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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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42 records · Page 3

Unraveling the mechanism of recognition of the 3’ splice site of the adenovirus major late promoter intron by the alternative splicing factor PUF60

Pre-mRNA splicing is critical for achieving required amounts of a transcript at a given time and for regulating production of encoded protein. A given pre-mRNA may be spliced in many ways, or not at all, giving rise to multiple gene products. Numerous splicing factors are recruited to pre-mRNA splice sites to ensure proper splicing. One such factor, the 60 kDa poly(U)-binding splicing factor (PUF60), is recruited to sites that are not always spliced, but rather function as alternative splice sites. In this study, we characterized the interaction of PUF60 with a splice site from the adenovirus major late promoter (the AdML 3' splice site, AdML3’). We found that the PUF60–AdML3’ dissociation constants are in the micromolar range, with the binding affinity predominantly provided by PUF60’s two central RNA recognition motifs (RRMs). A 1.95 Å crystal structure of the two PUF60 RRMs in complex with AdML3’ revealed a dimeric organization placing two stretches of nucleic acid tracts in opposing directionalities, which can cause looping of nucleic acid and explain how PUF60 affects pre-mRNA geometry to effect splicing. Solution characterization of this complex by light-scattering and UV/Vis spectroscopy suggested a potential 2:1 (PUF60 2 :AdML3’) stoichiometry, consistent with the crystal structure. This work defines the sequence specificity of the alternative splicing factor PUF60 at the pre-mRNA 3’ splice site. Our observations suggest that control of pre-mRNA directionality is important in the early stage of spliceosome assembly, and advance our understanding of the molecular mechanism by which alternative and constitutive splicing factors differentiate among 3’ splice sites.

59 BASIC BIOLOGICAL SCIENCES↗

Identification and Quantification of Photosynthetic Pigments in Algae (Laboratory Analytical Procedure (LAP))

The Laboratory Analytical Procedure (LAP) outlined here describes a method to quantitatively extract phytopigments from microalgae biomass, as well as to identify and quantify individual pigments based on separation and detection with a High-Performance Liquid Chromatography (HPLC) system coupled to a Diode Array Detector (DAD). Pigments were extracted with greater than 95 % extraction efficiency. Chromatographic conditions allowed for isomeric resolution between pigments and identification based on UV/Vis spectra and comparison to analytical standards.

09 BIOMASS FUELS↗

Modeling Charge Transfer Excitation with Variation After Response Quantum Monte Carlo (Final Technical Report)

The electronically excited states of molecules play critical roles both in spectroscopy and in technological application, ranging from UV/Vis absorption experiments to the production of solar fuels. However, certain types of excitations, such as charge transfer excitations, remain difficult to treat with existing methods such as time dependent density functional theory or linear response coupled cluster. Under this Early Career Research Award, we developed a number of different theoretical methods to address this issue, which began with Variational Monte Carlo methods and branched into multiple types of excited-state-specific quantum chemistry.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Computational and Experimental Investigation of Chiral and Achiral Two‐Dimensional Organic Lead Bromide Perovskites: Octahedral Distortions and Electronic and Optical Properties

A computational investigation is presented, in conjunction with synthesis and experimental characterization, into the structural, electronic, and optical properties of layered two-dimensional organic lead bromide perovskites. Materials based on the chiral (R/S)-4-fluoro-α-methylbenzylammonium (R/S-FMBA), which have been shown to lead to bright room-temperature circularly polarized luminescence, are contrasted with the similar achiral 4-fluorobenzylammonium (FBA). Using density functional theory (DFT) with van der Waals (vdW) corrections, relaxed structures (compared with X-ray diffraction, XRD) and optical absorption spectra (compared with experiments) are studied, as well as band structure and orbital character of transitions. A Python code is developed and provided to calculate octahedral distortions and compare DFT and XRD results, finding that vdW corrections are important for accuracy and that DFT overestimates octahedral tilt angles. (FMBA) 2 PbBr 4 shows among the largest tilt angle differences (often termed Δ β ) reported, 14°–15°, indicating strong inversion symmetry-breaking, which enables its chiral emission. A large resulting Dresselhaus spin-splitting effect is found. The lowest-energy optical transitions involve the perovskite only and are polarized within the layer. This work furthers understanding of structure-property relations with applications to optoelectronics and spintronics.

UV/vis spectroscopy↗

Direct Measurement of Crossover and Interfacial Resistance of Ion-Exchange Membranes in All-Vanadium Redox Flow Batteries

Among various components commonly used in redox flow batteries (RFBs), the separator plays a significant role, influencing resistance to current as well as capacity decay via unintended crossover. It is well-established that the ohmic overpotential is dominated by the membrane and interfacial resistance in most aqueous RFBs. The ultimate goal of engineering membranes is to improve the ionic conductivity while keeping crossover at a minimum. One of the major issues yet to be addressed is the contribution of interfacial phenomena in the influence of ionic and water transport through the membrane. In this work, we have utilized a novel experimental system capable of measuring the ionic crossover in real-time to quantify the permeability of ionic species. Specifically, we have focused on quantifying the contributions from the interfacial resistance to ionic crossover. The trade-off between the mass and ionic transport impedance caused by the interface of the membranes has been addressed. The MacMullin number has been quantified for a series of electrolyte configurations and a correlation between the ionic conductivity of the contacting electrolyte and the Nafion® membrane has been established. The performance of individual ion-exchange membranes along with a stack of various separators have been explored. We have found that utilizing a stack of membranes is significantly beneficial in reducing the electroactive species crossover in redox flow batteries compared to a single membrane of the same fold thickness. For example, we have demonstrated that the utilization of five layers of Nafion ® 211 membrane reduces the crossover by 37% while only increasing the area-specific resistance (ASR) by 15% compared to a single layer Nafion ® 115 membrane. Therefore, the influence of interfacial impedance in reducing the vanadium ion crossover is substantially higher compared to a corresponding increase in ASR, indicating that mass and ohmic interfacial resistances are dissimilar. We have expanded our analysis to a combination of commercially available ion-exchange membranes and provided a design chart for membrane selection based on the application of interest (short duration/high-performance vs. long-term durability). The results of this study provide a deeper insight into the optimization of all-vanadium redox flow batteries (VRFBs).

UV/Vis spectroscopy↗