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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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At least 145 records · Page 8

Correlating wavelength dependence in LiMn2O4 cathode photo-accelerated fast charging with deformations in local structure

The growth in electrified transportation has benefited from the massive worldwide research efforts used to discover and improve electrode materials and electrolytes. Nevertheless, lithium-ion batteries still suffer from a slow-charging limitation. Recently, it has been demonstrated that white light illumination of LiMn2O4 provokes faster charging, improving the kinetics of delithiation without the use of nanostructured active materials. In this work, we probe the mechanism of photo-accelerated fast charging and show that Mn d-d electronic transitions occurring under red light illumination are largely responsible for the increased charging rate. It is further demonstrated through X-ray absorption spectroscopy methods that LiMn2O4 Mn-Mn bond distances shorten after d-electron excitation. The shrinkage in the crystal volume beneficially contributes to delithiation kinetics by lowering the resistance to lithium-ion conduction. Advanced materials that can absorb light to modulate their structure may provide us with a new mechanistic pathway to pursue for increasing charge transfer rates.

25 ENERGY STORAGE↗

Role of calcium ions in phytochrome responses: an update

Recent findings related to the role of calcium ions in phytochrome responses are reviewed and summarized. Hypotheses tested are the activation of calmodulin by light-regulated Ca2+ transport in cells and the photoinduction of calmodulin-activated enzyme activities. Discussion focuses on evidence that Ca2+ helps to regulate phytochrome responses, calcium requirements for photoinduced spore germination in the fern Onoclea, Ca2+ fluxes and phytochrome function in the alga Mougeotia, calmodulin antagonist blocking of red-light stimulated chloroplast rotation, the role of phosphorylation in calmodulin-regulated responses, and phytochrome regulation of nuclear protein phosphorylation.

NASA Discipline Plant Biology↗

Photopic transduction implicated in human circadian entrainment

Despite the preeminence of light as the synchronizer of the circadian timing system, the phototransductive machinery in mammals which transmits photic information from the retina to the hypothalamic circadian pacemaker remains largely undefined. To determine the class of photopigments which this phototransductive system uses, we exposed a group (n = 7) of human subjects to red light below the sensitivity threshold of a scotopic (i.e. rhodopsin/rod-based) system, yet of sufficient strength to activate a photopic (i.e. cone-based) system. Exposure to this light stimulus was sufficient to reset significantly the human circadian pacemaker, indicating that the cone pigments which mediate color vision can also mediate circadian vision.

Non-NASA Center↗

A recent change in the brightness and form of the HH46 reflection nebula

A several-fold increase in the surface brightness of the scattered light component of the southern Herbig-Haro object HH46 took place between January 1984 and May 1986. A more subtle change in the shape of the nebula also occurred in that a small region, formerly only prominent in the infrared, is now the brightest part of the reflection nebula in visible red light. The change is due either to a flaring of the adjacent but still invisible young stellar object or to a partial clearing of the dust which still surrounds it. In May 1987, the nebula still appeared bright suggesting that the change may be a long-term one.

Graham, J. A.↗

UV-A/Blue-Light responses in algae

All life on earth depends on light. A variety of photoreceptors capture the light for a wide range of reactions. Photosynthetic organisms absorb the light necessary for energy transformation and charge separation facilitating photosynthesis. In addition to the bulk pigments there is a great diversity of photoreceptors present in minute concentrations that control development, metabolism and orientation of plants and microorganisms. Based on its spectral absorbance, the well-studied phytochrome system acts in the RL (red light) region as well as in the UV-A/BL (blue light) region where the above mentioned reactions are mediated by a variety of photoreceptors whose natures are largely unknown. Phyllogenetically the UV-A/BL photoreceptors seem to be more ancient pigments that eventually were replaced by the phytochrome system. However, there are many reports that suggest a coaction between the UV-A/BL receptors and the phytochrome system. In several cases the UV-A/BL activation is the prerequisite for the phytochrome reaction. Historically it was the German botanist Julius Sachs who first discovered in 1864 that phototropism in plants was due to BL reactions. It took over 70 years until Bunning (1937) and Galston and Baker (1949) rediscovered the BL response. Since then, an ever-increasing attention has been paid to this effect. In this contribution, the general aspect of UV-A/BL responses and especially the responsiveness of algae will be covered.

Senger, Horst↗

Radiation Blocking Lenses

Biomedical Optical Company of America's (BOCA) suntiger lenses, similar in principle to natural filters in the eyes of hawks and eagles, bar 99 percent of potentially harmful wavelengths, while allowing visually useful colors of light (red, orange, green) to pass through. They also improve visual acuity, night vision and haze or fog visibility. The lenses evolved from work done by James B. Stephens and Dr. Charles G. Miller of the Jet Propulsion Laboratory. They developed a formula and produced a commercial welding curtain that absorbs, filters, and scatters light. This research led to protective glasses now used by dentists, workers in hazardous environments, CRT operators and skiers.

Source record↗

Red fluorescence and 3-12 micron emission in NGC 2023, HD 44179, M 82, and Lynds 1780

A red excess observed in the Red Rectangle (HD 44179), was attributed to a possible molecular fluorescence mechanism was discovered in NGC 2023 and analyzed in subsequent work in this and other nebulae. An unexpected red light excess was also noticed in a high latitude dark cloud L 1780. The fluorescence was attributed to hydrogenated amorphous carbon by Duley (1985), on the basis of laboratory work. Alternatively, transitions between electronic states of free polycyclic aromatic hydrocarbon molecules, by-passing the cascade along the vibrational states was considered. In L 1780, the red excess was related to the 12 micron emission detected by IRAS. A quantitative comparison of the intensity of the red fluorescence and that of the 3 to 12 micron features is thus warranted in helping assess the physical properties of large interstellar molecules. The red fluorescence radiation, F(R), appears as a bump on the spectra between 0.6 and 0.9 micron. Values were deduced from the spectra for HD 44179, and for the high latitude cloud L 1780. Corrections for the extinction, both interstellar and internal to the nebulae, were included. The 3 to 12 micron brightness, F(IR), was obtained through integration of the spectra for NGC 2023, and for HD 44179 after removal of a smooth continuum due to hot large grains. The values of the ratio of fluorescence flux to the infrared flux, F(R)/F(IR), are summarized. Red fluorescence and infrared radiation are two separate ways to access to the size of the molecules through observation, and it is rewarding that both approaches give similar results. These findings bring a striking coherence into the physical description of the particles, and add further support to the initial attribution of the infrared features to polycyclic aromatic hydrocarbons (PAHs).

Ryter, Charles↗

Low Forward Voltage III-Nitride Red Micro-Light-Emitting Diodes on a Strain Relaxed Template with an InGaN Decomposition Layer

In this study, III-nitride red micro-light-emitting diodes (µLEDs) with ultralow forward voltage are demonstrated on a strain relaxed template. The forward voltage ranges between 2.00 V and 2.05 V at 20 A/cm 2 for device dimensions from 5 x 5 to 100 x 100 µm 2 . The µLEDs emit at 692 nm at 5 A/cm 2 and 637 nm at 100 A/cm 2 , corresponding to a blueshift of 55 nm due to the screening of the internal electric field in the quantum wells. The maximum external quantum efficiency and wall-plug efficiency of µLEDs are 0.31% and 0.21%, respectively. This suggests that efficient III-nitride red µLEDs can be realized with further material optimizations.

36 MATERIALS SCIENCE↗

Infrared supernova light curves and asymmetric stellar mass loss

Infrared dust emission echos from Type II supernovae are a natural consequence of the heating of circumstellar dust by the supernova light. Red supergiants, the likely progenitors of most Type II supernovae, are known in some cases to have asymmetric circumstellar envelopes. It is noted that an asymmetric dust distribution can have a substantial effect on the evolution of an infrared echo and results are presented for an ellipsoidal dust distribution. The angle between the symmetry axis and the line of sight is unknown in any particular case so that detailed observations of a number of supernovae will be necessary to test for asymmetries. Asymmetries may also be observable in the radio structure of supernovae and in a possible scattered-light echo.

Emmering, Robert T.↗

Pr-specific phytochrome phosphorylation in vitro by a protein kinase present in anti-phytochrome maize immunoprecipitates

Protein kinase activity has repeatedly been found to co-purify with the plant photoreceptor phytochrome, suggesting that light signals received by phytochrome may be transduced or modulated through protein phosphorylation. In this study immunoprecipitation techniques were used to characterize protein kinase activity associated with phytochrome from maize (Zea mays L.). A protein kinase that specifically phosphorylated phytochrome was present in washed anti-phytochrome immunoprecipitates of etiolated coleoptile proteins. No other substrate tested was phosphorylated by this kinase. Adding salts or detergents to disrupt low-affinity protein interactions reduced background phosphorylation in immunoprecipitates without affecting phytochrome phosphorylation, indicating that the protein kinase catalytic activity is either intrinsic to the phytochrome molecule or associated with it by high-affinity interactions. Red irradiation (of coleoptiles or extracts) sufficient to approach photoconversion saturation reduced phosphorylation of immunoprecipitated phytochrome. Subsequent far-red irradiation reversed the red-light effect. Phytochrome phosphorylation was stimulated about 10-fold by a co-immunoprecipitated factor. The stimulatory factor was highest in immunoprecipitates when Mg2+ was present in immunoprecipitation reactions but remained in the supernatant in the absence of Mg2+. These observations provide strong support for the hypothesis that phytochrome-associated protein kinase modulates light responses in vivo. Since only phytochrome was found to be phosphorylated, the co-immunoprecipitated protein kinase may function to regulate receptor activity.

NASA Discipline Plant Biology↗

Calcium requirement of phytochrome-mediated fern-spore germination: no direct phytochrome-calcium interaction in the phytochrome-initiated transduction chain

Phytochrome-mediated germination of fern spores of Dryopteris paleacea Sw. was initiated by a saturating red-light (R) irradiation after 20 h of imbibition. For its realization external Ca2+ was required, with a threshold at a submicromolar concentration, and an optimum was reached around 10(-4) M. At concentrations > or = 10(-1) M only a reduced response was obtained, based probably on an unspecific osmotic or ionic effect. The germination response was inhibited by La3+, an antagonist of Ca2+. From these results it is concluded that Ca2+ influx from the medium into the spores may be an important event in phytochrome-mediated germination. In the absence of Ca2+ the R-stimulated system remained capable of responding to Ca2+, added as late as 40 h after R. Moreover, Ca2+ was effective even if added after the active form of phytochrome, Pfr, had been abolished by far-red (FR) 24 h after R. Thus, the primary effect of Pfr, that initiates the transduction chain, does not require calcium. "Coupling" of Pfr to subsequent dark reactions has been investigated by R-FR irradiations with various dark intervals. The resulting "escape kinetics" were characterized by a lag phase (6 h) and half-maximal escape from FR reversibility (19 h). These kinetics were not significantly changed by the presence or absence of calcium. Thus, direct interaction of Pfr and calcium is not a step in the transduction chain initiated by the active form of phytochrome.

Non-NASA Center↗

Effect of Display Color on Pilot Performance and Describing Functions

A study has been conducted with the full-spectrum, calligraphic, computer-generated display system to determine the effect of chromatic content of the visual display upon pilot performance during the landing approach maneuver. This study utilizes a new digital chromatic display system, which has previously been shown to improve the perceived fidelity of out-the-window display scenes, and presents the results of an experiment designed to determine the effects of display color content by the measurement of both vertical approach performance and pilot-describing functions. This method was selected to more fully explore the effects of visual color cues used by the pilot. Two types of landing approaches were made: dynamic and frozen range, with either a landing approach scene or a perspective array display. The landing approach scene was presented with either red runway lights and blue taxiway lights or with the colors reversed, and the perspective array with red lights, blue lights, or red and blue lights combined. The vertical performance measures obtained in this experiment indicated that the pilots performed best with the blue and red/blue displays. and worst with the red displays. The describing-function system analysis showed more variation with the red displays. The crossover frequencies were lowest with the red displays and highest with the combined red/blue displays, which provided the best overall tracking, performance. Describing-function performance measures, vertical performance measures, and pilot opinion support the hypothesis that specific colors in displays can influence the pilots' control characteristics during the final approach.

Chase, Wendell D.↗

Dirhodium(II,II) Complexes as Panchromatic Single-Molecule Photocatalysts for Hydrogen Evolution

The growing global energy demand and climate change have prompted a shift from carbon-based fuels to sustainable energy sources. Hydrogen production by harnessing solar energy and using abundant proton sources represents an attractive approach to addressing this crisis. Single-molecule single-chromophore photocatalysts, capable of both absorbing the incident photon and catalyzing the chemical transformation, are able to circumvent energy losses present in multicomponent systems that require a photosensitizer and a catalyst, often employing additional redox relay molecules. Here, the series of complexes derived from cis-[Rh 2 (μ-DPhF) 2 (μ-bncn) 2 ] 2+ (1; DPhF = N,N′-diphenylformamidinate, bncn = benzo[c]cinnoline) discussed in this Account presents robust and air-stable single-molecule photocatalysts with panchromatic absorption from the ultraviolet spectral region to the near-infrared (NIR), with high turnover frequencies of ∼20 to 30 h –1 under red light irradiation. For comparison, other single-molecule hydrogen-evolving photocatalysts reported to date exhibit low photocatalytic efficiency, are not operable in the visible or NIR regions, and are unstable under an ambient atmosphere.

Absorption↗

Role of the Character of the Excited State of Singly Reduced Rh 2 (II,II) Intermediates on Photocatalytic Activity

Singly reduced intermediates have recently been implicated as photoactive intermediates in a number of important reactions; however, their photophysical properties remain poorly understood. A series of dirhodium(II,II) complexes, cis-[Rh 2 (p-R-Form) 2 (bncn) 2 ] 2+ (bncn = benzo[c]cinnoline; p-R-Form = N,N′-di-p-R-phenylformamidinate), where R = −OCH 3 (1), −CH 3 (2), −H (3), −F (4), −Cl (5), and −CF 3 (6), and their respective radical anions were prepared and their excited state properties were investigated. Complex 3 acted as a singlemolecule photocatalyst for H 2 production with red light. Substitution on the formamidinate ligands in 1−6 affected the energy of the Rh 2 (δ*)/Form(π,nb) highest occupied molecular orbital (HOMO), consistent with the metal/ligand-to-ligand charge transfer ( 1 ML-LCT) absorption maxima and the 3 ML-LCT excited state lifetime, ranging from 1.6 ns in 1 to 54 ns in 6 in CH 3 CN. The highest turnover number for photocatalytic H 2 evolution was observed for 3, and the lowest values were for 1 and 6. The radical anion, [Rh 2 ] − , formed during photocatalysis, was shown to absorb a photon and undergo a second reduction. The lifetimes of the doublet excited states of [3] − and [6] − were 0.49 and 0.24 ns, respectively. Calculations showed that the lowest energy excited state in [3] − was 2 ML-LCT, whereas that in [6] − was a bncn − → Rh 2 (σ*) ligand-to-metal charge transfer ( 2 LMCT) state. The 2 LMCT state stabilized across the series from [1] − to [6] − , pointing at its role in modulating the photophysical properties. This work highlights the importance of the reductive quenching of [Rh 2 ] − and the generation of the doubly reduced species to effectively catalyze hydrogen evolution.

Absorption↗

The initial charge separation step in oxygenic photosynthesis

Photosystem II is crucial for life on Earth as it provides oxygen as a result of photoinduced electron transfer and water splitting reactions. The excited state dynamics of the photosystem II-reaction center (PSII-RC) has been a matter of vivid debate because the absorption spectra of the embedded chromophores significantly overlap and hence it is extremely difficult to distinguish transients. Here, we report the two-dimensional electronic-vibrational spectroscopic study of the PSII-RC. The simultaneous resolution along both the visible excitation and infrared detection axis is crucial in allowing for the character of the excitonic states and interplay between them to be clearly distinguished. In particular, this work demonstrates that the mixed exciton-charge transfer state, previously proposed to be responsible for the far-red light operation of photosynthesis, is characterized by the Chl D1 + Phe radical pair and can be directly prepared upon photoexcitation. Further, we find that the initial electron acceptor in the PSII-RC is Phe, rather than P D1 , regardless of excitation wavelength.

59 BASIC BIOLOGICAL SCIENCES↗

A red-emitting carborhodamine for monitoring and measuring membrane potential

Biological membrane potentials, or voltages, are a central facet of cellular life. Optical methods to visualize cellular membrane voltages with fluorescent indicators are an attractive complement to traditional electrode-based approaches, since imaging methods can be high throughput, less invasive, and provide more spatial resolution than electrodes. Recently developed fluorescent indicators for voltage largely report changes in membrane voltage by monitoring voltage-dependent fluctuations in fluorescence intensity. However, it would be useful to be able to not only monitor changes but also measure values of membrane potentials. This study discloses a fluorescent indicator which can address both. We describe the synthesis of a sulfonated tetramethyl carborhodamine fluorophore. When this carborhodamine is conjugated with an electron-rich, methoxy (-OMe) containing phenylenevinylene molecular wire, the resulting molecule, CRhOMe, is a voltage-sensitive fluorophore with red/far-red fluorescence. Using CRhOMe, changes in cellular membrane potential can be read out using fluorescence intensity or lifetime. In fluorescence intensity mode, CRhOMe tracks fast-spiking neuronal action potentials (APs) with greater signal-to-noise than state-of-the-art BeRST 1 (another voltage-sensitive fluorophore). CRhOMe can also measure values of membrane potential. The fluorescence lifetime of CRhOMe follows a single exponential decay, substantially improving the quantification of membrane potential values using fluorescence lifetime imaging microscopy (FLIM). The combination of red-shifted excitation and emission, mono-exponential decay, and high voltage sensitivity enable fast FLIM recording of APs in cardiomyocytes. The ability to both monitor and measure membrane potentials with red light using CRhOMe makes it an important approach for studying biological voltages.

59 BASIC BIOLOGICAL SCIENCES↗

Cyanobacteriochromes: A Rainbow of Photoreceptors

Widespread phytochrome photoreceptors use photoisomerization of linear tetrapyrrole (bilin) chromophores to measure the ratio of red to far-red light. Cyanobacteria also contain distantly related cyanobacteriochrome (CBCR) proteins that share the bilin-binding GAF domain of phytochromes but sense other colors of light. CBCR photocycles are extremely diverse, ranging from the near-UV to the near-IR. Photoisomerization of the bilin triggers photoconversion of the CBCR input, thereby modulating the biochemical signaling state of output domains such as histidine kinase bidomains that can interface with cellular signal transduction pathways. CBCRs thus can regulate several aspects of cyanobacterial photobiology, including phototaxis, metabolism of cyclic nucleotide second messengers, and optimization of the cyanobacterial light-harvesting apparatus. This review examines spectral tuning, photoconversion, and photobiology of CBCRs and recent developments in understanding their evolution and in applying them in synthetic biology.

59 BASIC BIOLOGICAL SCIENCES↗