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At least 811 records · Page 45

Large-scale Manufacturing of Nanoparticulate-based Lubrication Additives for Improved Energy Efficiency and Reduced Emissions

This project was funded under the Department of Energy (DOE) Lab Call on Nanomanufacturing for Energy Efficiency and was directed toward the development of novel boron-based nanocolloidal lubrication additives for improving the friction and wear performance of machine components in a wide range of industrial and transportation applications. Argonne's research team concentrated on the scientific and technical aspects of the project, using a range of state-of-the art analytical and tribological test facilities. Argonne has extensive past experience and expertise in working with boron-based solid and liquid lubrication additives, and has intellectual property ownership of several. There were two industrial collaborators in this project: Ashland Oil (represented by its Valvoline subsidiary) and Primet Precision Materials, Inc. (a leading nanomaterials company). There was also a sub-contract with the University of Arkansas. The major objectives of the project were to develop novel boron-based nanocolloidal lubrication additives and to optimize and verify their performance under boundary-lubricated sliding conditions. The project also tackled problems related to colloidal dispersion, larger-scale manufacturing and blending of nano-additives with base carrier oils. Other important issues dealt with in the project were determination of the optimum size and concentration of the particles and compatibility with various base fluids and/or additives. Boron-based particulate additives considered in this project included boric acid (H 3 BO 3 ), hexagonal boron nitride (h-BN), boron oxide, and borax. As part of this project, we also explored a hybrid MoS 2 + boric acid formulation approach for more effective lubrication and reported the results. The major motivation behind this work was to reduce energy losses related to friction and wear in a wide spectrum of mechanical systems and thereby reduce our dependence on imported oil. Growing concern over greenhouse gas emissions was also a major reason. The transportation sector alone consumes about 13 million barrels of crude oil per day (nearly 60% of which is imported) and is responsible for about 30% of the CO 2 emission. When we consider manufacturing and other energy-intensive industrial processes, the amount of petroleum being consumed due to friction and wear reaches more than 20 million barrels per day (from official energy statistics, U.S. Energy Information Administration). Frequent remanufacturing and/or replacement of worn parts due to friction-, wear-, and scuffing-related degradations also consume significant amounts of energy and give rise to additional CO 2 emission. Overall, the total annual cost of friction- and wear-related energy and material losses is estimated to be rather significant (i.e., as much as 5% of the gross national products of highly industrialized nations). It is projected that more than half of the total friction- and wear-related energy losses can be recovered by developing and implementing advanced friction and wear control technologies. In transportation vehicles alone, 10% to 15% of the fuel energy is spent to overcome friction. If we can cut down the friction- and wear-related energy losses by half, then we can potentially save up to 1.5 million barrels of petroleum per day. Also, less friction and wear would mean less energy consumption as well as less carbon emissions and hazardous byproducts being generated and released to the environment. New and more robust anti-friction and -wear control technologies may thus have a significant positive impact on improving the efficiency and environmental cleanliness of the current legacy fleet and future transportation systems. Effective control of friction in other industrial sectors such as manufacturing, power generation, mining and oil exploration, and agricultural and earthmoving machinery may bring more energy savings. Therefore, this project was timely and responsive to the energy and environmental objectives of DOE and our nation. In this project, most of the boron-based materials with known and potential anti-friction and -wear properties have been manufactured as colloidal additives and tested for their effectiveness in controlling friction and wear. Unlike other anti-friction and -wear additives, which consist of zinc, molybdenum, sulfur, phosphorus, and even chlorine, lubricious boron compounds considered in this project are made of boron, oxygen, nitrogen, and hydrogen, which are more environmentally benign. Among others, boric acid is a natural mineral (known in mineralogy as "sassolite"). Based on our earlier exploratory research, it was found to offer the best overall prospect in terms of performance improvements, environmental friendliness, and ease of manufacturing and, hence, cost effectiveness. Hexagonal boron nitride and borax also offered good prospects for improving the tribological properties of lubricated sliding surfaces. Boron oxide particles were found to be rather hard and somewhat abrasive and, hence, were not considered beyond the initial screening studies. In our bench-top tribological evaluation, we also demonstrated that those additives which worked well with engine oils could work equally well with very common gear oils. When added at appropriate concentrations, such gear oils were found to provide significant resistance to micropitting and scuffing failures in bench-top tribological test systems. Their traction coefficients were also reduced substantially and their scuffing limits were improved considerably. Such impressive tribological behavior of boron-based additives may have been due to their high chemical affinities to interact with sliding contact surfaces and to form slick and protective boundary films. Indeed, our surface studies have confirmed that most of the boron-based nanoparticulate additives prepared in our project possess a strong tendency to form a boron-rich boundary film on sliding contact surfaces. It is believed that the formation of such slick and highly durable boundary films is perhaps one of the fundamental reasons for their superior anti-friction, -wear, and -scuffing performance. Boron-based additives developed under this project have shown potential to reduce or replace the uses of environmentally unsafe sulfur- and phosphorus-bearing anti-wear and friction additives, such as zinc dialkyl dithiophosphate (ZDDP) and molybdenum dialkyl dithiocarbamate (MoDTC), in current lubricating oils. Because ZDDP and MoDTC were suspected of adversely impacting the performance of after-treatment catalysts in current engines, the Environmental Protection Agency (EPA) and other regulatory agencies are demanding that the concentrations of these catalysts in current oils be curtailed drastically. The boron-based nano-additives developed in this project may help reduce the use of ZDDP and MoDTC additives and, hence, help ease the poisoning effects on after-treatment catalysts. When used as lubricity additives, these boron additives can chemically interact with sliding or contacting surfaces and form a protective and slick boundary film, which can, in turn, help reduce friction and wear and increase resistance to scuffing. In the cases of traditional anti-friction and -wear additives mentioned, such protective boundary films result from phosphorus, sulfur, and other elements in the additive package, and again they have been under increased scrutiny in recent years, mainly because of their adverse effects on after-treatment devices. Overall, the boron-based nano-additive technology of this project was shown to hold promise for a broad range of industrial and transportation applications where lower friction and higher resistance to wear and scuffing are needed. Due to more stringent operating conditions of modern machinery, rolling, rotating, and sliding components have been failing to meet the projected lifetimes, mainly because of failures related to mechanical wear, corrosion, and scuffing. The novel boron-based additive technology developed under this project may help such machine components to function reliably by cutting down the friction and wear losses and by increasing resistance to scuffing.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

Request for Information from entities interested in commercializing Laboratory-developed homogeneous catalyst technology

Many industrial catalysts used for homogeneous hydrogenation and dehydrogenation of unsaturated substrates are derived from metal complexes that include (air-sensitive) ligands that are often expensive and difficult to synthesize. In particular, catalysts used for many hydrogenations are based on phosphorus containing ligands (in particular PNP pincer systems). These ligands are often difficult to make, are costly, are constrained to having two carbon atoms in the ligand backbone and are susceptible to oxidation at phosphorus, making their use somewhat complicated. Los Alamos researchers have recently developed a new and novel set of ligands that are based on a NNS (ENENES) skeleton (i.e. no phosphorus donors, just nitrogen and sulfur).

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Fire, dust, air and water: Improving aerosol biogeochemistry interactions in ACME. Final report

Aerosol-biogeochemistry interactions will have important consequences for human health, ecosystem services, and climate feedbacks over the next several decades. In this proposal we seek to link how human activities on land, including direct industrial emissions and landscape fires, impact the atmosphere and the biogeochemistry of the ocean and land. Our overall goal was to complement existing work at DOE labs to improve the capability and performance of the E3SM model in short-term, high-resolution projections of climate. Projections of ocean uptake of anthropogenic carbon are highly dependent on the details of the ocean physical and biogeochemistry parameterizations. Potentially equally important are the estimates of increases in iron and soluble nitrogen deposition in aerosols to the open ocean, but there are substantial uncertainties in these feedbacks. The E3SM land model simulates natural and anthropogenic fires, but improvement is needed to more accurately simulate fire responses to climate variability as well as fire contributions to terrestrial climate feedbacks. This proposal addressed four of the six priorities within the ACME/E3SM call by improving the representation of fire, industrial combustion sources, and desert dust and adding iron and soluble iron to the atmospheric chemistry (1). Our work focused on improving ocean biogeochemistry and the response of the oceans to anthropogenic atmospheric iron and nitrogen (3). We also improved the representation of land disturbance on fires and fire mediated carbon cycle feedbacks in the land model (4). Finally we had planned to couple the land, atmosphere and ocean biogeochemical systems (6) and explore how this coupling changes the feedbacks in the climate system. Our work under this proposal was separated into the following 5 tasks: i) improve representation of fire dynamics in both boreal and tropical ecosystems, ii) improve estimates of industrial emissions of iron and phosphorus, iii) improve representation of atmospheric iron, phosphorus and nitrogen transport, chemistry and deposition, iv) improve representation of iron, phosphorus and nitrogen deposition impacts on ocean biogeochemistry, and v) couple emissions into atmosphere, to deposition onto land and ocean biogeochemistry. For all 5 tasks, we conducted offline experiments of the historical period to enable comparison with available aerosol and land surface observations. We had planned to conduct fully coupled simulations, however, these will be conducted as part of the coupling in version 3 and 4 of the E3SM model, and thus have not been completed.

54 ENVIRONMENTAL SCIENCES↗

Strained Superlattice photocathode development using CBE and MBE

High polarization electron beams for accelerators are generated using strained superlattice GaAs-based photocathodes. A collaboration of researchers at University of California Santa Barbara and Jefferson Lab has been investigating growth of SSL photocathodes using either chemical- or molecular-beam epitaxy (CBE or MBE) to re-establish a source of high polarization photocathode material. While calibrating growth parameters for the now standard GaAs/GaAsP strained superlattice structure, the UCSB personnel encountered the drawbacks of growing structures with phosphorus in a MBE or CBE system, including high vapor pressure byproducts, phosphorus contamination in both the GaAs layer and all subsequent materials grown in that chamber, and highly flammable and toxic chamber residues. For these reasons, the UCSB team began additionally investigating strained superlattices of InAlGaAs/AlGaAs, which has been successfully demonstrated in the literature1, to be a high QE, high polarization photocathode material. For GaAs/GaAsP, varying phosphorus content affects both the band gap and polarization. However for InAlGaAs/AlGaAs, In and Al content can be varied independently and allows optimization of both polarization and bandgap. Several variations on InAlGaAs/AlGaAs superlattice photocathodes, including those with distributed Bragg reflector (DBR) structures to enhance QE, have been grown at UCSB and sent to Jefferson Lab for testing. The initial results are quite promising, with polarization over 80% and QE about 0.3%, and ongoing test results will be presented.

Stutzman, Marcy↗

Assessing Nutrient and Carbon Responses to Agricultural Conservation Practices in Two Midwest Watersheds

The United States is undertaking efforts to transition to a low-carbon economy in response to the heightened impacts of climate change, which are largely attributed to decades of carbon-intensive development. A concerted effort by the energy sector to achieve net-zero carbon emissions is aimed at strategically reducing the carbon footprint of the energy supply chain, particularly in the production of feedstocks for biofuels. The production of biofuels relies heavily on land use and management practices in biomass cultivation. Among other factors, soil organic carbon (SOC) plays a crucial role in the biofuel carbon cycle, impacting land productivity, greenhouse gas emissions, and water quality. The process of carbon drawdown during plant growth and storage helps to mitigate the release of carbon dioxide (CO 2 ) into the atmosphere. Another key parameter is the release of nitrous oxide (N 2 O) — a potent greenhouse gas with a global warming potential 273 times that of CO 2 — from soil. While prioritizing low-carbon production, sustainable bioenergy also necessitates improved water quality and ecosystem services. Agricultural conservation practices can contribute to enhanced soil health and reduce nutrient and sediment loss into streams. However, studies that explore the broader impact of these practices on soil carbon storage and N 2 O emissions at a watershed scale are limited. Specifically, our understanding of how low-carbon feedstock production and management affect nutrient cycle dynamics is incomplete. This study assesses watershed responses to land management practices in two agriculturally dominant watersheds: the Raccoon River watershed and the Southfork of Iowa River watershed. The study focuses on carbon and nutrient dynamics, characterizing spatial and temporal variations in SOC, N 2 O, and nutrient loadings to examine the relationship between nutrient and carbon responses and agricultural conservation practices. The study employs the newly developed Soil Water Analysis Tool for Carbon (SWAT-C) model, calibrated using 20 years’ of climate and water monitoring data, to simulate and evaluate two agricultural conservation practices: no-till and crop residue harvest with cover crop planting. We compared the calibrated SWAT-C model with a historical baseline model, which allowed us to analyze various aspects of the watershed, including stream flow, suspended sediments, nitrogen, phosphorus, organic carbon, SOC at different depths, and N 2 O emissions from topsoil. Our SWAT-C modeling results indicate that, compared with results from the historical baseline model, no-till practices are positively correlated with SOC accumulation, reduced N 2 O emissions, and decreased soil loss. We also observed no change or slightly increased nitrogen and phosphorus loss to water bodies in the watersheds compared with the baseline. Conversely, crop residue harvest with cover crop planting improved water quality by reducing nutrient and soil losses but also increased N 2 O emissions. This SWAT-C modeling study establishes the groundwork for further smaller-scale and/or sub-basin-level assessments of nitrogen, phosphorus, and carbon cycles. It provides valuable science-based insights to inform policy decisions — particularly in the context of transitioning to biofuel feedstock production in these watersheds — by addressing concerns about nutrient exports to local water bodies and, ultimately, the Mississippi River.

54 ENVIRONMENTAL SCIENCES↗

Diversity and Structure of Diazotrophic Communities in Mangrove Rhizosphere, Revealed by High-Throughput Sequencing

Diazotrophic communities make an essential contribution to the productivity through providing new nitrogen. However, knowledge of the roles that both mangrove tree species and geochemical parameters play in shaping mangove rhizosphere diazotrophic communities is still elusive. Here, a comprehensive examination of the diversity and structure of microbial communities in the rhizospheres of three mangrove species, Rhizophora apiculata , Avicennia marina , and Ceriops tagal , was undertaken using high-throughput sequencing of the 16S rRNA and nifH genes. Our results revealed a great diversity of both the total microbial composition and the diazotrophic composition specifically in the mangrove rhizosphere. Deltaproteobacteria and Gammaproteobacteria were both ubiquitous and dominant, comprising an average of 45.87 and 86.66% of total microbial and diazotrophic communities, respectively. Sulfate-reducing bacteria belonging to the Desulfobacteraceae and Desulfovibrionaceae were the dominant diazotrophs. Community statistical analyses suggested that both mangrove tree species and additional environmental variables played important roles in shaping total microbial and potential diazotroph communities in mangrove rhizospheres. In contrast to the total microbial community investigated by analysis of 16S rRNA gene sequences, most of the dominant diazotrophic groups identified by nifH gene sequences were significantly different among mangrove species. The dominant diazotrophs of the family Desulfobacteraceae were positively correlated with total phosphorus, but negatively correlated with the nitrogen to phosphorus ratio. Finally, the Pseudomonadaceae were positively correlated with the concentration of available potassium, suggesting that diazotrophs potentially play an important role in biogeochemical cycles, such as those of nitrogen, phosphorus, sulfur, and potassium, in the mangrove ecosystem.

59 BASIC BIOLOGICAL SCIENCES↗

Effects of Media Nutrient Variation on Microalgae Productivity and Economics During Semi-Continuous Cultivation

The development of large-scale microalgae growth for biofuel production is currently limited by the cost of biomass production. However, new approaches to infrastructure and cultivation practices are bringing the field closer to realization. Macronutrients in the cultivation media contribute significant costs, especially since their concentrations have not been optimized for specific strains and conditions. Environmental photobioreactors (ePBRs) were used to simulate cultivation under outdoor conditions, during which the nitrogen and phosphorus levels in the media were varied. The growth of two potential biofuel production strains, Picochlorum celeri and Tetraselmis striata, with varying nutrient inputs during summer and winter scripts, respectively, was studied. This study demonstrated that nitrogen and phosphorus in f/2 media could be reduced by more than 60% from the standard formulation, while maintaining growth rates in a semi-continuous harvesting approach. Experiments comparing the standard and reduced nutrient input concentrations were also conducted for both species in 820 L outdoor raceway ponds, in Mesa, AZ. P. celeri grown in these ponds in October had a growth rate of 10.6 ± 0.7 g/m 2 /day and 10.6 ± 0.3 g/m 2 /day for the standard and low-nutrient P. celeri ponds, respectively. T. striata grown in April–May had a growth rate of 16.6 ± 1.4 g/m 2 /day for the standard nutrient input ponds and 17.4 ± 1.1 g/m 2 /day for the low-nutrient input ponds, and in October 14.5 ± 0.6 g/m 2 /day for standard nutrient ponds and 14.4 ± 0.6 g/m 2 /day for low-nutrient ponds. These outdoor data therefore confirmed the indoor ePBR data. Techno-economic analysis shows that, if high growth rates can be attained at lower nutrient concentrations, a reduction of at least 60% in nutrient costs can be achieved. Such results highlight the importance of managing macronutrient media inputs, as these have a considerable contribution to biomass production costs in large-scale facilities. The analysis also points to the importance of maintaining high spent medium recycling rates in an industrial deployment, so as to minimize the losses of nitrogen and phosphorus compounds.

09 BIOMASS FUELS↗

A Generic Biogeochemical Module for Earth System Models: Next Generation BioGeoChemical Module (NGBGC), Version 1.0

Physical and biogeochemical processes regulate soil carbon dynamics and CO2 flux to and from atmosphere, influencing global climate changes. Integration of these processes into earth system models (e.g., community land models (CLM)), however, currently faces three major challenges: 1) extensive efforts are required to modify modeling structures and to rewrite computer programs to incorporate new or updated processes as new knowledge is being generated, 2) computational cost is prohibitively expensive to simulate biogeochemical processes in land models due to large variations in the rates of biogeochemical processes, and 3) various mathematical representations of biogeochemical processes exist to incorporate different aspects of fundamental mechanisms, but systematic evaluation of the different mathematical representations is difficult, if not possible. To address these challenges, we propose a new computational framework to easily incorporate physical and biogeochemical processes into land models. The new framework consists of a new biogeochemical module with a generic algorithm and reaction database so that new and updated processes can be incorporated into land models without the need to manually set up the ordinary differential equations to be solved numerically. The reaction database consists of processes of nutrient flow through the terrestrial ecosystems in plants, litter and soil. This framework facilitates effective comparison studies of biogeochemical cycles in an ecosystem using different conceptual models under the same land modeling framework. The approach was first implemented in CLM and benchmarked against simulations from the original CLM-CN code. A case study was then provided to demonstrate the advantages of using the new approach to incorporate a phosphorus cycle into the CLM model. To our knowledge, the phosphorus-incorporated CLM is a new model that can be used to simulate phosphorus limitation on the productivity of terrestrial ecosystems.

Fang, Yilin↗

Hall effect study of electron irradiated Si(Li)

Measurement of the Hall coefficient as a function of temperature between 15 and 300 K allows the separate determination of donor and acceptor concentrations in silicon samples which were irradiated at 240 K by 1-MeV electrons and then thermally annealed at 300 K. In both lithium- and phosphorus-doped silicon irradiation increased the acceptor concentration and decreased the donor concentration due to the formation of vacancy donor pairs. Annealing did not change either concentration in phosphorus-doped silicon and caused both concentrations to decrease in silicon doped with moderate amounts of lithium. In addition to this, in both lithium- and phosphorus-doped silicon the concentration and energy level of the A center were measured at each point in the sample's history. This experiment was limited to float-zoned silicon doped with less than 6 x 10 to the 14th power donors per cu cm.

Stannard, J.↗

Tailored emitter, low-resistivity, ion-implanted silicon solar cells

Open-circuit voltages as high as 0.645 V (AM0, 25 C) have been obtained by a new process developed for low-resistivity silicon. The process utilizes high-dose phosphorus implantation followed by furnace annealing and simultaneous oxide growth. The effect of the thermally grown oxide is a reduction of surface recombination velocity; the oxide also acts as a moderately efficient antireflection (AR) coating. Boron-doped, float-zone silicon with resistivities from 0.1 to 1.0 (omega)(cm) has been processed according to this sequence; results show that the highest open-circuit voltage is obtained with 0.1(omega)(cm) starting material. The effects of Auger recombination and bandgap narrowing caused by high doping concentrations in the n(+)junction region have been investigated by implanting phosphorus over a wide range of dose levels. The effects of emitter-phosphorus concentrations tailored to optimize electric fields in the emitter have also been investigated.

Minnucci, J. A.↗

Rust and schreibersite in Apollo 16 highland rocks - Manifestations of volatile-element mobility

Rust is a manifestation of halogen and volatile-metal mobility in the lunar environment. Schreibersite is stable as the primary phosphorus-bearing phase in the highland rocks, a consequence of the inherently low oxygen fugacity within impact-generated melts. Apatite and whitlockite are subordinate in these rocks. The partitioning of P into phosphide in impact-generated melts, and the failure of phosphate to crystallize, effects a decoupling of the halogens and phosphorus. Of the Apollo 16 rocks, 63% contain rust, 70% contain schreibersite, and 52% contain both phases, thereby establishing the pervasiveness of volatile-elements throughout the highland rocks. The major portion of these volatile-bearing phases occur in impact melt-rocks or in breccia matrices. Rhabdites of schreibersite in some of the FeNi grains indicate that there is a meteoritic contribution to the phosphorus in these rocks. Cl/P2O5 ratios in lunar highland rocks are a function of secondary effects, with any apparent Cl-P correlations being coincidential. The present observations preclude the validity of models based on such elemental ratios in these rocks. The presence of rust in the clast laden matrices of pristine rocks indicates fugitive element localization. Pristine clasts may have been contaminated. The basis for a pristine volatile chemistry is questioned.

Hunter, R. H.↗

Development of phosphorylated adhesives

The synthesis of epoxy prepolymers containing phosphorus was carried out in such a manner as to provide adhesives containing at least 5 percent of this element. The purpose of this was to impart fire retardant properties to the adhesive. The two epoxy derivatives, bis(4-glycidyl-oxyphenyl)phenylphosphine oxide and bis(4-glycidyl-2-methoxyphenyl)phenylphosphonate, and a curing agent, bis(3-aminophenyl)methylphosphine oxide, were used in conjunction with one another and along with conventional epoxy resins and curing agents to bond Tedlar and Polyphenylethersulfone films to Kerimid-glass syntactic foam-filled honeycomb structures. Elevated temperatures are required to cure the epoxy resins with the phosphorus-contaning diamine; however, when Tedlar is being bonded, lower curing temperatures must be used to avoid shrinkage and the concomitant formation of surface defects. Thus, the phosphorus-containing aromatic amine curing agent cannot be used alone, although it is possible to use it in conjunction with an aliphatic amine which would allow lower cure temperatures to be used. The experimental epoxy resins have not provided adhesive bonds quite as strong as those provided by Epon 828 when compared in peel tests, but the differences are not very significant. It should be noted, if optimum properties are to be realized. In any case the fire retardant characteristics of the neat resin systems obtained are quite pronounced, since in most cases the self-extinguishing properties are evident almost instantly when specimens are removed from a flame.

Bilow, N.↗

Flat-plate solar array project process development area, process research of non-CZ silicon material

The program is designed to investigate the fabrication of solar cells on N-type base material by a simultaneous diffusion of N-type and P-type dopants to form an P(+)NN(+) structure. The results of simultaneous diffusion experiments are being compared to cells fabricated using sequential diffusion of dopants into N-base material in the same resistivity range. The process used for the fabrication of the simultaneously diffused P(+)NN(+) cells follows the standard Westinghouse baseline sequence for P-base material except that the two diffusion processes (boron and phosphorus) are replaced by a single diffusion step. All experiments are carried out on N-type dendritic web grown in the Westinghouse pre-pilot facility. The resistivities vary from 0.5 (UC OMEGA)cm to 5 (UC OMEGA)cm. The dopant sources used for both the simultaneous and sequential diffusion experiments are commercial metallorganic solutions with phosphorus or boron components. After these liquids are applied to the web surface, they are baked to form a hard glass which acts as a diffusion source at elevated temperatures. In experiments performed thus far, cells produced in sequential diffusion tests have properties essentially equal to the baseline N(+)PP(+) cells. However, the simultaneous diffusions have produced cells with much lower IV characteristics mainly due to cross-doping of the sources at the diffusion temperature. This cross-doping is due to the high vapor pressure phosphorus (applied as a metallorganic to the back surface) diffusion through the SiO2 mask and then acting as a diffusant source for the front surface.

Campbell, R. B.↗

Calcium-regulated in vivo protein phosphorylation in Zea mays L. root tips

Calcium dependent protein phosphorylation was studied in corn (Zea mays L.) root tips. Prior to in vivo protein phosphorylation experiments, the effect of calcium, ethyleneglycol-bis-(beta-aminoethyl ether)-N-N' -tetraacetic acid (EGTA) and calcium ionophore (A-23187) on phosphorus uptake was studied. Calcium increased phosphorus uptake, whereas EGTA and A-23187 decreased it. Consequently, phosphorus concentration in the media was adjusted so as to attain similar uptake in different treatments. Phosphoproteins were analyzed by two-dimensional gel electrophoresis. Distinct changes in phosphorylation were observed following altered calcium levels. Calcium depletion in root tips with EGTA and A-23187 decreased protein phosphorylation. However, replenishment of calcium following EGTA and ionophore pretreatment enhanced phosphorylation of proteins. Preloading of the root tips with 32P in the presence of EGTA and A-23187 followed by a ten minute calcium treatment, resulted in increased phosphorylation indicating the involvement of calcium, calcium and calmodulin-dependent kinases. Calmodulin antagonist W-7 was effective in inhibiting calcium-promoted phosphorylation. These studies suggest a physiological role for calcium-dependent phosphorylation in calcium-mediated processes in plants.

NASA Discipline Plant Biology↗

Seasonal variations in urinary risk factors among patients with nephrolithiasis

Twenty-four hour urine specimens from 5,677 stone-forming patients throughout the United States were analyzed for seasonal variations in urinary risk factors for nephrolithiasis. Determinations were performed for urine volume, pH, calcium, oxalate, phosphorus, sodium, magnesium, citrate, sulfate, uric acid, and the relative supersaturation (RS) of calcium oxalate, brushite, monosodium urate, and uric acid. Criteria for significant seasonal variation included a significant difference in monthly means of risk factors, seasonal grouping of the data by the Student-Newman-Keuls multiple range test, consistent year-to-year trends and a physiologically significant range. Minimum urine volume of 1.54 +/- 0.70 SD L/day occurred in October while a maximum urine volume of 1.76 +/- 0.78 SD L/day was observed during February. Minimum urine pH of 5.94 +/- 0.64 SD was observed during July and August while a maximum pH of 6.18 +/- 0.61 SD was observed during February. Daily urinary excretion of sodium was lowest during August, 158 +/- 74 SD mEq/day and highest during February 177 +/- 70 SD mEq/day. The RS of brushite and uric acid were found to display significant pH-dependent seasonal variation with a maximum RS of uric acid 2.26 +/- 1.98 SD in June and a low of 1.48 +/- 1.30 SD in February. Maximum RS of brushite 2.75 +/- 2.58 was observed during February. Minimum RS of brushite 1.93 +/- 1.70 SD was observed in June. Phosphorus excretion displayed seasonal variation about a spring-fall axis with a maximum value 1042 +/- 373 SD mg/day in April and a minimum value of 895 +/- 289 SD mg/day. Urine volume, sodium, and pH were significantly lower during the summer (June, July, August) than in the winter (December, January, February). The RS of uric acid was higher, but that of brushite and monosodium urate was lower in the summer than in the winter. The seasonal changes observed in urine volume, pH, sodium, and the RS of brushite and uric acid are consistent with summertime sweating and increased physical activity. Seasonal variations in phosphorus excretion are probably dietary in origin. The summertime was characterized by an increased propensity for the crystallization of uric acid but not of calcium oxalate or calcium phosphate.

NASA Discipline Regulatory Physiology↗

Review of HxPyOz-Catalyzed H + OH Recombination in Scramjet Nozzle Expansions; and Possible Phosphoric Acid Enhancement of Scramjet Flameholding, from Extinction of H3PO4 + H2 - Air Counterflow Diffusion Flames

Recent detailed articles by Twarowski indicate that small quantities of phosphorus oxides and acids in the fuel-rich combustion products of H2 + phosphine (PH3) + air should significantly catalyze H, OH and O recombination kinetics during high-speed nozzle expansions -- to reform H2O, release heat, and approach equilibrium more rapidly and closely than uncatalyzed kinetics. This paper is an initial feasibility study to determine (a) if addition of phosphoric acid vapor (H3PO4) to a H2 fuel jet -- which is much safer than using PH3 -- will allow combustion in a high-speed scramjet engine test without adverse effects on localized flameholding, and (b) if phosphorus-containing exhaust emissions are environmentally acceptable. A well-characterized axisymmetric straight-tube opposed jet burner (OJB) tool is used to evaluate H3PO4 addition effects on the air velocity extinction limit (flame strength) of a H2 versus air counterflow diffusion flame. Addition of nitric oxide (NO), also believed to promote catalytic H-atom recombination, was evaluated for comparison. Two to five mass percent H3PO4 in the H2 jet increased flame strength 4.2%, whereas airside addition decreased it 1%. Adding 5% NO to the H2 caused a 2% decrease. Products of H-atom attack on H3PO4 produced an intense green chemiluminescence near the stagnation point. The resultant exothermic production of phosphorus oxides and acids, with accelerated H-atom recombination, released sufficient heat near the stagnation point to increase flame strength. In conclusion, the addition of H3PO4 vapor (or more reactive P sources) to hydrogen in scramjet engine tests may positively affect flameholding stability in the combustor and thrust production during supersonic expansion -- a possible dual benefit with system design / performance implications. Finally, a preliminary assessment of possible environmental effects indicates that scramjet exhaust emissions should consist of phosphoric acid aerosol, with gradual conversion to phosphate aerosol. This is compared to various natural abundances and sources.

Pellett, Gerald↗

Ionic liquids, electrolyte solutions including the ionic liquids, and energy storage devices including the ionic liquids

An ionic liquid including a phosphazene compound that has a plurality of phosphorus-nitrogen units and at least one pendant group bonded to each phosphorus atom of the plurality of phosphorus-nitrogen units. One pendant group of the at least one pendant group comprises a positively charged pendant group. Additional embodiments of ionic liquids are disclosed, as are electrolyte solutions and energy storage devices including the embodiments of the ionic liquid.

25 ENERGY STORAGE↗

High capacity organic radical mediated phosphorous anode for redox flow batteries

A battery includes a redox flow anode chamber coupled to an anode current collector, a separator, and an external container in fluid connection with the redox flow anode chamber. The external container has therein a solid phosphorus material. A first redox-active mediator and the second redox-active mediator are circulated through the half-cell electrode chamber and the external container. During a charging cycle the first redox-active mediator is reduced at the current collector electrode and the reduced first mediator reduces the phosphorus material, and wherein during a discharging cycle the second redox-active mediator is oxidized at the anode current collector electrode, and the second redox-active mediator is then reduced by the reduced phosphorus material. A method of operating a battery and a method of making a battery are also discussed.

Delnick, Frank M.↗