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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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195 records · Page 11

Light energy conservation processes in Halobacterium halobium cells

Proton pumping driven by light or by respiration generates an electrochemical potential difference across the membrane in Halobacterium halobium. The pH changes induced by light or by respiration in cell suspensions are complicated by proton flows associated with the functioning of the cellular energy transducers. A proton-per-ATP ratio of about 3 is calculated from simultaneous measurements of phosphorylation and the proton inflow. This value is compatible with the chemiosmotic coupling hypothesis. The time course of the light-induced changes in membrane potential indicates that light-driven pumping increases a dark pre-existing potential of about 130 mV only by a small amount (20 to 30 mV). The complex kinetic features of the membrane potential changes do not closely follow those of the pH changes, which suggests that flows of ions other than protons are involved. A qualitative model consistent with the available data is presented.

Bogomolni, R. A.↗

Photoelectrolysis of water at high current density - Use of laser light excitation of semiconductor-based photoelectrochemical cells

In the present paper, some results are given for UV laser light irradiation of the photoanode (SnO2, SrTiO3, or TiO2) in a cell for the light-driven electrolysis of H2O, at radiation intensities of up to 380 W/sq cm. The properties of the anode material are found to be independent of light intensity. Conversion of UV light to stored chemical energy in the form of 2H2/O2 from H2O was driven at a rate of up to 30 W/sq cm. High O2 evolution rates at the irradiated anodes without changes in the current-voltage curves are attributed to the excess oxidizing power associated with photogenerated holes. A test for this sort of hypothesis for H2 evolution at p-type materials is proposed.

Wrighton, M. S.↗

Photoconversion from the light-adapted to the dark-adapted state of bacteriorhodopsin

The dark and light adaptation of the bR(trans)570 (bacteriorhodopsin) and bR(cis)550 isomers is analyzed. The equilibrium between the two bR isomers in light-adapted purple membrane films is studied in terms of the wavelength of actinic light and hydration levels. Absorption spectra observed after light adaptations with red and yellow light reveal that red light is less efficient in converting bR(cis)550 to bR(trans)570 than yellow light and the amount of bR(cis)550 in a light-adapted sample increases with decreasing hydration. The rate constants of dark and light adaptation are evaluated; the rate constant of dark adaptation is independent of the hydration level and the rate constant of light adaptation increases with hydration. The acceleration of a dark adaptation by red light is investigated; the dependence of the accelerated dark adaptation on the light intensity is discussed. The action spectrum of light adaptation in a purple membrane suspension is compared with the absorption spectrum of bR(cis)550; correlation between the spectra reveals that cis-to-transconversion is due to excitation of bR(cis)550 and the mechanism of cis-to-trans conversion in film is not affected by humidity levels. It is noted that the light-driven trans-to-cis conversion is a single photon process. The branching at M410 from the all-trans into the 13-cis photocycle is examined.

Kouyama, T.↗

Photoelectrochemical fabrication of spectroscopic diffraction gratings, phase 2

This program was directed toward the production of Echelle diffraction gratings by a light-driven, electrochemical etching technique (photoelectrochemical etching). Etching is carried out in single crystal materials, and the differential rate of etching of the different crystallographic planes used to define the groove profiles. Etching of V-groove profiles was first discovered by us during the first phase of this project, which was initially conceived as a general exploration of photoelectrochemical etching techniques for grating fabrication. This highly controllable V-groove etching process was considered to be of high significance for producing low pitch Echelles, and provided the basis for a more extensive Phase 2 investigation.

Rauh, R. David↗

Light-induced phosphorylation of a membrane protein plays an early role in signal transduction for phototropism in Arabidopsis thaliana

Blue light is known to cause rapid phosphorylation of a membrane protein in etiolated seedlings of several plant species, a protein that, at least in etiolated pea seedlings and maize coleoptiles, has been shown to be associated with the plasma membrane. The light-driven phosphorylation has been proposed on the basis of correlative evidence to be an early step in the signal transduction chain for phototropism. In the Arabidopsis thaliana mutant JK224, the sensitivity to blue light for induction of first positive phototropism is known to be 20- to 30-fold lower than in wild type, whereas second positive curvature appears to be normal. While light-induced phosphorylation can be demonstrated in crude membrane preparations from shoots of the mutant, the level of phosphorylation is dramatically lower than in wild type, as is the sensitivity to blue light. Another A. thaliana mutant, JK218, that completely lacks any phototropic responses to up to 2 h of irradiation, shows a normal level of light-induced phosphorylation at saturation. Since its gravitropic sensitivity is normal, it is presumably blocked in some step between photoreception and the confluence of the signal transduction pathways for phototropism and gravitropism. We conclude from mutant JK224 that light-induced phosphorylation plays an early role in the signal transduction chain for phototropism in higher plants.

NASA Discipline Plant Biology↗

Identification of surface-exposed domains on the reducing side of photosystem I

Photosystem I (PSI) is a multisubunit enzyme that catalyzes the light-driven oxidation of plastocyanin or cytochrome c6 and the concomitant photoreduction of ferredoxin or flavodoxin. To identify the surface-exposed domains in PSI of the cyanobacterium Synechocystis sp. PCC 6803, we mapped the regions in PsaE, PsaD, and PsaF that are accessible to proteases and N-hydroxysuccinimidobiotin (NHS-biotin). Upon exposure of PSI complexes to a low concentration of endoproteinase glutamic acid (Glu)-C, PsaE was cleaved to 7.1- and 6.6-kD N-terminal fragments without significant cleavage of other subunits. Glu63 and Glu67, located near the C terminus of PsaE, were the most likely cleavage sites. At higher protease concentrations, the PsaE fragments were further cleaved and an N-terminal 9.8-kD PsaD fragment accumulated, demonstrating the accessibility of Glu residue(s) in the C-terminal domain of PsaD to the protease. Besides these major, primary cleavage products, several secondary cleavage sites on PsaD, PsaE, and PsaF were also identified. PsaF resisted proteolysis when PsaD and PsaE were intact. Glu88 and Glu124 of PsaF became susceptible to endoproteinase Glu-C upon extensive cleavage of PsaD and PsaE. Modification of PSI proteins with NHS-biotin and subsequent cleavage by endoproteinase Glu-C or thermolysin showed that the intact PsaE and PsaD, but not their major degradation products lacking C-terminal domains, were heavily biotinylated. Therefore, lysine-74 at the C terminus of PsaE was accessible for biotinylation. Similarly, lysine-107, or lysine-118, or both in PsaD could be modified by NHS-biotin.

Non-NASA Center↗

Proton transfer and energy coupling in the bacteriorhodopsin photocycle

A description of the rate constants and the energetics of the elementary reaction steps of the photocycle of bacteriorhodopsin has been helpful in understanding the mechanism of proton transport in this light-driven pump. The evidence suggests a single unbranched reaction sequence, BR-hv----K in equilibrium with L in equilibrium with M1----M2 in equilibrium with N in equilibrium with O----BR, where coupling to the proton-motive force is at the energetically and mechanistically important M1----M2 step. The consequences of site-specific mutations expressed homologously in Halobacterium halobium have revealed characteristics of the Schiff base deprotonation in the L----M1 reaction, the reorientation of the Schiff base from the extracellular to the cytoplasmic side in the M1----M2 reaction, and the reprotonation of the Schiff base in the M2----N reaction.

NASA Discipline Exobiology↗

A residue substitution near the beta-ionone ring of the retinal affects the M substates of bacteriorhodopsin

The switch in the bacteriorhodopsin photocycle, which reorients access of the retinal Schiff base from the extracellular to the cytoplasmic side, was suggested to be an M1----M2 reaction (Varo and Lanyi. 1991. Biochemistry. 30:5008-5015, 5016-5022). Thus, in this light-driven proton pump it is the interconversion of proposed M substates that gives direction to the transport. We find that in monomeric, although not purple membrane-lattice immobilized, D115N bacteriorhodopsin, the absorption maximum of M changes during the photocycle: in the time domain between its rise and decay it shifts 15 nm to the blue relative to the spectrum at earlier times. This large shift strongly supports the existence of two M substates. Since D115 is located near the beta-ionone ring of the retinal, the result raises questions about the possible involvement of the retinal chain or protein residues as far away as 10 A from the Schiff base in the mechanism of the switching reaction.

NASA Discipline Exobiology↗

NASA Tech Briefs, October 2009

Topics covered include: Light-Driven Polymeric Bimorph Actuators; Guaranteeing Failsafe Operation of Extended-Scene Shack-Hartmann Wavefront Sensor Algorithm; Cloud Water Content Sensor for Sounding Balloons and Small UAVs; Pixelized Device Control Actuators for Large Adaptive Optics; T-Slide Linear Actuators; G4FET Implementations of Some Logic Circuits; Electrically Variable or Programmable Nonvolatile Capacitors; System for Automated Calibration of Vector Modulators; Complementary Paired G4FETs as Voltage-Controlled NDR Device; Three MMIC Amplifiers for the 120-to-200 GHz Frequency Band; Low-Noise MMIC Amplifiers for 120 to 180 GHz; Using Ozone To Clean and Passivate Oxygen-Handling Hardware; Metal Standards for Waveguide Characterization of Materials; Two-Piece Screens for Decontaminating Granular Material; Mercuric Iodide Anticoincidence Shield for Gamma-Ray Spectrometer; Improved Method of Design for Folding Inflatable Shells; Ultra-Large Solar Sail; Cooperative Three-Robot System for Traversing Steep Slopes; Assemblies of Conformal Tanks; Microfluidic Pumps Containing Teflon[Trademark] AF Diaphragms; Transparent Conveyor of Dielectric Liquids or Particles; Multi-Cone Model for Estimating GPS Ionospheric Delays; High-Sensitivity GaN Microchemical Sensors; On the Divergence of the Velocity Vector in Real-Gas Flow; Progress Toward a Compact, Highly Stable Ion Clock; Instruments for Imaging from Far to Near; Reflectors Made from Membranes Stretched Between Beams; Integrated Risk and Knowledge Management Program -- IRKM-P; LDPC Codes with Minimum Distance Proportional to Block Size; Constructing LDPC Codes from Loop-Free Encoding Modules; MMICs with Radial Probe Transitions to Waveguides; Tests of Low-Noise MMIC Amplifier Module at 290 to 340 GHz; and Extending Newtonian Dynamics to Include Stochastic Processes.

Source record↗

Excited-State and Nonadiabatic Molecular Dynamics Methods with Broad Applicability

Electronically excited states play a pivotal role in the capture, transformation, storage, and emission of radiative energy. Despite much recent progress for small model systems, excited state properties and dynamics in many larger molecular devices and materials have remained elusive for experiment and theory. Nonadiabatic transitions between electronic states turn radiative energy into heat and are particularly difficult to control. This project aims to develop new electronic structure and nonadiabatic molecular dynamics (NAMD) methods to simulate, predict, and ultimately control the flow and transformation of excitation energy in a wide-range of light-driven molecular devices such as dyes, photocatalysts, and fluorescence emitters.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Exploring the Photophysics of N-Type Polymer N2200

The polymer interphase is a complex environment comprised of polymer chains, solvent molecules, and electrolyte ions. However, the microenvironments that these ingredients produce is both poorly-understood and difficult to investigate given the system's inherent structural heterogeneity. Nonetheless, a fundamental understanding of the structure, electrochemical behavior, and excited-state dynamics is a key prerequisite to optimizing devices based on such a system - for instance, photoelectrochemical cells for the direct, light-driven production of solar hydrogen, which may minimize efficiency losses compared to sequential light harvesting and electrochemical hydrogen production in separate but linked devices. This work combines transient absorption (TA) spectroscopy, which is a powerful tool for the observation of a variety of excited states on a femto- to microsecond timescale, with time-resolved microwave conductivity (TRMC) spectroscopy, which selectively probes the dynamics of free charge carriers (FC), of a blend of a donor polymer (PTB7-Th) and acceptor polymer (N2200) in a bulk heterojunction. Initial results indicate an extension of FC lifetime and homogenization of the microenvironment on a whole-film level, not just at the surface of the polymer; however, many questions are still under active investigation, including the changes in energy of the involved polaron states, effective conjugation length, FC mobility and migration distance, etc. Additional experiments regarding the photoinitiated behavior of the blend in different environments and on different timescales are ongoing.

charge recombination↗

Pre-steady-state kinetics of nanocrystal:molybdenum nitrogenase biohybrids reveals hole-scavenging efficiency is critical to N 2 reduction

Molybdenum (Mo) nitrogenase is a two-component enzyme complex that catalyzes the reduction of dinitrogen to ammonia and protons to hydrogen gas. We have shown that electrons for dinitrogen reduction can be delivered photochemically to the catalytic MoFe protein component by cadmium sulfide (CdS) nanocrystals. In this study, we used electron paramagnetic resonance spectroscopy to measure the transient populations of catalytic intermediates. We fit the populations with a pre-steady-state kinetic model, which allowed us to distinguish between productive and non-productive reaction pathways and extract the rate constants for the reaction. Our results demonstrated that the rate of catalytic electron delivery into MoFe protein increased with the concentration of the sacrificial electron donor. This enabled electron delivery to exceed the rate of hydride protonation, a relaxation pathway that competes with N 2 binding. Thus, managing the balance between electron transfer and hole transfer reactions is required to achieve a kinetic regime that favors N 2 reduction.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Characterizing Sustained Solar-to-Hydrogen Electrocatalysis at Low Cell Potentials Enabled by Crude Glycerol Oxidation

Unassisted solar-driven water electrolysis as a sustainable source for H 2 is limited by the high overpotential necessary to drive the oxygen evolution reaction (OER). Crude glycerol is an extremely alkaline byproduct of biodiesel synthesis that can be valorized or refined to produce more desirable chemicals. Glycerol can also be directly oxidized on an anode, replacing water oxidation, to reduce the applied cell potential requirements of electrolytic H 2 production or CO 2 reduction. An advantage of oxidizing glycerol in its crude form is the opportunity to valorize it without initial refinement. We describe an approach to replace the OER half-reaction with the sacrificial crude glycerol electrooxidation on a layered Au–Pt–Bi electrocatalyst on a Ni substrate. Compared to compositions with fewer components, the AuPtBi–Ni electrocatalyst improved the duration of performance and reduced the overall cell potential for glycerol electrooxidation in the extreme alkaline solutions representative of crude glycerol. These enhancements facilitated extended, unassisted hydrogen evolution from crude glycerol electrolysis, even under the power of a single-junction silicon solar cell at less than 1 sun illumination. We characterized the oxidation products of crude glycerol electrolysis and the subsequent products formed spontaneously in the electrolyte in the highly alkaline solution. This analysis helps to both identify the stoichiometric limits of glycerol oxidation at the low cell potentials of interest here and to understand the chemical control imparted by electrocatalysis on the ultimate compounds formed in the crude solution. Furthermore, the results for the AuPtBi electrocatalyst show that incorporating crude glycerol oxidation into integrated electrochemical systems can simultaneously simplify their design and significantly improve solar-to-hydrogen rates.

08 HYDROGEN↗

Photo-Swing CO2 Capture Using a Branched Polyethylenimine As Sorbents and TiN Light Absorber

Using branched polyethylenimine as the sorbent material for dilute CO2 capture, a photo-swing method is demonstrated in an industrially relevant support architecture using titanium nitride (TiN) nanosized light absorbers coupled with low-power LEDs with irradiances up to 420 mW cm-2. The photo-swing desorption process is applied to dry and humid streams of 400 ppm CO2 diluted in N2. Consistent with known sorption mechanisms for aminopolymers, humid CO2 streams increased the CO2 uptake, in our case by ~30%. The photo-swing CO2 capture desorbed ~83% and ~100% CO2 compared to thermally-driven desorption over the same period for a dry and humid CO2 stream, respectively. The photo-swing CO2 capture exhibits robust performance over >90 cycles without significant signs of photo(thermal) induced sorbent degradation. This work lays the groundwork for photo-swing DAC technology as a scalable, energy-efficient solution for CO2 capture, well-suited for modular systems in remote locations utilizing intermittent renewable energy sources.

36 MATERIALS SCIENCE↗

Early-stage dynamics of chloride ion–pumping rhodopsin revealed by a femtosecond X-ray laser

Chloride ion–pumping rhodopsin (ClR) in some marine bacteria utilizes light energy to actively transport Cl – into cells. How the ClR initiates the transport is elusive. Here, we show the dynamics of ion transport observed with time-resolved serial femtosecond (fs) crystallography using the Linac Coherent Light Source. X-ray pulses captured structural changes in ClR upon flash illumination with a 550 nm fs-pumping laser. High-resolution structures for five time points (dark to 100 ps after flashing) reveal complex and coordinated dynamics comprising retinal isomerization, water molecule rearrangement, and conformational changes of various residues. Combining data from time-resolved spectroscopy experiments and molecular dynamics simulations, this study reveals that the chloride ion close to the Schiff base undergoes a dissociation–diffusion process upon light-triggered retinal isomerization.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗