SEARCH · Engineering Papers
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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Quantum-mechanical effects can result in qualitatively different (and sometimes completely opposite) results for excitation energy transfer in plasmonic waveguides.
Concepts for the thermodynamically challenging synthesis of weak N–H bonds by photoinduced proton coupled electron transfer are explored. Upon irradiation with blue light, ammonia synthesis was achieved from the manganese nitride ( tBu Salen)MnN ( tBu Salen = ( S,S )-(+)- N,N' -bis(3,5-di-tert-butylsalicylidene)-1,2-cyclohexanediamine) in the presence of 9,10-dihydroacridine and a ruthenium photocatalyst in i PrOH solution. Although in one case the ruthenium complex bears a remote N–H bond that weakens to 41 kcal mol –1 upon irradiation, control experiments with the N -methylated analog demonstrate the ruthenium complex serves as a photoreductant rather than hydrogen-atom transfer catalyst in aprotic solvents. Luminescence quenching experiments support a ruthenium(II)/(III) cycle rather than a ruthenium(I)/(II) alternative. Identification of the manganese complex following ammonia synthesis was also accomplished.
Four principal intra-particle phenomena occur in a highly concerted manner during the pyrolysis of lignocellulosic materials: heat transfer, mass transfer, chemical reactions, and phase changes.
This work aims to reveal the determinant factors for proton locations and electron coupled proton transfer (ECPT) in biologically relevant hydrogen bonded systems. Pentafluorophenol-anion clusters [C6F5O-•H+•A-]- are chosen to model active sites of biological functions, with the anion A- being systematically varied to ensure the proton affinities (PAs) of the anions well cover the referenced PA of C6F5O- from being appreciably smaller, similar, and to significantly larger. Negative ion photoelectron spectroscopy of these clusters provides spectroscopic evidence showing that proton location in the anionic state is largely following the PA prediction, while ECPT is observed only for the clusters with the anion possessing the electron binding energy (EBE) significantly larger than that of the referenced C6F5O-. Theoretical calculations suggest these clusters are stabilized by forming single strong hydrogen bond between donor and acceptor, and the associated charge and MO analyses fully support the experimental observations. The current holistic cluster model study indicates that PA is the right determinant that can be used to predict the proton location and describe hydrogen bonding structures, while both PA and EBE of anionic groups play important roles in facilitating ECPT process. This work was supported by U.S. Department of Energy (DOE), Office of Basic Energy Sciences, Division of Chemical Science, Geosciences, and Biosciences (X.-B.W.), and performed using EMSL, a national scientific user facility sponsored by DOE’s Office of Biological and Environmental Research and located at Pacific Northwest National Laboratory, which is operated by Battelle Memorial Institute for the DOE. Part of this work was supported by the National Natural Science Foundation of China (No-11604046 for JZ; No. 11727810 for ZRS), as well as “Chenguang Program” by Shanghai Education Development Foundation, Shanghai Municipal Education Commission (No. 16CG38) and Natural Science Foundation of Shanghai (No. 16ZR1448100) (JZ).
Iron oxide nanoparticles undergo self-assembly into well-ordered monolayer films of macroscopic size at the air-water interface. This self-assembly process is the result of the van der Waals forces between the constituent particles. For roughly spherical particles, this monolayer is a 2D hexagonal close packed lattice. With Grazing Incidence X-Ray Diffraction (GID), one can obtain global statistical information about the film’s spacing and correlation length. Herein, we demonstrate that comparable structural information can be obtained by a novel Fourier transform analysis method applied to Scanning Electron Microscopy (SEM) images taken of the film after it has been transferred to a silicon substrate. This consists of using numerical methods to isolate the lattice structure of the monolayer in the SEM image to which a 2D discrete Fourier Transform is applied and the result integrated. This results in Bragg peak information akin to that obtained from GID, whose structure shows the same hexagonal close packed lattice with similar spacing and of greater peak contrast. Furthermore, this analysis technique may prove to be a suitable alternative or compliment to GID for many applications.
Understanding the role of fine coherent precipitates in the micromechanical behavior of precipitate-strengthened shape memory alloys (SMAs), which still remains a mystery heretofore, is of crucial importance to the design of advanced SMAs with optimal functional and mechanical properties. Here, we investigate the lattice strain evolution of, and the stress partition between the nanoscale Ni{sub 4}Ti{sub 3} precipitates and the matrix in a precipitate-strengthened Ni-Ti SMA during different deformation stages by in-situ synchrotron high-energy X-ray diffraction technique. We found that, during R-phase reorientation and stress-induced martensitic transformation, which both involve the shear deformation process, the lattice strain of the nanoscale precipitates drastically increases by a magnitude of 0.5%, which corresponds to an abrupt increase of ∼520 MPa in internal stress. This indicates that stress repartition occurs and most of the stress is transferred to the precipitates during the shear deformation of the matrix. It is further revealed that the nanoscale precipitates which only have a low volume fraction bear a considerable amount of applied stress during all deformation stages investigated, implying that the nanoscale precipitates play an important role in the deformation behavior of the precipitate-strengthened Ni-Ti SMAs.
We demonstrate that spin transfer torque nano-oscillators (STNO) can act as wireless sensors for local current. The STNO acts as a transducer that converts weak direct currents into microwave field oscillations that we detect using an inductive coil. We detect direct currents in the range of 300–700 μA and report them wirelessly to a receiving induction coil at distances exceeding 6.5 mm. This current sensor could find application in chemical and biological sensing and industrial inspection.
The pronounced capacity fade in Ni-rich layered oxide lithium ion battery cathodes observed when cycling above 4.1 V (versus Li/Li{sup +}) is associated with a rise in impedance, which is thought to be due to either bulk structural fatigue or surface reactions with the electrolyte (or combination of both). Here, we examine the surface reactions at electrochemically stressed Li{sub 1–x}Ni{sub 0.8}Co{sub 0.15}Al{sub 0.05}O{sub 2} binder-free powder electrodes with a combination of electrochemical impedance spectroscopy, spatially resolving electron microscopy, and spatially averaging X-ray spectroscopy techniques. We circumvent issues associated with cycling by holding our electrodes at high states of charge (4.1 V, 4.5 V, and 4.75 V) for extended periods and correlate charge-transfer impedance rises observed at high voltages with surface modifications retained in the discharged state (2.7 V). The surface modifications involve significant cation migration (and disorder) along with Ni and Co reduction, and can occur even in the absence of significant Li{sub 2}CO{sub 3} and LiF. These data provide evidence that surface oxygen loss at the highest levels of Li{sup +} extraction is driving the rise in impedance.
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Lipid droplet (LD) utilization is an important cellular activity that regulates energy balance and release of lipid second messengers. Because fatty acids exhibit both beneficial and toxic properties, their release from LDs must be controlled. Here we demonstrate that yeast Sfh3, an unusual Sec14-like phosphatidylinositol transfer protein, is an LD-associated protein that inhibits lipid mobilization from these particles. We further document a complex biochemical diversification of LDs during sporulation in which Sfh3 and select other LD proteins redistribute into discrete LD subpopulations. The data show that Sfh3 modulates the efficiency with which a neutral lipid hydrolase-rich LD subclass is consumed during biogenesis of specialized membrane envelopes that package replicated haploid meiotic genomes. These results present novel insights into the interface between phosphoinositide signaling and developmental regulation of LD metabolism and unveil meiosis-specific aspects of Sfh3 (and phosphoinositide) biology that are invisible to contemporary haploid-centric cell biological, proteomic, and functional genomics approaches.
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Here, we theoretically investigate the feasibility of applying spin squeezing to a light pulse atom interferometer in the presence of large momentum transfer using off resonant Raman transitions, in order to enhance the sensitivity of accelerometry close to the Heisenberg limit. We also show how to implement this scheme in a dual-species atom interferometer for a precision test of the equivalence principle by measuring the Eötvös parameter, and to identify the spin squeezing protocol that is best suited for such an experiment. For a space borne platform in low Earth orbit, such a scheme may eventually enable the measurement of the Eötvös parameter with a sensitivity of the order of 10 -20 within 150 days when 10 5 atoms are employed in each cycle of the experiment.
A reversible density driven insulator to metal to insulator transition in high-spin MnS 2 is experimentally observed, leading with a colossal electrical resistance drop of $10^8$ Omega by 12 GPa. Density functional theory simulations reveal the metallization to be unexpectedly driven by previously unoccupied $S_{2}^{-2}$ $\sigma^{*}_{3p}$ antibonding states crossing the Fermi level. This is a unique variant of the charge transfer insulator to metal transition for negative charge transfer insulators having anions with an unsaturated valence. By 36 GPa the emergence of the low-spin insulating arsenopyrite ($P2_1/c$) is confirmed, and the bulk metallicity is broken with the system returning to an insulative electronic state.
Electric fields play a key role in enzymatic catalysis and can enhance reaction rates by 100,000-fold, but the same rate enhancements have yet to be achieved in thermochemical heterogeneous catalysis. In this work, we probe the influence of catalyst potential and interfacial electric fields on heterogeneous Brønsted acid catalysis. We observed that variations in applied potential of ~380 mV led to a 100,000-fold rate enhancement for 1-methylcyclopentanol dehydration, which was catalyzed by carbon-supported phosphotungstic acid. Mechanistic studies support a model in which the interfacial electrostatic potential drop drives quasi-equilibrated proton transfer to the adsorbed substrate prior to rate-limiting C–O bond cleavage. Large increases in rate with potential were also observed for the same reaction catalyzed by Ti/TiO y H x and for the Friedel Crafts acylation of anisole with acetic anhydride by carbon-supported phosphotungstic acid.
Producing enantioenriched molecules from racemic mixtures is essential for manufacturing. Traditional methods such as resolution, deracemization and enantioconvergent catalysis primarily involve separating or converting enantiomers without altering their structures, or functionalization of stereocentres at or proximal to functional groups. However, there are challenges in enantioselectively forging C–H bonds that are remote from functional groups via hydrogen atom transfer (HAT) with these methods. Here we introduce a strategy for the photoenzymatic stereoablative enantioconvergence of γ-chiral oximes using repurposed flavin-dependent ene-reductases. A photoinduced single-electron reduction of the γ-chiral oxime by an ene-reductase generates an iminyl radical, which then undergoes stereoablative 1,5-HAT at the γ-stereocentre. Subsequent chiral reconstruction through enzymatic HAT and spontaneous imine hydrolysis yields the γ-chiral ketone with high enantioselectivity. This work provides a robust method for remote stereoablative enantioconvergent HAT and broadens the synthetic utility of photobiocatalysis.
Atmospheric hyperspectral VNIR sensing struggles with sub-pixel variability of clouds and limited spectral resolution mixing molecular lines. Our generalized radiative transfer model addresses both issues with new propagation kernels characterized by power-law decay in space.
In order to efficiently image a non-absorbing sample (a phase object), dedicated phase contrast optics are required. Typically, these optics are designed with the assumption that the sample is weakly scattering, implying a linear relation between a sample’s phase and its transmission function. In the strongly scattering, nonlinear case, the standard optics are ineffective, and the transfer functions used to characterize them are uninformative. We use the Fisher information (FI) to assess the efficiency of various phase imaging schemes and to calculate an information transfer function (ITF). We show that a generalized version of Zernike phase contrast is efficient given sufficient prior knowledge of the sample. We show that with no prior knowledge, a random sensing measurement yields a significant fraction of the available information. Finally, we introduce a generalized approach to common path interferometry that can be optimized to prioritize sensitivity to particular sample features. Each of these measurements can be performed using Fourier lenses and phase masks.
Hydrodynamics and heat transfer of heated air flowing in tube with turbilizers on heat transfer surface