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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 37 records · Page 2

Multimodal Instrument Platform for High-Pressure MAS-NMR and IR Spectroscopic Interrogation

This project developed and tested a high-pressure (HP) flow-through instrument platform that combines HP- magic angle spinning nuclear magnetic resonance (MAS-NMR) spectroscopy for interrogating reactivity at interfaces between solid materials and HP fluids with HP- infrared (IR) spectroscopy for measuring fluid composition. Solid-fluid interfacial reactivity is usually dependent on concentrations of species within the fluid; thus, knowledge of the fluid composition measured by IR is critical to understanding solid-fluid interfacial reactivity probed by NMR. This new system adds to PNNL’s core capabilities in Chemical and Material Sciences to support fundamental programs in catalysis, interfacial molecular science, and geosciences, as well as in Earth and Biological Sciences to support energy production and storage, efforts to mitigate the impacts energy production systems, attenuation of contaminant plumes, and design of subsurface engineered systems for energy production and waste disposal.

36 MATERIALS SCIENCE↗

Phytochrome-mediated germination and early development in spores of Dryopteris filix-mas L.: phase-specific and non phase-specific inhibition by staurosporine

The alkaloid staurosporine, currently known as the most potent inhibitor of protein kinase C, PKC, was tested for its ability to inhibit phytochrome-mediated spore germination in Dryopteris filix-mas L., evaluated by the induction of chlorophyll synthesis. Approximately half-maximal inhibition was obtained at a concentration of 10(-5) M. This effect of staurosporine was phase-specific and was found during the same period in which the presence of extracellular calcium is necessary for realization of the light signal. Furthermore, the ability of staurosporine to prevent progression of a germinated spore into early gametophyte development, evaluated by the accumulation of chlorophyll, was examined. Again, staurosporine (10(-5) M) significantly diminished chlorophyll accumulation, determined quantitatively in vivo by single-cell measurements, in a non-phase specific way. The fact that the phase-specific inhibitory effect of staurosporine in preventing germination was coincident with the phase-specific requirement of Ca2+ suggests that both Ca2+ and staurosporine affect the same step in the signal-transduction chain. A phosphorylation event catalysed by PKC or any Ca2+ -dependent protein kinase is proposed as the target of staurosporine and Ca2+.

Non-NASA Center↗

Milli-Arcsecond (MAS) Imaging with SmallSat Enabled Super-resolution

The objective of this project is to demonstrate a new imaging technology with unprecedented capabilities for scientific exploration. This technology innovation will enable extremely high-resolution imaging capability, otherwise unattainable with conventional approaches. It is based on a unique combination of novel diffractive optical sensing (photon sieve), advanced image processing, and small satellite formation flying. The spatial resolution of current solar instruments are more than 100 times coarser than the size of energy dissipation features in coronal heating (<100 km) since conventional optics cannot be figured to near diffraction-limited accuracy at extreme ultraviolet (EUV) wavelengths. This project will demonstrate the feasibility of imaging of a few milli-arcseconds (MAS) to study the structure and development of these dissipation regions.

Farzad Kamalabadi↗

Magnetically coupled loading chamber and apparatus for in situ MAS NMR: operating under either high or low pressure

A sample chamber holder for MAS-NMR capable of operating at both low and high pressures. In one example the sample chamber holder is made up of a sample holder body defining a sample chamber therein, a connector configured to operatively statically hold an in situ rotor within the sample chamber; a coupler configured to operatively connect the sampler holder body to a magnetically coupled rotation member. The magnetically coupled rotation member is configured to engage and rotate a sealing cap from an NMR rotor in such a way so as to allow an NMR cap to be alternatively opened or sealed in-situ while the NMR rotor remains statically positioned in an NMR device.

Hu, Jian Z.↗

Determination of the chemical shift tensor anisotropy and asymmetry of strongly dipolar coupled protons under fast MAS

Orientationally-dependent interactions such as dipolar coupling, quadrupolar coupling, and chemical shift anisotropy (CSA) contain a wealth of spatial information that can be used to elucidate molecular conformations and dynamics. To determine the sign of the chemical shift tensor anisotropy parameter (δ aniso ), both the |m| = 1 and |m| = 2 components of the CSA need to be symmetry allowed, while the recoupling of the |m| = 1 term is accompanied with the reintroduction of homonuclear dipolar coupling components. Therefore, previously suggested sequences which solely recouple the |m| = 2 term cannot determine the sign a 1 H's δ aniso in a densely-coupled network. Here, we demonstrate the CSA recoupling of strongly dipolar coupled 1 H spins using the $Cn^1_n (90_{0}360_{180}540_{0}360_{180}90_{0})$ sequence. This pulse scheme recouples both the |m| = 1 and |m| = 2 CSA terms but the scaling factors for the homonuclear dipolar coupling terms are zeroed. Consequently, the sequence is sensitive to the sign of δ aniso but is not influenced by homonuclear dipolar interactions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Determination of the mutual orientation between proton CSA tensors mediated through band-selective 1 H– 1 H recoupling under fast MAS

We report the mutual orientation of nuclear spin interaction tensors provides critical information on the conformation and arrangement of molecules in chemicals, materials, and biological systems at an atomic level. Proton is a ubiquitous and important element in a variety of substances, and its NMR is highly sensitive due to their virtually 100% natural abundance and large gyromagnetic ratio. Nevertheless, the measurement of mutual orientation between the 1 H CSA tensors has remained largely untouched in the past due to strong 1 H– 1 H homonuclear interactions in a dense network of protons. In this study, we have developed a proton-detected 3D 1 H CSA/ 1 H CSA/ 1 H CS correlation method that utilizes three techniques to manage homonuclear interactions, namely fast magic-angle spinning, windowless C-symmetry-based CSA recoupling (windowless-ROCSA), and a band-selective 1 H– 1 H polarization transfer. The asymmetric 1 H CSA/ 1 H CSA correlated powder patterns produced by the C-symmetry-based methods are highly sensitive to the sign and asymmetry parameter of the 1 H CSA, and the Euler angle β as compared to the symmetric pattern obtained by the existing γ-encoded R-symmetry-based CSA/CSA correlation methods and allows a larger spectral area for data fitting. These features are beneficial for determining the mutual orientation between the nuclear spin interaction tensors with improved accuracy.

1H CSA↗

Probing Pore Size and Connectivity in Porous Silicas Using 13C MAS NMR Spectroscopy of Supercritical Methane

Measuring the pore size and pore-size distributions and exploring the fluid-exchange dynamics between different types of pores in porous materials remains a significant experimental challenge but is critical to understanding catalysis, chromatography, nutrient cycling, and a whole range of geochemical phenomena, including shale gas and tight gas extraction. Here, we present the results of 1D 13 C NMR and 2D exchange spectroscopy (EXSY) NMR investigations of a porous silica using supercritical methane (scCH 4 ) as a direct probe of pore size and fluid exchange between pore types. The results show that the 13 C chemical shift of scCH 4 adsorbed in nanometer-scale silica pores becomes more negative with increasing pore diameter, in agreement with trends reported for gas hydrates, zeolites, MOFs, and clays and other microporous (<10 nm pores) geochemical materials. These 13 C chemical shifts follow a natural log–linear trend with pore size in the vacuum-dried porous silicas studied here, allowing one to predict pore size based on the 13 C chemical shift in dry silica nanopores. The EXSY and 1D 13 C NMR results both show that CH 4 exchanges between pore and bulk fluid environments over rate scales from 0.01 to 1 kHz in vacuum-dried samples and that exchange dynamics must be considered when interpreting 13 C NMR of pore-adsorbed CH 4 . Introducing H 2 O to the system causes the 13 C chemical shift to become more negative with increasing H 2 O content as a result of H 2 O preferentially filling small pores, forcing CH 4 to occupy larger pores that are better connected to the bulk environment. Likewise, the 1D 13 C data show a decreased distribution of exchange rates between pore-adsorbed and bulk CH 4 in the presence of H 2 O.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Cooperating systems: Layered MAS

Distributed intelligent systems can be distinguished by the models that they use. The model developed focuses on layered multiagent system conceived of as a bureaucracy in which a distributed data base serves as a central means of communication. The various generic bureaus of such a system is described and a basic vocabulary for such systems is presented. In presenting the bureaus and vocabularies, special attention is given to the sorts of reasonings that are appropriate. A bureaucratic model has a hierarchy of master system and work group that organizes E agents and B agents. The master system provides the administrative services and support facilities for the work groups.

Rochowiak, Daniel↗

Recent Monitoring of Suspended Sediment Patterns along Louisiana's Coastal Zone using ER-2 based MAS Data and Terra Based MODIS Data

The University nf Wisconsin and Louisiana State University have teamed to study the forcing of winter season cold frontal wind systems on sediment distribution patterns and geomorphology in the Louisiana coastal zone. Wind systems associated with cold fronts have been shown to model coastal circulation and resuspend sediments along the micro tidal Louisiana coast (Roberts et at. 1987, Moeller et al. 1993). Remote sensing data is being used to map and track sediment distribution patterns for various wind conditions. Suspended sediment is a building material for coastal progradation and wetlands renewal, but also restricts access to marine nursery environments and impacts oyster bed health. Transferring a suspended sediment concentration (SSC) algorithm to EOS MODerate resolution Imaging Spectroradiometer (MODIS; Barnes et al. 1998) observations may enable estimates of SSC globally.

Moeller, Christopher C.↗

Managing the Evolution of an Enterprise Architecture using a MAS-Product-Line Approach

We view an evolutionary system ns being n software product line. The core architecture is the unchanging part of the system, and each version of the system may be viewed as a product from the product line. Each "product" may be described as the core architecture with sonre agent-based additions. The result is a multiagent system software product line. We describe an approach to such n Software Product Line-based approach using the MaCMAS Agent-Oriented nzethoclology. The approach scales to enterprise nrchitectures as a multiagent system is an approprinre means of representing a changing enterprise nrchitectclre nnd the inferaction between components in it.

Pena, Joaquin↗

High-temperature NMR MAS probe with optimized temperature gradient across sample rotor

A rotor housing assembly for NMR spectroscopy. An elongate rotor has a distal drive end, a proximal end and an internal sample space positioned along its length between the drive and proximal ends. The rotor is driveable about a rotation axis by a drive gas flow. A rotor housing has an interior space in which the rotor is at least partially received. At least one first heated gas flow inlet is positioned opposite the internal sample space, through which a first heated gas flow is controllably flowable into the interior space to heat it and the rotor. At least a pair of spaced apart second heated gas flow outlets are axially spaced from the first heated gas flow inlet to controllably convey a second heated gas flow to heat distal and proximal areas of the sample space to minimize a temperature gradient extending axially within the sample space.

Mehta, Hardeep S.↗

MODIS airborne simulator visible and near-infrared calibration, 1991 FIRE-Cirrus field experiment. Calibration version: FIRE King 1.1

Calibration of the visible and near-infrared channels of the MODIS Airborne Simulator (MAS) is derived from observations of a calibrated light source. For the 1991 FIRE-Cirrus field experiment, the calibrated light source was the NASA Goddard 48-inch integrating hemisphere. Laboratory tests during the FIRE Cirrus field experiment were conducted to calibrate the hemisphere and from the hemisphere to the MAS. The purpose of this report is to summarize the FIRE-Cirrus hemisphere calibration, and then describe how the MAS was calibrated from observations of the hemisphere data. All MAS calibration measurements are presented, and determination of the MAS calibration coefficients (raw counts to radiance conversion) is discussed. Thermal sensitivity of the MAS visible and near-infrared calibration is also discussed. Typically, the MAS in-flight is 30 to 60 degrees C colder than the room temperature laboratory calibration. Results from in-flight temperature measurements and tests of the MAS in a cold chamber are given, and from these, equations are derived to adjust the MAS in-flight data to what the value would be at laboratory conditions. For FIRE-Cirrus data, only channels 3 through 6 were found to be temperature sensitive. The final section of this report describes comparisons to an independent MAS (room temperature) calibration by Ames personnel using their 30-inch integrating sphere.

Arnold, G. Thomas↗