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At least 109 records · Page 6

The Role of Self-Organized Criticality in the Substorm Phenomenon and its Relation to Localized Reconnection in the Magnetospheric Plasma Sheet

Evidence is presented that suggests there is a significant self-organized criticality (SOC) component in the dynamics of substorms in the magnetosphere. Observations of BBFs, fast flows, localized dipolarizations, plasma turbulence, etc. are taken to show that multiple localized reconnection sites provide the basic avalanche phenomenon in the establishment of SOC in the plasma sheet. First results are presented from a continuing plasma physical study of this avalanche process. A one-dimensional resistive MHD model of a magnetic field reversal is discussed. Resistivity, in this model, is self-consistently generated in response to the excitation of an idealized current-driven instability. When forced by convection of magnetic flux into the field reversal region, the model yields rapid magnetic field annihilation through a dynamic behavior that is shown to exhibit many of the characteristics of SOC. Over a large range of forcing strengths, the annihilation rate is shown to self-adjust to balance the rate at which flux is convected into the reversal region. Several analogies to magnetotail dynamics are discussed: (1) It is shown that the presence of a localized criticality in the model produces a remarkable stability in the global configuration of the field reversal while simultaneously exciting extraordinarily dynamic internal evolution. (2) Under steady forcing, it is shown that a loading-unloading cycle may arise that, as a consequence of the global stability, is quasi-periodic and, therefore, predictable despite the presence of internal turbulence in the field distribution. Indeed, it is shown that the global loading-unloading cycle is a consequence of the internal turbulence. (3) It is shown that, under steady, strong forcing the loading-unloading cycle vanishes. Instead, a recovery from a single unloading persists indefinitely. The field reversal is globally very steady while internally it is very dynamic as field annihilation goes on at the rate necessary to match the strong forcing. From this result we speculate that steady magnetospheric convection events result when the plasma sheet has been driven close to criticality over an extended spatial domain. During these events, we would expect to find localized reconnection sites distributed over the spatial domain of near criticality and we would expect to find plasma sheet transport in that domain to be closely related to that of BBF and fast flow events.

Klimas, Alex J.↗

Aerosol Particle Mixing State and Composition at AMF3 (Interim Field Campaign Report)

The campaign is designed to support deployment of aerosol sampling equipment at the U.S. Department of Energy Atmospheric Radiation Measurement (ARM) user facility’s third ARM Mobile Facility (AMF3) to enable both singe-particle and bulk characterization of the aerosol particles at the field site in Bankhead National Forest, northern Alabama. We are proposing to do this work as part of our proposal “Generalizing aerosol mixing state: synthesis from observations and connection to models,” which has the pre-proposal tracking number PRE-0000035878. The full proposal has Dr. Rachel O’Brien as the Principal Investigator (PI) and Dr. Andy Ault and Dr. Nicole Riemer as Co-PIs. We sought to deploy instruments in winter 2025 and summer 2025 to obtain samples in different seasons, but were delayed by AMF3 set-up and availability of students and PIs. We just completed our first deployment this summer (2025) and we are interested in obtaining samples during this upcoming fall and winter to see the seasonal trends in aerosol mixing state at the site. This will provide a comparison of the impact of biogenic emissions on the mixing state and the chemical composition of the aerosol particles. Overall, the proposed study will provide key information regarding the mixing state of aerosol particles at AMF3 with direct ties to impacts of the particles on cloud formation and light scattering/absorption. From our deployment that ended las week we have some visible observations from our samples. We are observing a regular amount of black carbon on stage 6 of our Micro-Orifice Uniform Deposit Impactor (MOUDI) and we have also observed some short, large increases in aerosol loading. We hope to continue observations of these two features to determine the sources/aging for the black carbon and the physical mixing state as well as the sources for the short (a few minutes) increases in the aerosol loading and determine if the source for these is dust or sea salt or another source. We are also interested in comparing the black carbon we see here to samples collected during the agriculture burns in January/February and in comparing the larger particles to bioaerosols in the spring. To obtain these comparisons, we will need to collect more samples in the other seasons. Finally, we have some size-resolved particle collectors that can be deployed at the same time as the tethered balloon launches. We have discussed with Swarup China about trying to get the timing to work in August and we are interested in coordinating again later, if possible. This will give us ground-level and vertical aerosol mixing state sample sets that will be very exciting to analyze.

54 ENVIRONMENTAL SCIENCES↗

The Jet Propulsion Laboratory low-cost solar array project, 1974-1986

The overall objective of the photovoltaic program is to ensure that photovoltaic conversion systems play a significant role in the nation's energy supply by stimulating an industry capable of providing approximately 50 GWe of installed electricity generating capacity by the year 2000. In order to achieve this overall objective, several time-phased program goals have been defined. Near-term goals are to achieve photovoltaic flat-plate module or concentrator array prices of $2 per peak watt (1975 dollars) at an annual production rate of 20 peak megawatts in 1982. At this price level, energy costs should range from 100 to 200 mills/kwh. Mid-term goals are to achieve photovoltaic flat-plate module or concentrator array prices of $0.50 per peak watt (in 1975 dollars), and an annual production rate of 500 peak megawatts in 1986. Studies project that photovoltaic systems will begin to compete for both distributed and larger load-center utility-type applications and thereby open up significant markets for large-scale photovoltaic systems. Far term goals are to achieve the photovoltaic flat-plate module or concentrator array price goal of $0.10 to $0.30 per peak watt in 1990 (in 1975 dollars), and an annual production rate of 10 to 20 peak gigawatts in 2000. At this price range, energy cost should be in the range of 40 to 60 mills. kwh and be cost effective for utility applications. Achievement of these goals can make photovoltaic systems economically competitive with other energy sources for dispersed on-site applications as well as for central power generation.

Maycock, P. D.↗

Natural and Anthropogenic Aerosol Trends from Satellite and Surface Observations and Model Simulations over the North Atlantic Ocean from 2002 to 2012

Aerosols contribute to Earths radiative budget both directly and indirectly, and large uncertainties remain in quantifying aerosol effects on climate. Variability in aerosol distribution and properties, as might result from changing emissions and transport processes, must be characterized. In this study, variations in aerosol loading across the eastern seaboard of theUnited States and theNorthAtlanticOcean during 2002 to 2012 are analyzed to examine the impacts of anthropogenic emission control measures using monthly mean data from MODIS, AERONET, and IMPROVE observations and Goddard Chemistry Aerosol Radiation and Transport (GOCART) model simulation.MODIS observes a statistically significant negative trend in aerosol optical depth (AOD) over the midlatitudes (-0.030 decade(sup-1)). Correlation analyses with surface AOD from AERONET sites in the upwind region combined with trend analysis from GOCART component AOD confirm that the observed decrease in the midlatitudes is chiefly associated with anthropogenic aerosols that exhibit significant negative trends from the eastern U.S. coast extending over the western North Atlantic. Additional analysis of IMPROVE surface PM(sub 2.5) observations demonstrates statistically significant negative trends in the anthropogenic components with decreasing mass concentrations over the eastern United States. Finally, a seasonal analysis of observational datasets is performed. The negative trend seen by MODIS is strongest during spring (MAM) and summer (JJA) months. This is supported by AERONET seasonal trends and is identified from IMPROVE seasonal trends as resulting from ammonium sulfate decreases during these seasons.

Jongeward, Andrew R.↗

Fracture analysis of stiffened panels under biaxial loading with widespread cracking

An elastic-plastic finite-element analysis with a critical crack-tip opening angle (CTOA) fracture criterion was used to model stable crack growth and fracture of 2024-T3 aluminum alloy (bare and clad) panels for several thicknesses. The panels had either single or multiple-site damage (MSD) cracks subjected to uniaxial or biaxial loading. Analyses were also conducted on cracked stiffened panels with single or MSD cracks. The critical CTOA value for each thickness was determined by matching the failure load on a middle-crack tension specimen. Comparisons were made between the critical angles determined from the finite-element analyses and those measured with photographic methods. Predicted load-against-crack extension and failure loads for panels under biaxial loading, panels with MSD cracks, and panels with various numbers of stiffeners were compared with test data whenever possible. The predicted results agreed well with the test data even for large-scale plastic deformations. The analyses were also able to predict stable tearing behavior of a large lead crack in the presence of MSD cracks. The analyses were then used to study the influence of stiffeners on residual strength in the presence of widespread fatigue cracking. Small MSD cracks were found to greatly reduce the residual strength for large lead cracks even for stiffened panels.

Newman, J. C., Jr.↗

Fracture analysis of stiffened panels under biaxial loading with widespread cracking

An elastic-plastic finite-element analysis with a critical crack-tip-opening angle (CTOA) fracture criterion was used to model stable crack growth and fracture of 2024-T3 aluminum alloy (bare and clad) panels for several thicknesses. The panels had either single or multiple-site damage (MSD) cracks subjected to uniaxial or biaxial loading. Analyses were also conducted on cracked stiffened panels with single or MSD cracks. The critical CTOA value for each thickness was determined by matching the failure load on a middle-crack tension specimen. Comparisons were made between the critical angles determined from the finite-element analyses and those measured with photographic methods. Predicted load-against-crack extension and failure loads for panels under biaxial loading, panels with MSD cracks, and panels with various number of stiffeners were compared with test data, whenever possible. The predicted results agreed well with the test data even for large-scale plastic deformations. The analyses were also able to predict stable tearing behavior of a large lead crack in the presence of MSD cracks. The analyses were then used to study the influence of stiffeners on residual strength in the presence of widespread fatigue cracking. Small MSD cracks were found to greatly reduce the residual strength for large lead cracks even for stiffened panels.

Newman, J. C., Jr.↗

Development of the Resource Prospector Planetary Rover

The Resource Prospector (RP) is an In-­‐Situ Resource Utilization (ISRU) lunar rover mission under study by NASA. RP is planned to launch in 2020 to prospect for subsurface volatiles and to extract oxygen from lunar regolith. The mission will address several of NASA's "Strategic Knowledge Gaps" for lunar exploration. The mission will also address the Global Exploration Roadmap's strategic goal of using local resources for human exploration. The distribution of lunar subsurface volatiles drives the mission requirement for mobility. The spatial distribution is hypothesized to be governed by impact cratering with the top 0.5 m being patchy at scales of 100 m. The mixing time scale increases with depth (less frequent larger impacts). Consequently, increased mobility reduces the depth requirement for sampling. The target RP traverse will extend 1 km radially from the landing site to sample craters of varying sizes. Sampling craters with different ages will reveal possible volatile emplacement history. In 1 Ga, approximately 60-­70 craters of 10 m diameter form per km2. Thus, the rover will need to sample at least ten of these craters, which may require a total traverse path length of 2-­‐3 km. During 2014-­2015, we developed an initial prototype rover for RP. The current design is a solar powered, four-­wheeled vehicle, with hub motor drive, offset four wheel steering, and active suspension. Active suspension provides capabilities including changing vehicle ride height, traversing comparatively large obstacles, and controlling load on the wheels. All-­wheel steering enables the vehicle to point arbitrarily while roving, e.g., to keep the solar array pointed at the sun while in motion. The offset steering combined with active suspension improves driving in soft soil. The rover's on-­board software utilizes NASA's Core Flight Software, which is a reusable flight software environment. During 2015, we completed the initial rover software build, which provides low-­level hardware interfaces, basic mobility control, waypoint driving, odometry, basic error checking, and camera services. Development of the prototype rover has enabled maturation of many of the subsystems to TRL 5. During the next year, we will conduct integrated testing of concepts of operation, navigation, and remote driving tools. In addition, we will perform environmental tests including radiation (avionics), thermal and thermal/vacuum (mechanisms), and gravity offload (mobility).

robotics↗

Test and Analysis of a Buckling-Critical Large-Scale Sandwich Composite Cylinder

Structural stability is an important design consideration for launch-vehicle shell structures and it is well known that the buckling response of such shell structures can be very sensitive to small geometric imperfections. As part of an effort to develop new buckling design guidelines for sandwich composite cylindrical shells, an 8-ft-diameter honeycomb-core sandwich composite cylinder was tested under pure axial compression to failure. The results from this test are compared with finite-element-analysis predictions and overall agreement was very good. In particular, the predicted buckling load was within 1% of the test and the character of the response matched well. However, it was found that the agreement could be improved by including composite material nonlinearity in the analysis, and that the predicted buckling initiation site was sensitive to the addition of small bending loads to the primary axial load in analyses.

Schultz, Marc R.↗

Design and Use of a Large-Scale Liquid Helium Conversion System

A large-scale liquid helium (LHe) to high-pressure (HP) gas conversion system has been implemented at the John F. Kennedy Space Center (KSC). Helium is used by the Space Shuttle, Titan, Atlas, and Delta programs for prelaunch processing, during launch count-down, and for postlaunch securing. The first phase of modifications to the Compressor Converter Facility (CCF), operational in April 1998, allowed the facility to accept bulk liquid helium from tanker containers and to off-load the helium at super-critical pressures. The second phase of modifications, planned to be operational by January 2001, will implement a 227-cubic-meter (m(sup 3)) on-site liquid helium storage system. This paper describes the design and operation of the current system and discusses the design and implementation for the second phase system.

Knudsen, P. N.↗

Aerosols in polluted versus nonpolluted air masses Long-range transport and effects on clouds

To assess the influence of anthropogenic aerosols on the physics and chemistry of clouds in the northeastern United States, aerosol and cloud-drop size distributions, elemental composition of aerosols as a function of size, and ionic content of cloud water were measured on Whiteface Mountain, NY, during the summers of 1981 and 1982. In several case studies, the data were cross-correlated with different air mass types - background continental, polluted continental, and maritime - that were advected to the sampling site. The results are the following: (1) Anthropogenic sources hundreds of kilometers upwind cause the small-particle (accumulation) mode number to increase from hundreds of thousands per cubic centimeter and the mass loading to increase from a few to several tens of micrograms per cubic meter, mostly in the form of sulfur aerosols. (2) A significant fraction of anthropogenic sulfur appears to act as cloud condensation nuclei (CCN) to affect the cloud drop concentration. (3) Clouds in Atlantic maritime air masses have cloud drop spectra that are markedly different from those measured in continental clouds. The drop concentration is significantly lower, and the drop size spectra are heavily skewed toward large drops. (4) Effects of anthropogenic pollutants on cloud water ionic composition are an increase of nitrate by a factor of 50, an increase of sulfate by more than one order of magnitude, and an increase of ammonium ion by a factor of 7. The net effect of the changes in ionic concentrations is an increase in cloud water acidity. An anion deficit even in maritime clouds suggests an unknown, possibly biogenic, source that could be responsible for a pH below neutral, which is frequently observed in nonpolluted clouds.

Pueschel, R. F.↗

Absorption Properties of Mediterranean Aerosols Obtained from Multi-year Ground-based and Satellite Remote Sensing Observations

Aerosol absorption properties are of high importance to assess aerosol impact on regional climate. This study presents an analysis of aerosol absorption products obtained over the Mediterranean Basin or land stations in the region from multi-year ground-based AERONET and satellite observations with a focus on the Absorbing Aerosol Optical Depth (AAOD), Single Scattering Albedo (SSA) and their spectral dependence. The AAOD and Absorption Angstrom Exponent (AAE) data set is composed of daily averaged AERONET level 2 data from a total of 22 Mediterranean stations having long time series, mainly under the influence of urban-industrial aerosols and/or soil dust. This data set covers the 17 yr period 1996-2012 with most data being from 2003-2011 (approximately 89 percent of level-2 AAOD data). Since AERONET level-2 absorption products require a high aerosol load (AOD at 440 nm greater than 0.4), which is most often related to the presence of desert dust, we also consider level-1.5 SSA data, despite their higher uncertainty, and filter out data with an Angstrom exponent less than 1.0 in order to study absorption by carbonaceous aerosols. The SSA data set includes both AERONET level-2 and satellite level-3 products. Satellite-derived SSA data considered are monthly level 3 products mapped at the regional scale for the spring and summer seasons that exhibit the largest aerosol loads. The satellite SSA dataset includes the following products: (i) Multi-angle Imaging SpectroRadiometer (MISR) over 2000-2011, (ii) Ozone Monitoring Instrument (OMI) near-UV algorithm over 2004-2010, and (iii) MODerate resolution Imaging Spectroradiometer (MODIS) Deep-Blue algorithm over 2005-2011, derived only over land in dusty conditions. Sun-photometer observations show that values of AAOD at 440 nm vary between 0.024 +/- 0.01 (resp. 0.040 +/- 0.01) and 0.050 +/- 0.01 (0.055 +/- 0.01) for urban (dusty) sites. Analysis shows that the Mediterranean urban-industrial aerosols appear "moderately" absorbing with values of SSA close to approximately 0.94-0.95 +/- 0.04 (at 440 nm) in most cases except over the large cities of Rome and Athens, where aerosol appears more absorbing (SSA approximately 0.89-0.90 +/- 0.04). The aerosol Absorption Angstrom Exponent (AAE, estimated using 440 and 870 nm) is found to be larger than 1 for most sites over the Mediterranean, a manifestation of mineral dust (iron) and/or brown carbon producing the observed absorption. AERONET level-2 sun-photometer data indicate the existence of a moderate East-West gradient, with higher values over the eastern basin (AAEEast. = 1.39/AAEWest. = 1.33) due to the influence of desert dust. The North-South AAE gradient is more pronounced, especially over the western basin. Our additional analysis of AERONET level-1.5 data also shows that organic absorbing aerosols significantly affect some Mediterranean sites. These results indicate that current climate models treating organics as nonabsorbing over the Mediterranean certainly underestimate the warming effect due to carbonaceous aerosols. A~comparative analysis of the regional SSA variability has been attempted using satellite data. OMI and MODIS data show an absorbing zone (SSA approximately 0.90 at 470-500 nm) over Northeastern Africa that does not appear in the MISR retrievals. In contrast, MISR seems able to observe the East-West SSA gradient during summer, as also detected by AERONET. Also, the analysis of SSA provided by satellites indicates that the aerosol over the Mediterranean Sea appears less absorbing during spring (MAM) than summer (JJA).

satellite remote sensing observations↗

Revealing the role of redox reaction selectivity and mass transfer in current–voltage predictions for ensembles of photocatalysts

Photocatalysts are conceptually simple reaction units where nanoscale semiconductors integrated with catalysts drive a pair of redox reactions on illumination. However, the proximity of reaction sites performing cathodic and anodic reactions poses dire challenges to realize large light-to-fuel conversion efficiencies. In this study, a powerful, yet straightforward, equivalent-circuit detail-balance modeling framework is developed and applied to evaluate the performance of photocatalytic systems featuring multiple light absorbers. Specifically, low bandgap iridium-doped strontium titanate is modeled as a Z-scheme photocatalyst to achieve desirable hydrogen evolution and iron-based redox shuttle oxidation reactions. Our model has unique capabilities to simulate competing redox reactions and address mass-transfer limitations. In a significant departure from state-of-the-art circuit models, our study develops tools to perform load-line analyses by incorporating a net electrochemical load curve that includes both desired and competing redox reactions. Consequently, reaction selectivity is predicted from equivalent circuit models for photocatalytic and photoelectrochemical systems. Our investigation into ensembles comprised of multiple, semi-transparent light absorbers reveals their potential to outperform a single, optically thick light absorber, particularly when operated under mass-transfer-limited conditions. However, this outcome hinges on minimizing mass-transfer rates of select redox species to prevent undesired reactions of hydrogen oxidation and/or redox shuttle reduction. Our findings demonstrate that reaction selectivity can be achieved by tuning asymmetry in redox species mass-transfer even with perfectly symmetric electrocatalytic charge-transfer coefficients. The influences of various kinetic, mass-transfer, and thermodynamic parameters are explored to offer crucial insights for synthesis of the next-generation of photocatalysts and selective coatings, and reactor designs.

25 ENERGY STORAGE↗

Handling Qualities of a Capsule Spacecraft During Atmospheric Entry

A piloted simulation was conducted to study handling qualities for capsule spacecraft entering the Earth s atmosphere. Eight evaluation pilots, including six pilot astronauts, provided Cooper-Harper ratings, workload ratings, and qualitative comments. The simulation began after descending through the atmospheric entry interface point and continued until the drogue parachutes deployed. There were two categories of piloting tasks, both of which required bank angle control. In one task category, the pilot followed a closed-loop bank angle command computed by the backup guidance system to manage g-loads during entry. In the other task category, the pilot used intuitive rules to determine the desired bank angle independently, based on an open-loop schedule of vertical speed, Mach, and total energy specified at several range-to-target gates along the entry trajectory. Pilots were able to accurately track the bank angle guidance commands and steered the capsule toward the recovery site with essentially the same range error as the benchmark autopilot trajectory albeit with substantially higher propellant usage, and the handling qualities for this task were satisfactory. Another key result was that the complex piloting task of atmospheric entry could be performed satisfactorily, even in the presence of large dispersions, by controlling bank angle to follow a simple open-loop schedule.

Bilimoria, Karl D.↗

Internship at NASA Kennedy Space Center's Cryogenic Test laboratory

NASA's Kennedy Space Center (KSC) is known for hosting all of the United States manned rocket launches as well as many unmanned launches at low inclinations. Even though the Space Shuttle recently retired, they are continuing to support unmanned launches and modifying manned launch facilities. Before a rocket can be launched, it has to go through months of preparation, called processing. Pieces of a rocket and its payload may come in from anywhere in the nation or even the world. The facilities all around the center help integrate the rocket and prepare it for launch. As NASA prepares for the Space Launch System, a rocket designed to take astronauts beyond Low Earth Orbit throughout the solar system, technology development is crucial for enhancing launch capabilities at the KSC. The Cryogenics Test Laboratory at Kennedy Space Center greatly contributes to cryogenic research and technology development. The engineers and technicians that work there come up with new ways to efficiently store and transfer liquid cryogens. NASA has a great need for this research and technology development as it deals with cryogenic liquid hydrogen and liquid oxygen for rocket fuel, as well as long term space flight applications. Additionally, in this new era of space exploration, the Cryogenics Test Laboratory works with the commercial sector. One technology development project is the Liquid Hydrogen (LH2) Ground Operations Demonstration Unit (GODU). LH2 GODU intends to demonstrate increased efficiency in storing and transferring liquid hydrogen during processing, loading, launch and spaceflight of a spacecraft. During the Shuttle Program, only 55% of hydrogen purchased was used by the Space Shuttle Main Engines. GODU's goal is to demonstrate that this percentage can be increased to 75%. Figure 2 shows the GODU layout when I concluded my internship. The site will include a 33,000 gallon hydrogen tank (shown in cyan) with a heat exchanger inside the hydrogen tank attached to a refrigerator capable of removing 850 Watts at 20 Kelvin (shown in green). The refrigerator and most of its supporting equipment will be kept in a standard shipping container (shown in pink). Currently, GODU is in the fabrication process and some of the large components have already been purchased.

Holland, Katherine↗

Stress Promotion of the 1958 Mw∼7.8 Fairweather Fault Earthquake and Others in Southeast Alaska by Glacial Isostatic Adjustment and Inter-earthquake Stress Transfer

We assess how recent glacial isostatic adjustment (GIA) and inter-earthquake stress transfer modulated the state of stress on major faults in Southeast Alaska, and how these effects may have influenced recent large and moderate earthquakes. The Glacier Bay Icefield has lost >3,000 km3 of ice since ca. 1770, with ice thinning up to 1.5 km, and the rest of southeast Alaska has been deglaciating since ca. 1900. The resulting GIA response in the solid earth produces present-day surface uplift rates of up to ∼4 cm/yr, among the fastest on Earth. This rapid deformation occurs directly alongside and atop the Fairweather Fault, which accommodates 4–5 cm/yr of right-lateral motion through slip in frequent large earthquakes, recently including a Mw∼7.8 earthquake in 1958. We find that the 1958 earthquake nucleated very close to the location of maximum GIA-induced Coulomb stress increase on the Fairweather Fault between 1770 and 1958 (estimated at ∼0.2–0.6 MPa), on the only section of fault where GIA-induced stress changes had involved both right-lateral shearing and unclamping. The September 10, 1899 Mw∼8.1 Yakutat Bay earthquake also promoted failure on at least the northwest part of the eventual 1958 rupture. In turn, the 1899 and 1958 earthquakes and GIA promoted failure along the St. Elias compressional margin, the site of a Mw∼7.4 event in 1979. While rapid tectonic loading is very likely the main driver of earthquakes in southeast Alaska, we estimate that 23 of 30 instrumentally constrained Mw ≥ 5.0 earthquakes in this region were also promoted by post-1770 GIA.

Chris Rollins↗

First-Principles Study of Molecular Hydrogen Activation by Defects in Boron Nitride

Here, we used density functional theory simulations in combination with ab initio thermodynamics to determine the H 2 partial pressure (p H2 )-dependent energetics associated with H 2 activation and recovery at various defect sites in hexagonal boron nitride (h-BN). We found that some defects are very reactive with hydrogen, thereby definitely trapping hydrogen in defective h-BN. However, depending on hydrogen partial pressure, less reactive defect sites can be populated. Because of the lower binding capability of these sites, they would allow hydrogen to be recycled and recovered. For small defect sizes, we found that hydrogen preferentially binds to nitrogen sites by forming N–H bonds, and if no N sites are available then boron sites would be the next to bind hydrogen. Hydrogen dissociation via frustrated Lewis pair is found to be more favorable than forming only N–H bonds but only if the defect size is large enough to accommodate steric effects. For specific conditions such as T = 400 K, p H2 = 1 bar, and only considering one molecular H 2 per defect, three defects, namely, the N monovacancy, 3V(1B2N), and hexagonal 6V(3B3N) could play a role in both the activation and recycling of H 2 as they would be reacting enough to allow a favorable splitting of H 2 while not binding too strongly to allow its recovery. More broadly, a range of p H2 and hydrogen loading conditions were investigated for different types of defects and the finding suggests that p H2 could be used to fine-tune the Gibbs free energy of hydrogenation, thereby allowing several types of defects at different hydrogen loading contents to play a role in the activation/recovery process of H 2 in defective h-BN.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Microgravity mediated changes in phytoferritin accumulation in soybean root cap cells

Phytoferritin is an iron-protein complex analogous to the ferritin found in mammalian, bacteria and fungi cells. Phytoferritin molecules are large proteins, about 10.5 nm in diameter, visualised in an electron microscope as discrete, electron dense particles with iron-containing core, where several thousand atoms of iron lie within the proteinaceous shell (apoferritin). In higher plants, a plastid stroma is the site of phytoferritin storage. Phytoferritin is seen in all types of plastids. It is considered to be a mechanism used by cells to store iron in a non-toxic form. Phytoferritin-bound iron may subsequently be used to form iron-containing components. It was shown that low levels of phytoferritin are synthesised in normal green leaves, whereas chlorotic leaves do not have a measurable amount of phytoferritin and leaves of iron-loaded seedlings contain a high level of total iron, and phytoferritin well-filled by iron. Phytoferritin accumulation was observed in photosynthetic inactivity chloroplasts during senescence and disease. In this study we analised the effects of microgravity and ethylene on production of phytoferritin in the root cap columella cells of soybean seedlings.

short duration↗

Concerted Proton–Electron Transfer Minimizes Substituent Effects on Adsorbed Phthalocyanine Electrocatalysis

Molecularly modified electrodes (MMEs) are potent electrocatalysts, but few principles exist for their rational design. Electrocatalysis by soluble molecules depends strongly on substituents that tune the catalyst redox potential (E 1/2 ), but it is unclear if this parameter similarly impacts MME catalysis. Herein, we employ the hydrogen evolution reaction (HER) as a test case for comparing carbon-adsorbed cobalt phthalocyanine (CoPc/C) and cobalt hexadecafluoro-phthalocyanine (CoFPc/C). By correlating HER activity and voltammetric data to total Co surface concentration across a wide range of catalyst loadings, we find that only 5–25% of adsorbed Co sites contribute to the Co(II/I) redox wave and that this subpopulation poorly correlates with catalytic activity. Instead, in the low-loading limit, catalytic activity correlates linearly with the majority Co(II/I)-silent Co population, revealing per-site turnover frequency (TOF) values for HER. Despite a 230 mV difference in Co(II/I) redox potentials, CoPc/C and CoFPc/C display TOF values differing by less than a factor of 3 when compared over a wide potential range. Mechanistic studies point to an inner-sphere concerted proton–electron transfer step as rate-determining, suggesting that the Co–H bond dissociation free energy (BDFE) rather than the Co(II/I) E 1/2 is thermodynamically relevant. Computational studies indicate that the fluoro-substituents lead to compensatory changes in Co(II/I) E 1/2 and Co(I) basicity, leaving the Co–H BDFE largely unchanged between CoPc and CoFPc and thereby manifesting in similar catalytic rates. Furthermore, these results highlight the limited effect of E 1/2 -tuning on MME catalytic activity and motivate the development of methods to directly alter active site–substrate BDFE.

Catalysts↗