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At least 1,099 records · Page 61

Fundamental Research Aimed at Diverting Excess Reducing Power in Photosynthesis to Orthogonal Metabolic Pathways

Photosystems are incredible biological machines that use sunlight to drive the conversion of carbon dioxide to sugar. The amount of sunlight available for photosynthesis sometimes exceeds the amount of energy plants can use. This excess energy has to be safely dissipated through non-productive biological processes. The ultimate goal of this project is to understand whether we can utilize that otherwise unused excess energy. In our previous work, we showed that, in principle, it is possible to attach a catalyst to photosystem I and generate H2 using light. Our current strategy is to genetically fuse parts of the photosystem I complex with a recently discovered oxygen-tolerant [FeFe] hydrogenase. Our rationale is that such chimeric proteins may potentially result in the natural incorporation of the photosystem I-hydrogenase link using the inherent genetic machinery of the cell. In this project, we aim to verify that light-driven hydrogen production in this construction is possible. Throughout the project, we designed nanoconstructs that showcase the plausibility of this technology, at least in vitro. We take advantage of these constructs to investigate details of the coupling between photosystem I and a H2-producing enzyme called [FeFe] hydrogenase. This part of the project reveals details of the electron transfer between photosystem I and the attached hydrogenase, providing information that can lead to new strategies for improved biological photocatalysis. We also researched efficient and robust tethering of the [FeFe] hydrogenase to photosystem I in cyanobacteria. This work will highlight successful design strategies to guide the future development of photosynthetic biohybrids. Uncovering the principles governing the utilization of otherwise unusable energy significantly further our understanding of cyanobacterial photosynthesis. The work proposed establishes the feasibility of diverting excess energy under high light conditions to orthogonal enzymatic pathways and set design rules for efficient utilization of such a strategy for scientific and industrial applications in biosensing, renewable energy, and high-value chemicals production. The work addresses the DOE-BES Photosynthetic Systems program goal to develop a multidimensional understanding of photosystems that would provide specific metrics that instruct strategies for improving biological photosynthesis and for guiding the future development of bioreactors and biomimetic energy systems.

Photosynthetic systems, hydrogenase, cyanobacteria↗

Liquid Abrasive Cutter Power Generation Unit Requirements

This document details the requirements for the purchase of a power generating unit (PGU) for an updated Liquid Abrasive Cutter (LAC) for use in field conditions. The system will provide high pressure water and will be integrated with existing waterjet cutting attachments to cut various materials. The system will be standalone, requiring only water, and electrical energy. Cutting heads, attachments, and a garnet delivery system are not included in this specification. This system is an evolution of the existing LAC (developed at LLNL). The PGU specified herein will have the ability to operate on electrical power via an electric motor, and accept input power from a variety of sources, such as an engine-driven generator, battery pack, solar, shore power, or micro-grid.

42 ENGINEERING↗

Andrieslombaardite, RhSbS, a new platinum-group mineral from the platiniferous Onverwacht Pipe, Republic of South Africa

A hundred years after the discovery of the Merensky Reef in 1924, it is appropriate to present the new mineral andrieslombaardite in honour of Andries Frederik Lombaard who was instrumental in its discovery. Andrieslombaardite, RhSbS, was first described as an unknown mineral from placer deposits associated with the Tulameen Alaskan-Uralian type complex, British Colombia, Canada (Raicevic and Cabri, 1976) but has since been reported from several other deposits including the platiniferous Driekop, Mooihoek, and Onverwacht pipes in the eastern Bushveld Complex, South Africa. The mineral and the name were approved by the Commission on New Minerals Nomenclature and Classification (CNMNC) of the International Mineralogical Association (IMA no. 2022-076) based on data in the co-type samples from Onverwacht and a co-type sample from the Yubdo stream, Birbir River, Ethiopia. Andrieslombaardite in the Onverwacht sample is a single 8 x 20 μm grain attached to laurite in a matrix of altered silicate and Fe-oxyhydroxide minerals. In the Yubdo samples, there are many grains of pale brownish gray andrieslombaardite up to 25 x 55 μm in size, included in Pt-Fe alloys, some associated with erlichmanite, and others attached to bornite and chalcopyrite. The reflectance values (R%) measured in air and in oil at the COM wavelengths are 48.3 and 33.0 (470 nm), 49.3 and 34.0 (546 nm), 51.0 and 35.9 (589 nm), and 51.8 and 36.7 (650 nm). The colour values x, y, Y, λd, and Pe in air are 0.317, 0.322, 50.3, 580, and 3.2, and in oil are 0.319, 0.324, 35.6, 579, and 4.5. The composition of andrieslombaardite is ideally RhSbS, but it contains variable amounts of Fe, Pt, Pd, and Ir that may substitute for Rh. The mineral is cubic with unit-cell dimensions of a = 6.0278(4) Å, V = 219.01(6) Å 3 and Z = 4. It was synthesised at 400 and 550°C using stoichiometric elemental amounts. It is a member of the cobaltite group. The mineralisation of the intrusive dunite pipes was probably introduced at high temperatures, under magmatic conditions. The primary assemblages were to a certain degree overprinted and redistributed by low-temperature hydrothermal fluids. The Pt-Fe alloys from Yubdo containing PGM inclusions such as andrieslombaardite in the Yubdo-Alaskan-type complex were formed at some post-magmatic stage owing to PGE remobilisation during hydrothermal or metamorphic episodes.

58 GEOSCIENCES↗

Metabolic activity and community structure of prokaryotes associated with particles in the twilight zone of the South China Sea

The twilight zone is an important depth of the ocean where particulate organic matter (POM) remineralization takes place, and prokaryotes contribute to more than 70% of the estimated remineralization. However, little is known about the microbial community and metabolic activity associated with different particles in the twilight zone. The composition and distribution of particle-attached prokaryotes in the twilight zone of the South China Sea (SCS) were investigated using high-throughput sequencing and quantitative PCR, together with the Biolog Ecoplate™ microplates culture to analyze the microbial metabolic activity. We found that α- and γ-Proteobacteria dominating at the lower and upper boundary of the twilight zone, respectively; Methanosarcinales and Halobacteriales of the Euyarchaeota occupied in the larger particles at the upper boundary. Similar microbial community existed between euphotic layer and the upper boundary. Higher amount of shared Operational Taxonomic Units (OTUs) in the larger particles along the water depths, might be due to the fast sinking and major contribution of carbon flux of the larger particles from the euphotic layer. In addition to polymers as the major carbon source, carbohydrates and amino acids were preferentially used by microbial community at the upper and lower boundary, respectively. This could potentially be attributed to the metabolic capabilities of attached microbial groups in different particles, and reflected the initial preference of the carbon source by the natural microbes in the twilight zone as well. The microbial structure and carbon metabolic profiles could be complemented with metatranscriptomic analysis in future studies to augment the understanding of the complex carbon cycling pathways in the twilight zone.

Liu, Hao↗

A Glimpse into Photodetachment Spectra of Giant and Nested Fullerene Anions

We focus on the study of the photodetachment of bare, i.e., single-cage (CN)− as well as nested (multi-cage) (CN@CM@…)− singly charged fullerene anions. We calculate the attached electron’s wavefunctions, energies, oscillator strengths and photodetachment cross sections of the C60−, C240−, C540−, (C60@C240)−, (C60@C540)−, (C240@C540)− and (C60@C240@C540)− fullerene anions, where the attached electron is captured into the ground s-state by the resultant external field provided by all fullerene cages in the anion. The goal is to gain insight into the changes in behavior ofphotodetachment of this valence electron as a function of the different geometries and potentials of the various underlying fullerenes or nested fullerenes (fullerene onions) both due to their increasing size and due to “stuffing” of a larger bare fullerene with smaller fullerenes. To meet this goal, we opt for a simple semi-empirical approximation to this problem: we approximate each individual fullerene cage by a rigid potential sphere of a certain inner radius, thickness and potential depth, as in numerous other model studies performed to date. The results reveal a number of rather significant differences in the wavefunctions, oscillator strengths and photodetachment cross sections among these fullerene anions, some of which are completely counter-intuitive. The results obtained can serve as a “zeroth-order-touchstone” for future studies of single-cage and nested fullerene anions by more rigorous theories and/or experiments to build upon this work to assess the importance of interactions omitted in the present study.

Dolmatov, Valeriy K.↗

Structural Insights into Mechanisms Underlying Mitochondrial and Bacterial Cytochrome c Synthases

Mitochondrial holocytochrome c synthase (HCCS) is an essential protein in assembling cytochrome c (cyt c) of the electron transport system. HCCS binds heme and covalently attaches the two vinyls of heme to two cysteine thiols of the cyt c CXXCH motif. Human HCCS recognizes both cyt c and cytochrome c1 of complex III (cytochrome bc1). HCCS is mutated in some human diseases and it has been investigated recombinantly by mutational, biochemical, and reconstitution studies in the past decade. Here, we employ structural prediction programs (e.g., AlphaFold 3) on HCCS and its two substrates, heme and cytochrome c. The results, when combined with spectroscopic and functional analyses of HCCS and variants, provide insights into the structural basis for heme binding, apocyt c binding, covalent attachment, and release of the holocyt c product. Results from in vitro reconstitution of purified human HCCS using cyt c and cyt c1 peptides as acceptors are consistent with the structural modeling of substrate binding. Reconstitution of HCCS and cyt c1 provides an approach to studying cyt c1 assembly, which has been refractile to recombinant in vivo reconstitution (unlike HCCS and cyt c). We propose a structural basis for release of the holocyt c product from HCCS based on in vitro studies and on cryoEM structures of the bacterial cyt c synthase (CcsBA) active site. We analyze the kinetoplastid mitochondrial synthase (KCCS), and hypothesize a molecular evolutionary path from mitochondrial endosymbiosis to the current HCCS.

Biochemistry & Molecular Biology↗

Effect of Active Lengthening and Shortening on Small-Angle X-ray Reflections in Skinned Skeletal Muscle Fibres

Our purpose was to use small-angle X-ray diffraction to investigate the structural changes within sarcomeres at steady-state isometric contraction following active lengthening and shortening, compared to purely isometric contractions performed at the same final lengths. We examined force, stiffness, and the 1,0 and 1,1 equatorial and M3 and M6 meridional reflections in skinned rabbit psoas bundles, at steady-state isometric contraction following active lengthening to a sarcomere length of 3.0 µm (15.4% initial bundle length at 7.7% bundle length/s), and active shortening to a sarcomere length of 2.6 µm (15.4% bundle length at 7.7% bundle length/s), and during purely isometric reference contractions at the corresponding sarcomere lengths. Compared to the reference contraction, the isometric contraction after active lengthening was associated with an increase in force (i.e., residual force enhancement) and M3 spacing, no change in stiffness and the intensity ratio I 1,1 /I 1,0 , and decreased lattice spacing and M3 intensity. Compared to the reference contraction, the isometric contraction after active shortening resulted in decreased force, stiffness, I 1,1 /I 1,0 , M3 and M6 spacings, and M3 intensity. This suggests that residual force enhancement is achieved without an increase in the proportion of attached cross-bridges, and that force depression is accompanied by a decrease in the proportion of attached cross-bridges. Furthermore, the steady-state isometric contraction following active lengthening and shortening is accompanied by an increase in cross-bridge dispersion and/or a change in the cross-bridge conformation compared to the reference contractions.

59 BASIC BIOLOGICAL SCIENCES↗

Molecular Dynamic Studies of Dye–Dye and Dye–DNA Interactions Governing Excitonic Coupling in Squaraine Aggregates Templated by DNA Holliday Junctions

Dye molecules, arranged in an aggregate, can display excitonic delocalization. The use of DNA scaffolding to control aggregate configurations and delocalization is of research interest. Here, we applied Molecular Dynamics (MD) to gain an insight on how dye–DNA interactions affect excitonic coupling between two squaraine (SQ) dyes covalently attached to a DNA Holliday junction (HJ). We studied two types of dimer configurations, i.e., adjacent and transverse, which differed in points of dye covalent attachments to DNA. Three structurally different SQ dyes with similar hydrophobicity were chosen to investigate the sensitivity of excitonic coupling to dye placement. Each dimer configuration was initialized in parallel and antiparallel arrangements in the DNA HJ. The MD results, validated by experimental measurements, suggested that the adjacent dimer promotes stronger excitonic coupling and less dye–DNA interaction than the transverse dimer. Additionally, we found that SQ dyes with specific functional groups (i.e., substituents) facilitate a closer degree of aggregate packing via hydrophobic effects, leading to a stronger excitonic coupling. This work advances a fundamental understanding of the impacts of dye–DNA interactions on aggregate orientation and excitonic coupling.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Retrospective on Recent DOE-Funded Studies Concerning the Extraction of Rare Earth Elements & Lithium from Geothermal Brines (Final Report)

Rare earth elements (REE) and lithium are non-toxic metals that are considered critical materials due to their use in electronics, magnets, batteries, and a wide variety of industrial processes important for the economy and military preparedness. Demand for REE and lithium is increasing and these critical materials are imported, so identifying and exploiting domestic sources of REE and lithium is a national priority. The U.S. Department of Energy (DOE) Geothermal Technologies Office (GTO) has been in the forefront of sponsoring research investigating the potential recovery of REE, lithium, and other critical minerals from geothermal brines. It has been proposed that the future of geothermal energy should include “hybrid systems” that combine electricity generation with other revenue-generating activities, such as recovery of valuable and critical minerals, including REE and lithium. Two recent GTO funding opportunities have focused on the recovery of REE and other valuable minerals from geothermal brines. The research supported by the GTO’s mineral recovery program is focused on three areas: resource characterization, technology for the extraction of REE, and technology for the extraction of lithium (Tables 1 and 2). This report is a retrospective study examining the outcome of GTO’s two recent mineral recovery programs (DE-FOA-0001016 in FY 2014 and DE-FOA-0001376 in FY 2016). In this report, the knowledge, technology, and techniques that were developed by researchers funded by GTO are summarized and discussed. Four projects were funded to assess the concentrations and amounts of REE found in geothermal brines and oil field produced waters. The GTO-funded studies compiled publically available data on REE concentrations from brines and produced water from all over the USA. In addition, new samples were collected and characterized from major geothermal and hydrocarbon basins in the Western USA. The studies examined the relationship between lithology and REE concentrations and developed models examining the influence of geology on REE concentrations in produced brines. It was determined that REE are frequently found at higher concentrations in oil field produced water than geothermal brines, but that some geothermal areas had significant REE resources. Significant reservoirs of REE were identified in the Western USA. In some cases, concentrations of REE were more than 1000 times the concentrations found in seawater. Collectively, these studies represent a comprehensive picture of REE resources associated with geothermal and hydrocarbon systems in the USA. The studies did not examine lithium resources, but in some cases, lithium concentration data was collected. Data from these studies are housed in the Geothermal Data Repository (GDR) and represent a significant information resource and it is recommended that these data be further analyzed in a future study. Eight projects were funded to develop new technology for REE extraction from geothermal fluids. These projects investigated sorption as an approach for removal and recovery of REE from geothermal brines. The projects investigated cutting-edge technology for selective sorption of ions from complex solutions, including the application of metal-organic frameworks and biosorbent proteins. The REE sorption studies tested different combinations of metal-binding ligands and solid supports. The most promising metal-binding ligands for REE included phosphonic acid, thiol, and carboxylic acid functional groups. Ligands were attached or incorporated into a wide variety of solid supports. In most cases, attachment was via covalent bonding to organic resins, polymers, or silica-based supports. Most of the REE projects were conducted at a low technology readiness level (TRL) and showed promise, but direct comparison between technologies was not possible based on the available information. It is recommended that testing and reporting be standardized to the extent possible to facilitate comparisons between technologies. Two projects were directed at novel lithium extraction technology. Both projects investigated the use of inorganic sorbents, including manganese oxides. One study also examined the use of metal- ion imprinted polymers as selective ion-exchange resins for the separation of lithium and manganese from brines. Both approaches showed promise for the selective extraction of lithium from brines, including potentially geothermal brines. Results from these GTO studies indicated that selective REE and lithium extraction is possible, but interference from co-occurring solutes, such as calcium, magnesium, or heavy metals, will interfere with process efficiency and negatively impact process economics. Techno-economic analysis conducted as part of the resource and technology studies suggest extraction of REE from geothermal brines is unlikely to be economically viable, especially since non-geothermal produced waters frequently have higher REE concentrations. It is recommended that benchmarks for techno-economic analysis be established to the extent possible for future studies, to facilitate direct comparison of various technologies. Based on the collective results of this program, it appears that hybrid geothermal power would benefit more from recovery of lithium and other metals, rather than REE. It is recommended that future studies be conducted at a higher- TRL and that sorbents be tested against actual geothermal fluid samples. Prior higher-TRL efforts to extract metals from geothermal brines should be further evaluated for lessons learned.

36 MATERIALS SCIENCE↗

Mixing states of Amazon basin aerosol particles transported over long distances using transmission electron microscopy

The Amazon basin is important for understanding the global climate because of its carbon cycle and as a laboratory for obtaining basic knowledge of the continental background atmosphere. Aerosol particles play an important role in the climate and weather, and knowledge of their compositions and mixing states is necessary to understand their influence on the climate. For this study, we collected aerosol particles from the Amazon basin during the Green Ocean Amazon (GoAmazon2014/5) campaign (February to March 2014) at the T3 site, which is located about 70 km from Manaus, and analyzed them using transmission electron microscopy (TEM). TEM has better spatial resolution than other instruments, which enables us to analyze the occurrences of components that attach to or are embedded within other particles. Based on the TEM results of more than 10 000 particles from several transport events, this study shows the occurrences of individual particles including compositions, size distributions, number fractions, and possible sources of materials that mix with other particles. Aerosol particles during the wet season were from both natural sources such as the Amazon forest, Saharan desert, Atlantic Ocean, and African biomass burning and anthropogenic sources such as Manaus and local emissions. These particles mix together at an individual particle scale. The number fractions of mineral dust and sea-salt particles increased almost 3-fold when long-range transport (LRT) from the African continent occurred. Nearly 20 % of mineral dust and primary biological aerosol particles had attached sea salts on their surfaces. Sulfates were also internally mixed with sea-salt and mineral dust particles. The TEM element mapping images showed that several components with sizes of hundreds of nanometers from different sources commonly occur within individual LRT aerosol particles. We conclude that many aerosol particles from natural sources change their compositions by mixing during transport. The compositions and mixing states of these particles after emission result in changes in their hygroscopic and optical properties and should be considered when assessing their effects on climate.

54 ENVIRONMENTAL SCIENCES↗

Mixing states of Amazon-basin aerosol particles transported over long distances using transmission electron microscopy

The Amazon basin is important for understanding the global climate both because of its carbon cycle and as a laboratory for obtaining basic knowledge of the continental background atmosphere. Aerosol particles play an important role in the climate and weather, and knowledge of their compositions and mixing states is necessary to understand their influence on the climate. For this study, we collected aerosol particles from the Amazon basin during the Green Ocean Amazon (GoAmazon2014/5) campaign (February to March 2014) at the T3 site, which locates about 70 km from Manaus, and analyzed using transmission electron microscopy (TEM). TEM has better spatial resolution than other instruments, which enables us to analyse the occurrences of components that attach to or are embedded within other particles. Based on the TEM results of more than 10,000 particles from several transport events, this study shows the occurrences of individual particles including compositions, size distributions, number fractions, and possible sources of materials that mix with other particles. Aerosol particles during the wet season were from both natural sources such as the Amazon forest, Saharan desert, Atlantic Ocean, and African biomass burning and anthropogenic sources such as Manaus and local emissions. These particles mix together at an individual particle scale. The number fractions of mineral dust and sea-salt particles increased almost three-fold when long-range transport (LRT) from the African continent occurred. Nearly 20 % of mineral dust and primary biological aerosol particles attached sea salts on their surfaces. Sulfates were also internally mixed with sea-salt and mineral dust particles. The TEM element mapping images showed that several components with sizes of hundreds of nanometres from different sources commonly occur within individual LRT aerosol particles. We conclude that many aerosol particles from natural sources change their compositions by mixing during transport. The compositions and mixing states of these particles after emission result in changes in their hygroscopic and optical properties and should be considered when assessing their effects on climate.

54 ENVIRONMENTAL SCIENCES↗

Performance of a Prototype Heliostat Having a Twisting Mechanism to Maintain Focus Throughout the Day

A prototype heliostat has been designed and built with a rectangular reflector whose shape is altered automatically through the day, to maximize concentration at the receiver. The shape changes needed to form solar disc images, which give the highest possible concentration, can be realized by twisting the reflector from its corners, provided that a target-oriented, dual-axis mount is used. Then a cam mechanism connected to the second (cross) axis drive, turning with the angle of incident sunlight, may be used to twist the reflector as needed. Our prototype reflector comprises a single glass mirror, 2.4 m x 3.3 m, attached to a steel frame. Four diagonal back struts extend from the central mechanism out to the rectangular frame corners. The glass mirror of the prototype is attached to the steel frame by 58 screw actuators. Before twisting the frame, the glass shape is adjusted to the biconic shape needed to form a 1 m diameter disc image on a 113 m distant target when sunlight is incident at 60°. To form disc images over the full range of angles of incidence from 0° (normal incidence) to 70°, the struts push the corners up and down by up to 17 mm. A reflectometry metrology system has been used to set the 58 adjustment screws for the initial shape to an accuracy of ≤ 0.6 mrad, and to measure the accuracy of the different twisted shapes. The prototype will be tested at NSTTF early next year.

14 SOLAR ENERGY↗

Dispensing system eliminates torsion in deployed hoses

Dispensing system uses a rotating drum, transfer arm, and stationary drum to deploy, reel in, and store an attached hose. This system which eliminates torsion and minimizes strain and wear of flexible hoses, is used for handling flexible cables that have one end permanently attached to an outlet or connector.

Source record↗

Tool permits damage-free removal of solar cell

Modified soldering iron extracts a wrap-around solar cell that is attached with solder or adhesive to a substrate without destroying the cell removed or damaging adjacent cells. Heat, vacuum, and compressed air, operated from a special head attached to the soldering iron, loosen, extract, and protect the cell.

Beckley, J. E., Jr.↗

Instrument accurately measures small temperature changes on test surface

Calorimeter apparatus accurately measures very small temperature rises on a test surface subjected to aerodynamic heating. A continuous thin sheet of a sensing material is attached to a base support plate through which a series of holes of known diameter have been drilled for attaching thermocouples to the material.

Harvey, W. D.↗

Versatile impact hand tool

Improved cartridge-actuated impact hand tool includes a common power head and four attachments to punch holes, drive forced entry fasteners, hammer, and shear. The attachments are self-contained and easily fitted to the power head assembly.

Hodil, E. R.↗

Shaker slip-plate adapter

Magnesium adapter ties in all of the attachment bosses on a horizontal slip table and makes a rigid coupling which terminates in a single row of attachment bosses at the edge of the horizontal plate. This eliminates ineffective dissipation of the driving force in vibration tests.

Holm, O. S.↗