Biophysical analysis of the Mycobacteria tuberculosis peptide binding protein DppA reveals a stringe
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Fernando, Dinesh M.↗
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Results for “clifford”
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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Raman Spectroscopy Coupled with Chemometric Analysis for Speciation and Quantitative Analysis of Aqueous Phosphoric Acid Systems
Complex chemical systems that exhibit varied and matrix-dependent speciation are notoriously difficult to monitor and characterize on-line and in real-time. Optical spectroscopy is an ideal tool for in situ characterization of chemical species that can enable quantification as well as species identification. Chemometric modeling, a multivariate method, has been successfully paired with optical spectroscopy to enable measurement of analyte concentrations even in complex solutions where univariate methods such as Beer’s law analysis fail. Here, Raman spectroscopy is used to quantify the concentration of phosphoric acid and its three deprotonated forms during a titration. In this system, univariate approaches would be difficult to apply due to multiple species being present simultaneously within the solution as pH is varied. Locally Weighted Regression (LWR) modeling was used to determine phosphate concentration from spectral signature. LWR results, in tandem with Multivariate Curve Resolution modeling, provide direct measurement of the concentration of each phosphate species using only the Raman signal. Furthermore, results are presented within the context of fundamental solution chemistry, including Pitzer equations to compensate for activity coefficients and non-idealities associated with high ionic strength systems.
46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗
Realization of a Photoelectrochemical Cascade for the Generation of Methanol: A Liquid Solar Fuel
Not Available
3-terminal tandems↗
On-Line Monitoring of Gas-Phase Molecular Iodine Using Raman and Fluorescence Spectroscopy Paired with Chemometric Analysis
Molten salt reactors (MSRs) have the potential to safely support green energy goals. However, licensing and deployment of these systems will be aided through development of new technology. This includes on-line monitoring tools for real-time compositional analysis. Of particular interest is quantifying iodine within reactor off-gas streams to support design and operational control of reactor off-gas treatment systems. Here we discuss the development of advanced Raman spectroscopy systems for the on-line analysis of I 2(g) within the gas phase. Signal response is explored with two Raman instruments utilizing a 532 nm and a 671 nm excitation source, as a function of I 2(g) pressure and temperature. Furthermore, the applicability of chemometric modeling for advanced analysis of data is explored. Raman spectroscopy paired with chemometric analysis is demonstrated to be a powerful route to analyzing I 2(g) composition within the gas phase, which lays the foundation for applications within molten salt reactor off-gas analysis and other significant chemical processes producing iodine species.
21 SPECIFIC NUCLEAR REACTORS AND ASSOCIATED PLANTS↗
Infrared Spectroelectrochemical Insights into Rhenium-Based Supramolecular Assemblies for Electron Storage and Transfer
Three supramolecular square assemblies featuring Re(CO)3Cl corners and monodentate pyridyl linkers [4,4′-bipyridine, (1a), pyrazine (2a), and 1,2-di(4-pyridyl)ethylene (3a), where a denotes the native state] were synthesized and studied via infrared spectroelectrochemistry (IR-SEC). IR-SEC revealed that the length of the bridging ligand and degree of electronic coupling in rhenium squares greatly impact the reduction pathway in both inert and CO2 atmospheres; notably, the squares are capable of interacting with CO2 after only ligand reduction, thereby avoiding the need for an additional reductive event to generate the rhenium anion. This mechanism differs from that of mononuclear complexes, highlighting how unique redox properties can be endowed by electronic coupling in supramolecular systems.
Koehne, Sydney Marie↗
A Structure-based Design Approach for Generating High Affinity BRD4 D1-Selective Chemical Probes
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Cui, Huarui↗
Impact of Flow Configurations on Response Time and Data Quality in Real-Time, In-Line Fourier Transform Infrared (FTIR) Monitoring of Viscous Flows
The real-time, in-line monitoring of continuous flow concentrations is widely conducted via infrared (IR) spectrometry by using a flow cell connected to a reactive flow stream. For protective purposes, the IR sensor tip is typically offset from the flow. This offset can cause the formation of a stagnant boundary layer above the sensor, especially when dealing with high-viscosity fluids. As a result, the IR signal response time is often controlled by the slow diffusional exchange of fluid in the boundary layer, as confirmed via 2D computational fluid dynamics (CFD) simulations. We evaluated several flow configuration modifications in a typical IR flow cell in order to identify the changes to the flow dynamics that enable improved response times with minimal changes to the cell configuration: the use of (i) vertical flow, where the standard horizontal flow over the sensor is redirected to contact vertically with the sensor, (ii) a static mixer to create radial flow momentum above the IR sensor, and (iii) horizontal or vertical nozzles to direct the flow toward the IR sensor. The vertical flow configuration did not show any significant improvement over the standard horizontal flow configuration. However, the static mixer, horizontal nozzle, and vertical nozzle configurations all resulted in markedly improved response times and signal quality, albeit at the expense of a higher pressure drop across the flow cell. These results point toward straightforward, user-accessible modifications of in-line IR flow cells that result in significant improvements in signal stability and acquisition times.
42 ENGINEERING↗
Role of Mass Transport in Electrochemical CO 2 Reduction to Methanol Using Immobilized Cobalt Phthalocyanine
Not Available
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Precise Genomic Riboregulator Control of Metabolic Flux in Microbial Systems
Not Available
59 BASIC BIOLOGICAL SCIENCES↗
Fano Resonance in CO 2 Reduction Catalyst Functionalized Quantum Dots
Molecular catalyst functionalized semiconductor quantum dots (QDs) are a promising modular platform for developing novel hybrid photocatalysts. The interaction between adsorbed catalyst vibrations and the QD electron intraband absorption can influence the photophysical properties of both the QD and the catalysts and potentially their photocatalysis. In CdSe QDs functionalized by the CO 2 reduction catalyst, Re(CO) 3 (4,4’-bipyridine-COOH)Cl, we observe that the transient Fano resonance signal resulting from coupling of the catalyst CO stretching mode and the QD conduction band electron mid-IR intraband absorption appears on an ultrafast time scale and decays with the electron population, irrespective of the occurrence of photoreduced catalysts. The Fano asymmetry factor increases with an increase in the adsorbed catalyst number and a decrease in QD sizes. The latter can be attributed to an enhanced charge transfer interaction between the more strongly quantum-confined QD conduction band and catalyst LUMO levels. These results provide a more in-depth understanding of interactions in excited QD-catalyst hybrid photocatalysts.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Cambered Bipyridyl Ligand with Extended Aryl System Enables Electrochemical Reduction of Carbon Dioxide and Bicarbonate by Mn(bpy)(CO) 3 Br-type Catalyst Immobilized on Carbon Nanotubes
Heterogeneous materials containing molecular catalytic sites show promise for electrocatalytic reduction of CO 2 to energy-enriched carbon products. Interactions between the catalyst and the heterogeneous support increasingly are recognized as important in governing product selectivity and rate. Recent work on Mn(R-bpy)(CO) 3 Br type catalysts immobilized on multiwalled carbon nanotubes (MWCNT) demonstrated control of electrocatalytic behavior with steric modification of the molecular catalyst. Phenyl groups installed in the 4,4' positions of the bipyridine ligand (ph-bpy) maximized performance through π–π interactions with the MWCNT support. Herein we report the outcome of extending the ligand π system with Mn(nap-bpy)(CO) 3 Br (nap-bpy = 4,4'-di(naphthalen-1-yl)-2,2'-bipyridine) and Mn(pyr-bpy)(CO) 3 Br (pyr-bpy = 4,4'-di(pyren-1-yl)-2,2'-bipyridine) immobilized on MWCNT. We demonstrate exceptional electrocatalysis with Mn(nap-bpy)(CO) 3 Br/MWCNT (FE CO > 92%; J CO = 16.5 mA/cm 2 ) and find that this catalyst electrochemically reduces bicarbonate in the absence of deliberately added CO 2 at a remarkable overall selectivity of >80% for carbon products (FE HCOO – = 52% and FE CO = 29%). We show diminishing returns to simply adding aromatic character to the bipyridyl ligand with Mn(pyr-bpy)(CO) 3 Br/MWCNT and observe a unique cambering of the Mn(nap-bpy)(CO) 3 Br bipyridyl ligand that we believe enables selective catalysis. Mechanistic studies were carried out on Mn(nap-bpy)(CO) 3 Br/MWCNT using a novel thin-film infrared spectroelectrochemical (IR-SEC) technique. These experiments observe the immobilized Mn(nap-bpy)(CO) 3 Br undergo single electron reduction to a Mn-centered radical that binds CO 2 in a reduction-coupled process.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Surface-Functionalized, Two-Dimensional Polymer Electrochromic Layers as Ultrafast, Multi-State Infrared Optical Gates
Electrochromic devices have widespread application potential, but the currently available switching speeds limit broad real-world implementation of this technology. Here, we report surface-engineered two-dimensional polymers with ionophilic pores that offer unprecedented switching speeds in solid-state, two-terminal, electrochromic devices. In particular, we demonstrate that a crystalline donor–acceptor 2DP functionalized with ethylene glycol oligomers exhibits multistate infrared absorption that is 4× faster (t c = 320 ms) with 3× coloration efficiency (491 cm 2 C –1 ) compared to an alkyl functionalized 2DP constructed from the same chromophores. The functionalized nanoporous surfaces enable rapid switching in these materials under either oxidative or reductive conditions, allowing us to access a range of robust, stable optical responses in a single electrochromic layer. These attributes led us to leverage surface-functionalized 2DPs as multistate infrared logic gates. Collectively, this work demonstrates that surface engineering of nanoporous crystalline lattices is a promising approach to co-optimize the electronic and ionic conductivities required to achieve rapidly switchable electrochromic layers. Beyond speed and efficiency, the demonstration of multistate infrared characteristics shows that electrochromic frameworks are useful in integrated optoelectronic circuits. This positions surface-engineered 2DPs as improved electrochromic coatings and a new material platform for photonic information processing and adaptive devices.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Enhanced Microseismicity During Production Pumping Cessation at the San Emidio Geothermal Field (Nevada, USA) in December 2016
Abstract Tectonic activity, geothermal fluids, and microseismic events (MSEs) tend to occur in similar locations as a result of spatiotemporal changes in the subsurface stress state. To quantify this association, we analyze data from a dense seismic array deployed at the San Emidio geothermal field, Nevada for 1 week in December 2016 to coincide with a 19.45‐hr shutdown of all injection and production pumping operations. 123 MSEs were detected, of which 101 occurred during the shutdown. The spatial association of the MSEs with the production wells suggests a causal relationship between the production cessation and the MSEs. Here we performed a detailed analysis to investigate reservoir material properties, distribution of seismically activated faults, and local stress state. We determined the hypocenters, magnitudes, and focal mechanisms for the MSEs, P‐wave tomographic velocity model, and local stress tensor. The results show that most MSEs occurred near the production wells. Magnitudes fall between −2.2 and 0.0 with larger events located closer to the production wells. Most MSEs occurred within a westward‐dipping normal fault zone in the reservoir associated with anomalously low P‐wave velocity values. The focal mechanism and stress inversion results show predominantly normal faulting with the maximum horizontal stress oriented north‐south. We suggest that the MSEs during shutdown were triggered on pre‐existing, small‐scale, critically stressed fault patches in the reservoir as the pore pressure increased around the production wells when the production pumping ceased. We interpret the larger MSE magnitudes closer to the production wells as a result of higher pore pressure increase.
15 GEOTHERMAL ENERGY↗
Earth Sciences Are the Model Sciences of the Anthropocene
After 4.5 billion years as a dynamic and evolving planet, Earth today continues to evolve but with new dynamics. Earth scientists writ large have special opportunities and responsibilities to accelerate our understanding of the changes that are transforming our most remarkable home.
Richter, Daniel↗