adding In; this was confirmed by density functional (DFT) calculations, which revealed that the nature of the valence band maximum and conduction band minimum strongly relate to the chemistry and that the band gap drops by adding In. The as-grown films were highly resistive except for pure In 2 O 3 , which possesses p-type conductivity, likely arising from In vacancy-related acceptor states. N-type conductivity was induced in all films after H-anneal. DFT calculations revealed that the presence of In decreases the electron effective mass, which is consistent with the electrical transport measurements that showed higher electron mobility for higher In percentage. The work revealed the successful band gap engineering of IGO and the modification of its band structure while maintaining high-quality films by MOCVD.

36 MATERIALS SCIENCE↗

(Invited) All-Solid-State Batteries Using Li 7 La 3 Zr 2 O 12 Garnet Electrolyte Framework

All-solid-state batteries (ASSB) using LLZO (variants of Li 7 La 3 Zr 2 O 12 ) garnet solid electrolyte with lithium metal anode potentially offer higher energy density and improved safety. Rational design of cell architecture as well as manufacturing scalability are key aspects to consider as the technology readiness level advances. A thick composite cathode layer attached to a thin solid electrolyte layer is desirable to obtain superior energy densities. Furthermore, the architecture within the composite cathode may be engineered to contain directional conduction paths of lithium ions or electrons for enhanced rate capabilities. Here, we demonstrate a functioning bulk-type LLZO based all-solid-state battery with a practical form factor incorporating the above described design concepts. Freeze-tape-casting (FTC), a scalable and environmentally friendly ceramic processing method, is used to construct 3D porous LLZO scaffolds composed of vertical arrays of LLZO walls. The thin solid-electrolyte layer is fabricated by tape-casting (TC). By sintering the stacks of FTC and TC green tapes, porous/dense bilayers and porous/dense/porous trilayers of LLZO frameworks are obtained. An ASSB was constructed using a porous/dense bilayer by infiltrating LiNi 0.6 Mn 0.2 Co 0.2 O 2 cathode powder and carbon black into the porous layer and adhering lithium metal foil to the dense side. We find it crucial to introduce a plastic crystal based soft solid electrolyte to the porous layer to electrochemically connect all cathode components, obviating the need for co-sintering to establish contact. The soft nature of the plastic crystal based solid-electrolyte may be able to accommodate the volume change of the cathode material as it cycles. In this device, which contained no liquid component, the initial discharge capacities were similar to those observed in a lithium ion battery configuration using the same cathode powder at C/10 rates.

25 ENERGY STORAGE↗

Designing Catalysts for Dehydrogenation of Methane for Reducing Greenhouse Gas during Natural Gas Extraction

Catalytic conversion of methane (CH 4 ) into useful products is critical for maximizing the utility of natural gas output and for reducing green house gas release associated with flaring (burning off CH 4 at natural gas extraction sites). One particular useful technique is methane dry reforming (DRM), which involves the chemical reaction of CH 4 with carbon dioxide (CO 2 ) to generate carbon monoxide (CO), hydrogen gas (H 2 ), and subsequently other useful products. New and improved catalysts are required to facilitate efficient dry methane reforming. In this report, we apply the Density Functional Theory (DFT) computational technique to investigate a catalyst consisting of small nickel clusters (Ni n , n < 10) on ceria (Ce0 2 (111) surfaces) support. One main thrust of this project is to study the initial CH 4 and CO 2 reactions with the catalyst. We find that CH 4 exhibits barrierless reactive adsorption on to the catalyst. In order words, this step is likely not the rate-determining step. A second thrust is to perform detailed studies of the catalyst itself and examine the role of oxygen vacancies. Using a specific DFT method and a hypothesis about the absence of the Ce(III) redox state, we obtain predictions about oxygen vacancies in good agreement with experimental observations.

03 NATURAL GAS↗

An epigenetic gene silencing pathway selectively acting on transgenic DNA in the green alga Chlamydomonas

Abstract Silencing of exogenous DNA can make transgene expression very inefficient. Genetic screens in the model alga Chlamydomonas have demonstrated that transgene silencing can be overcome by mutations in unknown gene(s), thus producing algal strains that stably express foreign genes to high levels. Here, we show that the silencing mechanism specifically acts on transgenic DNA. Once a permissive chromatin structure has assembled, transgene expression can persist even in the absence of mutations disrupting the silencing pathway. We have identified the gene conferring the silencing and show it to encode a sirtuin-type histone deacetylase. Loss of gene function does not appreciably affect endogenous gene expression. Our data suggest that transgenic DNA is recognized and then quickly inactivated by the assembly of a repressive chromatin structure composed of deacetylated histones. We propose that this mechanism may have evolved to provide protection from potentially harmful types of environmental DNA.

Neupert, Juliane↗

Penetration depth at green wavelengths in turbid waters

A laboratory and field measurement program was conducted to determine apparent remote sensing penetration depths at a wavelength of 520 nm. Tests were made for various types of sediments under controlled conditions in a laboratory. Field tests were conducted in several different water bodies over a wide range of solar elevation angles. Laboratory results indicate that apparent penetration depth is significantly influenced by mineral content and/or size of suspended sediments. Field measurements show wide variation in apparent penetration depth, even when suspended solids concentration is nearly constant. Apparent penetration depth does not appear to be a strong function of solar elevation angle so long as the water mixture remains constant.

Whitlock, C. H.↗