Crystal structure of Pseudomonas aeruginosa bacteriophytochrome: Photoconversion and signal transduction
Abstract not provided
Yang, Xiaojing↗
SEARCH · Engineering Papers
Results for “photoconversion”
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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Decarboxylation via a higher electronic excited state drives LSSmOrange photoconversion
Please check the README.txt file from the supplementary files for more information about the dataset.
Serial Femtosecond Crystallography↗
CONJUGATED POLYMERS AND POLYELECTROLYTES IN SOLAR PHOTOCONVERSION, Final Technical Report
This DOE-supported program investigated the fundamental properties of conjugated polyelectrolytes, with emphasis placed on studies of excited state energy transport, self-assembly into conjugated polyelectroyte (CPE) based films and colloids, and exciton transport and charge injection in CPE films constructed atop wide bandgap semiconductors. In the most recent grant period we have also extended efforts to examine the properties of low-bandgap donor-acceptor conjugated polyelectrolytes that feature strong visible light absorption and the ability to adsorb to metal-oxide interfaces.
14 SOLAR ENERGY↗
Molecular and Structural Probes of Defect States in Quantum Dots for Photoconversion
The objective of this research on quantum confined nanocrystals is to develop a fundamental understanding of the chemical properties of ligand-nanocrystal interfaces that will enable the control of defect-driven charge recombination in these systems. With this control, quantum confined nanocrystals may represent a cost effective means of absorbing light over the full solar spectrum for the production of electricity and fuels from sunlight. New spectroscopic techniques will be developed in this project that allow a direct correlation of molecular structural information about the ligand-nanocrystal interactions with the corresponding density and energetic distribution of surface defects and the influence that these defects have on charge transport and recombination. The insight that is gained will provide a molecular basis for the rational development of novel pathways for the of use quantum dots in systems for solar energy transduction.
14 SOLAR ENERGY↗
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.↗
Controlling the Properties of Matter with Quantum Dots
Solar cells and photodetectors could soon be made from new types of materials based on semiconductor quantum dots, thanks to new insights based on ultrafast measurements capturing real-time photoconversion processes. Photoconversion is a process wherein the energy of a photon, or quantum of light, is converted into other forms of energy, for example, chemical or electrical. Semiconductor quantum dots are chemically synthesized crystalline nanoparticles that have been studied for more than three decades in the context of various photoconversion schemes including photovoltaics (generation of photo-electricity) and photo-catalysis (generation of “solar fuels”). The appeal of quantum dots comes from the unmatched tunability of their physical properties, which can be adjusted by controlling the size, shape and composition of the dots. At Los Alamos, the research connects to the institutional mission of solving national security challenges through scientific excellence, in this case focusing on novel physical principles for highly efficient photoconversion, charge manipulation in exploratory device structures and novel nanomaterials.
14 SOLAR ENERGY↗
Crystal structure of the fluorescent protein from Dendronephthya sp. in both green and photoconverted red forms
The fluorescent protein from Dendronephthya sp. (DendFP) is a member of the Kaede-like group of photoconvertible fluorescent proteins with a His62-Tyr63-Gly64 chromophore-forming sequence. Upon irradiation with UV and blue light, the fluorescence of DendFP irreversibly changes from green (506 nm) to red (578 nm). The photoconversion is accompanied by cleavage of the peptide backbone at the C α —N bond of His62 and the formation of a terminal carboxamide group at the preceding Leu61. The resulting double C α =C β bond in His62 extends the conjugation of the chromophore π system to include imidazole, providing the red fluorescence. Here, the three-dimensional structures of native green and photoconverted red forms of DendFP determined at 1.81 and 2.14 Å resolution, respectively, are reported. This is the first structure of photoconverted red DendFP to be reported to date. The structure-based mutagenesis of DendFP revealed an important role of positions 142 and 193: replacement of the original Ser142 and His193 caused a moderate red shift in the fluorescence and a considerable increase in the photoconversion rate. It was demonstrated that hydrogen bonding of the chromophore to the Gln116 and Ser105 cluster is crucial for variation of the photoconversion rate. The single replacement Gln116Asn disrupts the hydrogen bonding of Gln116 to the chromophore, resulting in a 30-fold decrease in the photoconversion rate, which was partially restored by a further Ser105Asn replacement.
59 BASIC BIOLOGICAL SCIENCES↗
Fabrication of CdSe nanoparticles sensitized TiO2 nanotube arrays via pulse electrodeposition for photoelectrochemical application
Highlights: • Anodization method approach for the synthesis of TiO{sub 2} nanotubes. • CdSe nanoparticle/TiO{sub 2} nanotube arrays were assembled via pulse electrochemical deposition technique. • Duty cycles were applied in order to enhance the properties of CdSe/TiO{sub 2} nanostructure. • PEC analysis verified that CdSe/TiO{sub 2} structure prepared at 50% duty cycle gave best photocurrent response. • Photoconversion efficiency of CdSe/TiO{sub 2} nanostructure was approximately 59 times greater than TiO{sub 2} nanotubes. - Abstract: Solar energy is an alternative sustainable energy resource that can be harvested using photoelectrochemical cell comprised of inorganic sensitized nanostructured oxide semiconductor electrode. In this work, pulse electrodeposition was used to deposit CdSe onto titanium dioxide nanotube arrays (TiO{sub 2} NTAs). TiO{sub 2} NTAs are commonly used in the nanostructured photoelectrochemical cells due to their high surface area, fewer interfacial grain boundaries and excellent charge transfer between interfaces. Duty cycle of pulse electrodeposition played an important role in the formation of CdSe nanoparticles. A significant enhancement in the photoelectrochemical performance was observed for the heterostructure of CdSe/TiO{sub 2} NTAs. CdSe/TiO{sub 2} NTAs prepared at 50% duty cycle exhibited maximum photocurrent of 1.94 mA cm{sup −2} and photoconversion efficiency of 1.18% which was 59 times higher than bare TiO{sub 2} NTAs. These results demonstrated that significant enhancement in the photoconversion efficiency could be obtained by incorporating CdSe as sensitizer into the TiO{sub 2} nanotube arrays via pulse electrodeposition technique.
77 NANOSCIENCE AND NANOTECHNOLOGY↗
Simulation of the real efficiencies of high-efficiency silicon solar cells
The temperature dependences of the efficiency η of high-efficiency solar cells based on silicon are calculated. It is shown that the temperature coefficient of decreasing η with increasing temperature decreases as the surface recombination rate decreases. The photoconversion efficiency of high-efficiency silicon-based solar cells operating under natural (field) conditions is simulated. Their operating temperature is determined self-consistently by simultaneously solving the photocurrent, photovoltage, and energy-balance equations. Radiative and convective cooling mechanisms are taken into account. It is shown that the operating temperature of solar cells is higher than the ambient temperature even at very high convection coefficients (~300 W/m{sup 2} K). Accordingly, the photoconversion efficiency in this case is lower than when the temperature of the solar cells is equal to the ambient temperature. The calculated dependences for the open-circuit voltage and the photoconversion efficiency of high-quality silicon solar cells under concentrated illumination are discussed taking into account the actual temperature of the solar cells.
14 SOLAR ENERGY↗
Protein–chromophore interactions controlling photoisomerization in red/green cyanobacteriochromes
Abstract Photoreceptors in the phytochrome superfamily use 15,16-photoisomerization of a linear tetrapyrrole (bilin) chromophore to photoconvert between two states with distinct spectral and biochemical properties. Canonical phytochromes include master regulators of plant growth and development in which light signals trigger interconversion between a red-absorbing 15Z dark-adapted state and a metastable, far-red-absorbing 15E photoproduct state. Distantly related cyanobacteriochromes (CBCRs) carry out a diverse range of photoregulatory functions in cyanobacteria and exhibit considerable spectral diversity. One widespread CBCR subfamily typically exhibits a red-absorbing 15Z dark-adapted state similar to that of phytochrome that gives rise to a distinct green-absorbing 15E photoproduct. This red/green CBCR subfamily also includes red-inactive examples that fail to undergo photoconversion, providing an opportunity to study protein–chromophore interactions that either promote photoisomerization or block it. In this work, we identified a conserved lineage of red-inactive CBCRs. This enabled us to identify three substitutions sufficient to block photoisomerization in photoactive red/green CBCRs. The resulting red-inactive variants faithfully replicated the fluorescence and circular dichroism properties of naturally occurring examples. Converse substitutions restored photoconversion in naturally red-inactive CBCRs. This work thus identifies protein–chromophore interactions that control the fate of the excited-state population in red/green cyanobacteriochromes.
59 BASIC BIOLOGICAL SCIENCES↗
Fluorescent protein Dendra2 as a ratiometric genetically encoded pH-sensor
Fluorescent protein Dendra2 is a monomeric GFP-like protein that belongs to the group of Kaede-like photoconvertible fluorescent proteins with irreversible photoconversion from a green- to red-emitting state when exposed to violet-blue light. In an acidic environment, photoconverted Dendra2 turns green due to protonation of the phenolic group of the chromophore with pKa of about 7.5. Thus, photoconverted form of Dendra2 can be potentially used as a ratiometric pH-sensor in the physiological pH range. However, incomplete photoconversion makes ratiometric measurements irreproducible when using standard filter sets. Here, we describe the method to detect fluorescence of only photoconverted Dendra2 form, but not nonconverted green Dendra2. We show that the 350 nm excitation light induces solely the fluorescence of photoconverted protein. By measuring the red to green fluorescence ratio, we determined intracellular pH in live CHO and HEK 293 cells. Thus, Dendra2 can be used as a novel ratiometric genetically encoded pH sensor with emission maxima in the green-red spectral region, which is suitable for application in live cells. - Highlights: • Dendra2 is a monomeric green-to-red photoconvertible fluorescent protein. • Photoconverted form of Dendra2 fluoresces green at low pH and red at high pH. • It can be used as a ratiometric pH sensor using photoconverted Dendra2-specific excitation peak. • Dendra2 is suitable for pH measurements in physiological range in live cells.
60 APPLIED LIFE SCIENCES↗
Nitrogen doped carbon quantum dots as a green luminescent sensitizer to functionalize ZnO nanoparticles for enhanced photovoltaic conversion devices
Highlights: • Hydrothermal synthesis for highly green luminescent nitrogen doped carbon quantum dots (NCQDs) was proposed. • ZnO NPs were prepared by CTAB assisted low temperature reaction method. • High green luminescence was observed from NCQDs. • NCQDs are applied as light harvesting material in ZnO photoanodes. • Enhanced photoconversion efficiency was observed with NCQDs. - Abstract: A simple and facile hydrothermal approach for the synthesis of highly green luminescent nitrogen doped carbon quantum dots (NCQDs) is reported. The prepared NCQDs show narrow size distribution of 2–3 nm, abundant surface functional groups and good water solubility. To showcase the potential of these NCQDs as a solar light harvesting material, we designed NCQDs sensitized ZnO nanoparticles based photoanodes for photovoltaic solar cells. As a result, NCQDs sensitized ZnO photoanodes exhibited 75% higher photoconversion efficiency when compared to that of bare ZnO photoanodes. The characterization and optical properties of NCQDs sensitized ZnO photoanodes is also discussed.
36 MATERIALS SCIENCE↗
Eutectic Processing of Semiconductor Colloidal Nanocrystals for Energy Applications
Colloidal semiconductor nanocrystals (NCs) offer a costeffective platform for light-energy conversion in X-ray scintillators, photovoltaics, lasers, and display technologies. Yet, device-relevant NCs often require complex heterostructured compositions, where lattice imperfections compromise the efficiency and stability of photoconversion processes. Here, we show that a simple synthetic detour through a eutectic state of II−VI semiconductor NCs (e.g., CdSe, ZnSe) with halide salts (e.g., CdCl 2 , ZnCl 2 ) overcomes this limitation by melting and reconstructing NC lattices into defect-free alloyed and core/shell architectures. Applied to ternary CdSeTe NCs, this process produces downconverters with record brightness and minimal line widths, delivering a 3-fold increase in film-side external quantum efficiency of commercial CdTe photovoltaic modules (First Solar Inc.). Meanwhile, eutectic processing of CdSe-based core/shell emitters yields an 8-fold enhancement in their photoluminescence stability under backlight operation, addressing the reliability bottleneck for display technologies. Together, these findings establish eutectic NC processing as a scalable route to efficient, durable photoconversion materials for energy applications.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Spin-exchange carrier multiplication in manganese-doped colloidal quantum dots
Abstract Carrier multiplication is a process whereby a kinetic energy of a carrier relaxes via generation of additional electron–hole pairs (excitons). This effect has been extensively studied in the context of advanced photoconversion as it could boost the yield of generated excitons. Carrier multiplication is driven by carrier–carrier interactions that lead to excitation of a valence-band electron to the conduction band. Normally, the rate of phonon-assisted relaxation exceeds that of Coulombic collisions, which limits the carrier multiplication yield. Here we show that this limitation can be overcome by exploiting not ‘direct’ but ‘spin-exchange’ Coulomb interactions in manganese-doped core/shell PbSe/CdSe quantum dots. In these structures, carrier multiplication occurs via two spin-exchange steps. First, an exciton generated in the CdSe shell is rapidly transferred to a Mn dopant. Then, the excited Mn ion undergoes spin-flip relaxation via a spin-conserving pathway, which creates two excitons in the PbSe core. Due to the extremely fast, subpicosecond timescales of spin-exchange interactions, the Mn-doped quantum dots exhibit an up-to-threefold enhancement of the multiexciton yield versus the undoped samples, which points towards the considerable potential of spin-exchange carrier multiplication in advanced photoconversion.
36 MATERIALS SCIENCE↗
Photosensing and Thermosensing by Phytochrome B Require Both Proximal and Distal Allosteric Features within the Dimeric Photoreceptor
Phytochromes (Phys) encompass a diverse collection of bilin-containing photoreceptors that help plants and microorganisms perceive light through photointerconversion between red light (Pr) and far-red light (Pfr)-absorbing states. In addition, Pfr reverts thermally back to Pr via a highly enthalpic process that enables temperature sensation in plants and possibly other organisms. Through domain analysis of the Arabidopsis PhyB isoform assembled recombinantly, coupled with measurements of solution size, photoconversion, and thermal reversion, we identified both proximal and distal features that influence all three metrics. Included are the downstream C-terminal histidine kinase-related domain known to promote dimerization and a conserved patch just upstream of an N-terminal Period/Arnt/Sim (PAS) domain, which upon removal dramatically accelerates thermal reversion. We also discovered that the nature of the bilin strongly influences Pfr stability. Whereas incorporation of the native bilin phytochromobilin into PhyB confers robust Pfr → Pr thermal reversion, that assembled with the cyanobacterial version phycocyanobilin, often used for optogenetics, has a dramatically stabilized Pfr state. Taken together, we conclude that Pfr acquisition and stability are impacted by a collection of opposing allosteric features that inhibit or promote photoconversion and reversion of Pfr back to Pr, thus allowing Phys to dynamically measure light, temperature, and possibly time.
59 BASIC BIOLOGICAL SCIENCES↗
Optimization of TiO{sub 2} photoelectrode with titanium isopropoxide for flexible dye sensitized solar cells
Flexible DSSC uses plastic substrate such as polyethylene terephthalate (PET) to deposit photoelectrode, resulting in poor photoconversion efficiency of the solar cell due to the low temperature applied in the fabrication process. In this research, optimization process was examined in order to optimize the performance of flexible DSSC by adding titanium isopropoxide (TTIP) as a binder to TiO{sub 2} paste for DSSC photoelectrode. Small portion of TTIP with molar percentages of 0%, 5%, and 10% were added to a mixture of TiO{sub 2} nanocrystaline, butanol, DI water, and reflector powder. The mixtures were stirred using a magnetic stirrer for 24 hours. Each of various pastes was then deposited on a plastic substrate with doctor blade method on 1 cm{sup 2} area. The films were sintered at temperature of 150 °C for 4 hours and soaked in dye solution for 24 hours. Furthermore, TiO{sub 2} photoelectrode and Pt counter electrode were assembled and injected by electrolyte. Flexible DSSCs were characterized by SEM and XRD to determine their morphological structures. J-V measurement was performed by sun simulator to calculate DSSC photoconversion efficiency. The optimum performance of flexible DSSC was achieved by DSSC with 10 mol% TTIP content.
75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
Correlating structural and photochemical heterogeneity in cyanobacteriochrome NpR6012g4
Phytochrome photoreceptors control plant growth, development, and the shade avoidance response that limits crop yield in high-density agricultural plantings. Cyanobacteriochromes (CBCRs) are distantly related photosensory proteins that control cyanobacterial metabolism and behavior in response to light. Photoreceptors in both families reversibly photoconvert between two photostates via photoisomerization of linear tetrapyrrole (bilin) chromophores. Spectroscopic and biochemical reprorts have demonstrated heterogeneity in both photostates, but the structural basis for such heterogeneity remains unclear. We discuss solution NMR structures for both photostates of the red/green CBCR NpR6012g4 from Nostoc punctiforme . In addition to identifying structural changes accompanying photoconversion, these structures reveal structural heterogeneity for residues Trp655 and Asp657 in the red-absorbing NpR6012g4 dark state, yielding two distinct environments for the phycocyanobilin chromophore. We use site-directed mutagenesis and fluorescence and absorbance spectroscopy to assign an orange-absorbing population in the NpR6012g4 dark state to the minority configuration for Asp657. This population does not undergo full, productive photoconversion, as shown by time-resolved spectroscopy and absorption spectroscopy at cryogenic temperature. Our research thus elucidate the spectral and photochemical consequences of structural heterogeneity in a member of the phytochrome superfamily, insights that should inform efforts to improve photochemical or fluorescence quantum yields in the phytochrome superfamily.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗