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At least 1,117 records · Page 62

De novo protein design of photochemical reaction centers

Abstract Natural photosynthetic protein complexes capture sunlight to power the energetic catalysis that supports life on Earth. Yet these natural protein structures carry an evolutionary legacy of complexity and fragility that encumbers protein reengineering efforts and obfuscates the underlying design rules for light-driven charge separation. De novo development of a simplified photosynthetic reaction center protein can clarify practical engineering principles needed to build new enzymes for efficient solar-to-fuel energy conversion. Here, we report the rational design, X-ray crystal structure, and electron transfer activity of a multi-cofactor protein that incorporates essential elements of photosynthetic reaction centers. This highly stable, modular artificial protein framework can be reconstituted in vitro with interchangeable redox centers for nanometer-scale photochemical charge separation. Transient absorption spectroscopy demonstrates Photosystem II-like tyrosine and metal cluster oxidation, and we measure charge separation lifetimes exceeding 100 ms, ideal for light-activated catalysis. This de novo-designed reaction center builds upon engineering guidelines established for charge separation in earlier synthetic photochemical triads and modified natural proteins, and it shows how synthetic biology may lead to a new generation of genetically encoded, light-powered catalysts for solar fuel production.

59 BASIC BIOLOGICAL SCIENCES↗

Harnessing Photoelectrochemistry for Wastewater Nitrate Treatment Coupled with Resource Recovery

Wastewater is a misplaced resource well suited to recover nutrients, value-added chemicals, energy, and clean water. A photoelectrochemical device is proposed to transform wastewater nitrates to ammonia and nitrous oxide, coupled with water oxidation. Numerical models were developed to quantify the dependence of process efficiencies and nitrogen-removal rates on light absorber band gaps, electrocatalytic kinetic parameters, competing oxygen reduction and hydrogen evolution reactions, and the reacting nitrate species concentrations that affect the mass-transfer limited current densities. With a single light-absorber and state-of-the-art catalysts, optimal solar-to-chemical efficiencies of 7% and 10% and nitrogen-removal rates of 260 and 395 gN m -2 day -1 are predicted for nitrate reduction to ammonia and nitrous oxide, respectively. The influence of competing reactions on the performance depends on the nitrate concentration and band gap of the light absorber modeled. Oxygen reduction is more dominant than hydrogen evolution to compete with the nitrate reduction reaction, but it is mass-transfer limited. Even with kinetic parameters that enhanced the driving forces for the competing reactions, the performance is only minimally affected by these reactions for optimally selected band gaps and nitrate concentrations larger than 100 mM. Here, theoretically predicted peak nitrogen removal rates and specific energy intensities are competitive with reported estimates for electrochemical and Sharon-Anammox processes for ammonia recovery and nitrogen removal, respectively. This result, together with the added benefit of harnessing sunlight to produce value-added products, indicates promise in the photoelectrochemical approach as a tertiary pathway to recover nutrients and energy from wastewater nitrates.

25 ENERGY STORAGE↗

Using Microporous Polytetrafluoroethylene Thin Sheets as a Flexible Solar Diffuser to Minimize Sunlight Glint to Cameras in Space

An innovative design of using microporous PTFE thin sheets as a solar diffuser for MLI blankets or mechanical structure has been developed. It minimizes sunlight or stray-light glint to cameras when it is incident on these components in space. A microporous black PTFE thin sheet solar diffuser has been qualified for flight at NASA GSFC and installed to the TAGSAM arm MLI, OCAMS PolyCam sunshade MLI and SamCam motor riser MLI in the NASA OSIRIS-REx mission to meet the SamCam camera BRDF requirement.

solar diffuser; flexible solar diffuser↗

Alternating Current Photovoltaic Effect

It is well known that the photovoltaic effect produces a direct current (DC) under solar illumination owing to the directional separation of light-excited charge carriers at the p–n junction, with holes flowing to the p-side and electrons flowing to the n-side. In this study, we found that apart from the DC generated by the conventional p–n photovoltaic effect, there is another new type of photovoltaic effect that generates alternating current (AC) in the nonequilibrium states when the illumination light periodically shines at the junction/interface of materials. The peak current of AC at high switching frequency can be much higher than that from DC. The AC cannot be explained by the established mechanisms for conventional photovoltaics; instead, it is suggested to be a result of the relative shift and realignment between the quasi-Fermi levels of the semiconductors adjacent to the junction/interface under the nonequilibrium conditions, which results in electron flow in the external circuit back and forth to balance the potential difference between two electrodes. By virtue of this effect, the device can work as a high-performance broadband photodetector with extremely high sensitivity under zero bias; it can also work as a remote power source providing extra power output in addition to the conventional photovoltaic effect.

36 MATERIALS SCIENCE↗

Unraveling the mechanism of tip-enhanced molecular energy transfer

Electronic Energy Transfer (EET) between chromophores is fundamental in many natural light-harvesting complexes, serving as a critical step for solar energy funneling in photosynthetic plants and bacteria. The complicated role of the environment in mediating this process in natural architectures has been addressed by recent scanning tunneling microscope experiments involving EET between two molecules supported on a solid substrate. These measurements demonstrated that EET in such conditions has peculiar features, such as a steep dependence on the donor-acceptor distance, reminiscent of a short-range mechanism more than of a Förster-like process. By using state of the art hybrid ab initio/electromagnetic modeling, here we provide a comprehensive theoretical analysis of tip-enhanced EET. In particular, we show that this process can be understood as a complex interplay of electromagnetic-based molecular plasmonic processes, whose result may effectively mimic short range effects. Therefore, the established identification of an exponential decay with Dexter-like effects does not hold for tip-enhanced EET, and accurate electromagnetic modeling is needed to identify the EET mechanism.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

World Record Demonstration of > 30% Thermophotovoltaic Conversion Efficiency

Thermophotovoltaic (TPV) devices are solid-state heat engines that convert thermal radiation into electricity using semiconductor diodes, and have applications in energy storage, primary power conversion, and waste heat recovery. Higher temperature emitters and wider band gap photovoltaics (PVs) generally afford higher TPV efficiencies. High temperature emitters are accessible in thermal energy storage applications. We have demonstrated a world record 31% +/- 2% TPV conversion efficiency with a 0.9 cm2 GaAs-based PV device under a 2430 °C thermal emitter, producing an electrical output power of 2.23 W. Critical to the result was the cell’s high reflectance of photon energies below the device band gap. Unlike solar PV, for which sub-band gap (SBG) light is lost, a TPV cell can reflect and recycle SBG light to the thermal emitter. The demonstration was made on a custom-built measurement platform in which a ~100 cm2 graphite thermal emitter was heated under vacuum up to 2430 °C. The TPV efficiency was evaluated by comparing the measured electrical output power of the TPV with the calorimetrically measured total net power incident on the cell. The measured TPV efficiency as a function of thermal emitter temperature was corroborated by our full system modeling predictions. As far as the authors are aware, this is the highest TPV conversion efficiency ever measured, and device improvements should yield > 40% efficiency in the near future.

27 ARPA - Advanced Research Projects Agency-Energy↗

Conference Support, 32nd Western Photosynthesis Conference 2023

This DOE-BES award provided conference support for the 32nd Western Photosynthesis Conference (WPC2023), held January 5–8, 2023 at the Bodega Bay Marine Laboratory in Bodega Bay, California. The Western Photosynthesis Conference is one of three regional photosynthesis meetings held annually in the United States and serves as a primary venue for early-career scientists—graduate students, postdoctoral researchers, and undergraduates—to present research and build professional networks alongside established investigators in the field. Photosynthesis research is central to the DOE Office of Science's Basic Energy Sciences mission, underpinning fundamental understanding of solar energy conversion, biofuels, and the biological transformation of light into chemical energy. DOE-BES funds were used, as proposed, to support registration and housing costs for 20 early-career participants (9 postdoctoral researchers, 9 graduate students, and 2 undergraduates) and to help defray travel costs for two junior invited speakers based outside California, for a total DOE-BES expenditure of $10,060. The meeting was executed as planned, with no significant deviations from the approved program, budget, or schedule. WPC2023 drew 76 registrants across six scientific topic areas, featured 8 of 9 invited/keynote speakers, and provided extensive opportunities for early-career scientists to present talks and posters, compete for recognition awards, and network with senior researchers in the field.

conference↗

OGLE-2017-BLG-0406: Spitzer Microlens Parallax Reveals Saturn-mass Planet Orbiting M-dwarf Host in the Inner Galactic Disk

We report the discovery and analysis of the planetary microlensing event OGLE-2017-BLG-0406, which was observed both from the ground and by the Spitzer satellite in a solar orbit. At high magnification, the anomaly in the light curve was densely observed by ground-based-survey and follow-up groups, and it was found to be explained by a planetary lens with a planet/host mass ratio of q=7.0×10{sup −4} from the light-curve modeling. The ground-only and Spitzer-“only” data each provide very strong one-dimensional (1D) constraints on the 2D microlens parallax vector π{sub E}. When combined, these yield a precise measurement of π{sub E} and of the masses of the host M{sub host}=0.56±0.07 M{sub ⊙} and planet M {sub planet} = 0.41 ± 0.05 M {sub Jup}. The system lies at a distance D {sub L} = 5.2 ± 0.5 kpc from the Sun toward the Galactic bulge, and the host is more likely to be a disk population star according to the kinematics of the lens. The projected separation of the planet from the host is a{sub ⊥}=3.5±0.3 au (i.e., just over twice the snow line). The Galactic-disk kinematics are established in part from a precise measurement of the source proper motion based on OGLE-IV data. By contrast, the Gaia proper-motion measurement of the source suffers from a catastrophic 10σ error.

79 ASTRONOMY AND ASTROPHYSICS↗

URSIES - An ultravariable resolution single interferometer echelle scanner.

Use of a Fabry-Perot interferometer in a Ramsay mount in tandem with an echelle Hilger monochromator with pinholes instead of slits. The instrument, URSIES, is enclosed within a pressure chamber filled with Freon. Photoelectric pulse counting techniques and pressure scanning are used to record the spectrum. This design has four basic advantages: (1) the resolution of the scanner is variable from 5.0 to 0.005 A, and the effective wavelength range is quite broad, from 3500 to 13,000 A; (2) a light gain of ten over conventional grating scanners at resolutions of 0.1 A or better is achieved; (3) very low levels of light from outside the wavelength passband reach the detector; for a resolution of 0.03 A at 6000 A this level is 5%; and (4) there are very low levels of scattered light from the pinholes when extended sources are observed. The scattered light from the instrument at the edge of the solar disk is found to be less than 1% from 4000 to 11,000 A. Measurements demonstrating these advantages are discussed.

Wyller, A. A.↗

An extreme ultraviolet photometer for solar observations from the Atmosphere Explorer satellites

A broadband photometer experiment is being fabricated for the Atmosphere Explorer C, D and E missions to record the solar irradiance in the 40 to 1250 A region with seven distinct passbands. The experiment consists principally of four spinal electron multipliers located behind a moving eight position filter wheel. Six metallic filters are used to spectrally isolate the solar irradiance. In addition three Al2O3 diodes, two with filters, are being used to record the solar irradiance over the range of orbital altitudes from perigee through apogee. A principal goal of the experiment will be to measure time dependence of the solar irradiance with respect to a storage ring synchrotron light source which has been calibrated in terms of the best currently available standards of irradiance.

Heath, D. F.↗

Atmospheric helium and geomagnetic field reversals.

The problem of the earth's helium budget is examined in the light of recent work on the interaction of the solar wind with nonmagnetic planets. It is proposed that the dominant mode of helium (He4) loss is ion pumping by the solar wind during geomagnetic field reversals, when the earth's magnetic field is very small. The interaction of the solar wind with the earth's upper atmosphere during such a period is found to involve the formation of a bow shock. The penetration altitude of the shock-heated solar plasma is calculated to be about 700 km, and ionization rates above this level are estimated for a cascade ionization (electron avalanche) process to average 10 to the 9th power ions/sq cm/sec. The calculated ionization rates and the capacity of the solar wind to remove ionized helium (He4) from the upper atmosphere during geomagnetic dipole reversals are sufficient to yield a secular equilibrium over geologic time scales. The upward transport of helium from the lower atmosphere under these conditions is found to be adequate to sustain the proposed loss rate.

Sheldon, W. R.↗

Six-color photometry of Iapetus, Titan, Rhea, Dione and Tethys

Six-color photometric observations made during Saturn's 1972/73 opposition enable us to separate the solar phase and orbital phase contributions to the observed light variations of Iapetus, Titan, Rhea, Dione and Tethys. Titan shows no orbital variations, but has phase coefficients which range from negligible values in the infrared to 0.014 mag/deg in the ultraviolet. Rhea has a bright leading side, a light curve amplitude of about 0.2 mag, and surprisingly large phase coefficients. Combined with other available information, the observations suggest a very porous, texturally complex surface layer. Dione has a leading side which is a few tenths of a magnitude brighter than the trailing side, but the light curve amplitude has little wavelength dependence and the phase coefficients are significantly smaller than those of Rhea, suggesting a less intricate surface texture. The leading side of Tethys is probably a few tenths of a magnitude brighter than the trailing side. Our Iapetus observations generally supplement the earlier work by Millis.

Noland, M.↗

The nucleus of M31

The nucleus of M31 was photographed at a resolution of 0.2 sec with the 91-cm balloon-borne Stratoscope II telescope. At the half-intensity level, the nucleus was observed to be elliptical with its major axis lying in position angle of 63 (plus or minus 5) deg. The peak surface brightness was 12.7 plus or minus 0.3 V mag per square second of arc assuming B - V = 1.0. The nucleus appears to be a separate feature from the bulge with a scale height of approximately 0.5 pc. The mass of the nucleus is of the order of 100 million solar masses, and the apparent visual mass-to-light ratio is of the order of 20.

Light, E. S.↗

A simple theory of back-surface-field /BSF/ solar cells

An earlier calculation of the I-V characteristics of solar cells contains a mistake. The current generated by light within the depletion layer is too large by a factor of 2. When this mistake is corrected, not only are all previous conclusions unchanged, but the agreement with experiment becomes better. Results are presented in graphical form of new computations which not only take account of the factor of 2, but also include more recent data on material parameters.

Von Roos, O.↗

Multichannel spectrophotometry of stellar flares

Stellar flares have been observed using the 32 channel spectrophotometer on the 5 m telescope. Net flare fluxes in the region 3200-7000 A are presented. A simple model of blackbody radiation and hydrogen recombination emission appears to fit the continuum points well. Owing to vignetting problems, only the region between 4200 and 7000 A was used for a detailed fit to the Planck function to obtain apparent temperatures and effective areas. The rise of each flare was associated with an increase of the area, while the initial steep decline of the light was associated with a similar decrease of the blackbody temperature. The maximum temperatures, coincident with maximum light, were 7500-9500 K, similar to values for solar flares. The hydrogen line emission rose simultaneously with the continuum but declined more slowly. The ratio of H sub gamma to H sub alpha was about 1.5 at the peak, declining to about 1.0 after the peak.

Mochnacki, S. W.↗

Solidification of high temperature molten salts for thermal energy storage systems

The solidification of phase change materials for the high temperature thermal energy storage system of an advanced solar thermal power system has been examined theoretically. In light of the particular thermophysical properties of candidate phase change high temperature salts, such as the eutectic mixture of NaF - MgF2, the heat transfer characteristics of one-dimensional inward solidification for a cylindrical geometry have been studied. The Biot number for the solidified salt is shown to be the critical design parameter for constant extraction heat flux. A fin-on-fin design concept of heat transfer surface augmentation is proposed in an effort to minimize the effects of the salt's low thermal conductivity and large volume change upon fusing.

Sheffield, J. W.↗

Determination of optimum sunlight concentration level in space for 3-5 cascade solar cells

Current-voltage curves were calculated for each cell in a cascade structure using a solar cell diode equation and superposition. Terms for the light generated current, diffusion current, space charge recombination current and series and shunt resistance are included. Individual current voltage curves are added in series with ohmic resistance losses for the cell interconnects to obtain the cascade cell performance. Temperature was varied with concentration, using several models, and ranged from 55 C at one Sun to between 80 and 200 C at 100 Suns. A variety of series resistance and internal resistances were used. Coefficients of the diffusion and recombination terms are strongly temperature dependent. The study indicates that maximum efficiency (30%) occurs in the 50 to 100X Sun concentration range, provided series resistance is below 0.015 ohm-sq cm and cell temperature is 80 C at 100 Suns.

Curtis, H. B.↗