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At least 1,063 records · Page 59

Elementary Energy Transfer Pathways in Allochromatium vinosum Photosynthetic Membranes

Allochromatium vinosum (formerly Chromatium vinosum) purple bacteria are known to adapt their light-harvesting strategy during growth according to environmental factors such as temperature and average light intensity. Under low light illumination or low ambient temperature conditions, most of the LH2 complexes in the photosynthetic membranes form a B820 exciton with reduced spectral overlap with LH1. To elucidate the reason for this light and temperature adaptation of the LH2 electronic structure, we performed broadband femtosecond transient absorption spectroscopy as a function of excitation wavelength in A. vinosum membranes. A target analysis of the acquired data yielded individual rate constants for all relevant elementary energy transfer (ET) processes. We found that the ET dynamics in high-light-grown membranes was well described by a homogeneous model, with forward and backward rate constants independent of the pump wavelength. Thus, the overall B800→B850→B890→ Reaction Center ET cascade is well described by simple triexponential kinetics. In the low-light-grown membranes, we found that the elementary backward transfer rate constant from B890 to B820 was strongly reduced compared with the corresponding constant from B890 to B850 in high-light-grown samples. The ET dynamics of low-light-grown membranes was strongly dependent on the pump wavelength, clearly showing that the excitation memory is not lost throughout the exciton lifetime. The observed pump energy dependence of the forward and backward ET rate constants suggests exciton diffusion via B850→ B850 transfer steps, making the overall ET dynamics nonexponential. Our results show that disorder plays a crucial role in our understanding of low-light adaptation in A. vinosum.

59 BASIC BIOLOGICAL SCIENCES↗

Metal Halide Perovskites Demonstrate Radiation Hardness and Defect Healing in Vacuum

Herein, we subject formamidinium lead iodide films to oxygen-containing gases (flowing O 2 or free diffusion of lab atmosphere), inert gases (flowing He, Ar, or N 2 ), and vacuum. Our films are irradiated by Cu Ka X-rays and held at 75 °C while X-ray diffraction is recorded. Under all gas conditions, we observe a reproducible 1.1 ± 0.5 A 3 perovskite lattice contraction from an initial unit cell volume of 256.5 ± 0.8 A 3 concurrent with continuous perovskite loss and lead iodide growth. Oxygen-containing gases increase the reaction rates without materially altering perovskite structural changes. Under the same temperature and irradiation conditions in vacuo, a self-healing reaction is observed, exhibited by a reproducible (0.9 ± 0.3 A 3 ) lattice expansion and stabilization of the perovskite. Furthermore, interactions between the perovskite, defects, and minority phases are simulated by generalized gradient approximation Perdew-Burke-Ernzerhof (GGA-PBE) density functional theory. Lattice contraction indicates an increase in the concentration of Schottky defects-pairs of formamidinium and iodine vacancies. Under irradiation in every atmospheric condition, a solid solution of Schottky defects with a concentration of several percent diffuses and precipitates forming lead iodide and consuming the defects. In the presence of ionized gases, this framework is modified to include the continual loss of formamidinium and iodine ions from the perovskite forming Schottky defects.

14 SOLAR ENERGY↗

Principles of proteome allocation are revealed using proteomic data and genome-scale models

Integrating omics data to refine or make context-specific models is an active field of constraint-based modeling. Proteomics now cover over 95% of the Escherichia coli proteome by mass. Genome-scale models of Metabolism and macromolecular Expression (ME) compute proteome allocation linked to metabolism and fitness. Using proteomics data, we formulated allocation constraints for key proteome sectors in the ME model. The resulting calibrated model effectively computed the “generalist” (wild-type) E. coli proteome and phenotype across diverse growth environments. Across 15 growth conditions, prediction errors for growth rate and metabolic fluxes were 69% and 14% lower, respectively. The sector-constrained ME model thus represents a generalist ME model reflecting both growth rate maximization and “hedging” against uncertain environments and stresses, as indicated by significant enrichment of these sectors for the general stress response sigma factor σS. Finally, the sector constraints represent a general formalism for integrating omics data from any experimental condition into constraint-based ME models. The constraints can be fine-grained (individual proteins) or coarse-grained (functionally-related protein groups) as demonstrated here. Furthermore, this flexible formalism provides an accessible approach for narrowing the gap between the complexity captured by omics data and governing principles of proteome allocation described by systems-level models.

59 BASIC BIOLOGICAL SCIENCES↗

The large deviation principle and steady-state fluctuation theorem for the entropy production rate of a stochastic process in magnetic fields

Fluctuation theorem is one of the major achievements in the field of nonequilibrium statistical mechanics during the past two decades. There exist very few results for steady-state fluctuation theorem of sample entropy production rate in terms of large deviation principle for diffusion processes due to the technical difficulties. Here we give a proof for the steady-state fluctuation theorem of a diffusion process in magnetic fields, with explicit expressions of the free energy function and rate function. The proof is based on the Karhunen-Loève expansion of complex-valued Ornstein-Uhlenbeck process.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

The effect of heat treatment and test parameters on the aqueous stress corrosion cracking of D6AC steel

The crack growth behavior of D6AC steel as a function of stress intensity, stress and corrosion history and test technique, under sustained load in natural seawater, 3.3 percent NaCl solution, distilled water, and high humidity air was investigated. Reported investigations of D6AC were considered with emphasis on thermal treatment, specimen configuration, fracture toughness, crack-growth rates, initiation period, threshold, and the extension of corrosion fatigue data to sustained load conditions. Stress history effects were found to be most important in that they controlled incubation period, initial crack growth rates, and apparent threshold.

Gilbreath, W. P.↗

An economic systems analysis of land mobile radio telephone services

This paper deals with the economic interaction of the terrestrial and satellite land-mobile radio service systems. The cellular, trunked and satellite land-mobile systems are described. Parametric equations are formulated to allow examination of necessary user thresholds and growth rates as functions of system costs. Conversely, first order allowable systems costs are found as a function of user thresholds and growth rates. Transitions between satellite and terrestrial service systems are examined. User growth rate density (user/year/km squared) is shown to be a key parameter in the analysis of systems compatibility. The concept of system design matching the price demand curves is introduced and examples are given. The role of satellite systems is critically examined and the economic conditions necessary for the introduction of satellite service are identified.

Leroy, B. E.↗

Microwave scattering from wind- and rain-roughened seas

Microwave scattering from wind- and rain-roughened seas is studied under the assumption that, for light wind and light rain, the processes contributing to the scatterometer signal are independent. It is argued that calibrations from exclusively rain and exclusively wind conditions are all that is needed to predict scatterometer cross section for combined conditions. It is demonstrated that scatterometer response to a rain-roughened water surface is linear, but the slope of the relationship is sensitive to drop-size distribution. It is concluded that first-order wind and rain can be regarded as independent processes. Average cross section varies linearly with rainfall rate, but the slope of the relationship is a function of drop-size distribution. For combined light rain plus light wind, sigma-c is found to be well predicted by the addition of wind and rain models.

Bliven, Larry F.↗

Laboratory Studies of the Optical Properties and Condensation Processes of Cosmic Dust Grains

A laboratory facility for conducting a variety of experiments on single isolated dust particles of astrophysical interest levitated in an electrodynamics balance has been developed at NASA/Marshall Space Flight Center. The objective of the research is to employ this experimental technique for studies of the physical and optical properties of individual cosmic dust grains of 0.1-100 micron size in controlled pressure/temperatures environments simulating astrophysical conditions. The physical and optical properties of the analogs of interstellar and interplanetary dust grains of known composition and size distribution will be investigated by this facility. In particular, we will carry out three classes of experiments to study the micro-physics of cosmic dust grains. (1) Charge characteristics of micron size single dust grains to determine the photoelectric efficiencies, yields, and equilibrium potentials when exposed to UV radiation. (2) Infrared optical properties of dust particles (extinction coefficients and scattering phase functions) in the 1-30 micron region using infrared diode lasers and measuring the scattered radiation. (3) Condensation experiments to investigate the condensation of volatile gases on colder nucleated particles in dense interstellar clouds and lower planetary atmospheres. The condensation experiments will involve levitated nucleus dust grains of known composition and initial mass (or m/q ratio), cooled to a temperature and pressure (or scaled pressure) simulating the astrophysical conditions, and injection of a volatile gas at a higher temperature from a controlled port. The increase in the mass due to condensation on the particle will be monitored as a function of the dust particle temperature and the partial pressure of the injected volatile gas. The measured data will permit determination of the sticking coefficients of volatile gases and growth rates of dust particles of astrophysical interest. Some preliminary results based on measurements of photoelectric emission and radiation pressure on single isolated 0.2 to 6.6 micron size silica particles exposed to UV radiation at 120-200 nm and green laser light at 532 nm are presented.

Abbas, M. M.↗

Activation of the ATP-ubiquitin-proteasome pathway in skeletal muscle of cachectic rats bearing a hepatoma

Rats implanted with Yoshida ascites hepatoma (YAH) show a rapid and selective loss of muscle protein due mainly to a marked increase (63-95%) in the rate of protein degradation (compared with rates in muscles of pair-fed controls). To define which proteolytic pathways contribute to this increase, epitrochlearis muscles from YAH-bearing and control rats were incubated under conditions that modify different proteolytic systems. Overall proteolysis in either group of rats was not affected by removal of Ca2+ or by blocking the Ca(2+)-dependent proteolytic system. Inhibition of lysosomal function with methylamine reduced proteolysis (-12%) in muscles from YAH-bearing rats, but not in muscles of pair-fed rats. When ATP production was also inhibited, the remaining accelerated proteolysis in muscles of tumor-bearing rats fell to control levels. Muscles of YAH-bearing rats showed increased levels of ubiquitin-conjugated proteins and a 27-kDa proteasome subunit in Western blot analysis. Levels of mRNA encoding components of proteolytic systems were quantitated using Northern hybridization analysis. Although their total RNA content decreased 20-38%, pale muscles of YAH-bearing rats showed increased levels of ubiquitin mRNA (590-880%) and mRNA for multiple subunits of the proteasome (100-215%). Liver, kidney, heart, and brain showed no weight loss and no change in these mRNA species. Muscles of YAH-bearing rats also showed small increases (30-40%) in mRNA for cathepsins B and D, but not for calpain I or heat shock protein 70. Our findings suggest that accelerated muscle proteolysis and muscle wasting in tumor-bearing rats result primarily from activation of the ATP-dependent pathway involving ubiquitin and the proteasome.

NASA Discipline Musculoskeletal↗

NASA Occupant Protection Standards Development

Current National Aeronautics and Space Administration (NASA) occupant protection standards and requirements are based on extrapolations of biodynamic models, which were based on human tests performed under pre-Space Shuttle human flight programs where the occupants were in different suit and seat configurations than is expected for the Multi Purpose Crew Vehicle (MPCV) and Commercial Crew programs. As a result, there is limited statistical validity to the occupant protection standards. Furthermore, the current standards and requirements have not been validated in relevant spaceflight suit, seat configurations or loading conditions. The objectives of this study were to develop new standards and requirements for occupant protection and rigorously validate these new standards with sub-injurious human testing. To accomplish these objectives we began by determining which critical injuries NASA would like to protect for. We then defined the anthropomorphic test device (ATD) and the associated injury metrics of interest. Finally, we conducted a literature review of available data for the Test Device for Human Occupant Restraint New Technology (THOR-NT) ATD to determine injury assessment reference values (IARV) to serve as a baseline for further development. To better understand NASA s environment, we propose conducting sub-injurious human testing in spaceflight seat and suit configurations with spaceflight dynamic loads, with a sufficiently high number of subjects to validate no injury during nominal landing loads. In addition to validate nominal loads, the THOR-NT ATD will be tested in the same conditions as the human volunteers, allowing correlation between human and ATD responses covering the Orion nominal landing environment and commercial vehicle expected nominal environments. All testing will be conducted without the suit and with the suit to ascertain the contribution of the suit to human and ATD responses. In addition to the testing campaign proposed, additional data analysis is proposed to mine existing human injury and response data from other sources, including military volunteer testing, automotive Crash Injury Research Engineering Network (CIREN), and IndyCar impact and injury data. These data sources can allow a better extrapolation of the ATD responses to off-nominal conditions above the nominal range that can safely be tested. These elements will be used to develop injury risk functions for each of the injury metrics measured from the ATD. These risk functions would serve as the basis for the NASA standards. Finally, we propose defining standard test methodology for evaluating future spacecraft designs against the IARVs, including developing a star-rating system to allow crew safety comparisons between vehicles.

Somers, Jeffrey T.↗

Real-Time Modeling of Thermal Interactions in Cryogenic Ball Bearings

Based on the integration of classical differential equations of motion of bearing elements, a real-time dynamic simulation of ball bearing performance is coupled with simultaneous modeling of thermal interactions between the bearing elements. The transient heat generations are time averaged over a significantly larger time step before they are used to compute the changes in bearing temperature fields. Such an averaging algorithm eliminates the numerical difficulties associated with simultaneous integration of mechanical thermal differential equations with vastly different time scales. Under stable operation, the step change in temperatures at each thermal time step converges to a steady-state solution. Following is a list of accomplishments in the present investigation: (1) A real-time dynamic performance of both 440C and hybrid ball bearings in a LOX environment is modeled in both transient and steady-state time domains, as the inner race accelerates to a prescribed operating speed. (2) The frictional interactions at the ball to race contacts are modeled by experimentally measured traction coefficients as a function of slide-to-roll ratios. (3) Bearing heat generation, as defined by the heat transferred to circulating LOX, is validated against experimental values determined by measured LOX temperatures under prescribed pressures and flow rates. The predicted heat generation is in good agreement with the experimental values. (4) The steady-state solutions are shown to be independent of initial conditions. This establishes convergence of the numerical integration of a differential equation of motion of the bearing elements. (5) Churning and drag losses in the circulating LOX constitutes the majority of bearing heat generation under the experimental test conditions. (6) The heat dissipated in frictional interactions in hybrid bearings is significantly lower in hybrid bearings in comparison to that simulated in all-steel bearings, while the churning and drag losses are relatively unchanged.

Gupta, P. K.↗

Iodine Adsorption by Ag-Aerogel under Prototypical Vessel Off-Gas Conditions

U.S. regulations will require the removal of 129 I from the off-gas streams of any used nuclear fuel (UNF) reprocessing plant prior to discharge of the off-gas to the environment. The required plant decontamination factor for iodine will vary based on fuel burnup, cooling time, and other factors but is very likely to be >1000 and could be as high as 8000. Multiple off-gas streams within a UNF reprocessing plant combine prior to environmental release, and each of these streams contains some amount of iodine. To achieve the decontamination factors (DFs) that are likely to be required by regulations, iodine removal from the vessel off-gas will be necessary. The vessel off-gas contains iodine at very dilute concentrations (ppb levels), and will also contain water vapor. Iodine species present are likely to include both elemental and organic iodides. There will also be solvent vapors and volatile radiolysis products. The United States has considered the use of silver-based sorbents for removal of iodine from UNF off-gas streams, but little is known about the behavior of those sorbents at very dilute iodine concentrations. The purpose of this study was to expose silver-functionalized silica aerogel (AgAerogel) to a prototypical vessel off-gas stream containing 40 ppb methyl iodide to obtain information about organic iodine capture by silver-sorbents at very low iodine concentrations. The design of this extended duration testing was such that information about the rate of adsorption, the penetration of the iodine species, and the overall system DF could be obtained. Results show that CH 3 I penetrates into a AgAerogel sorbent bed to a depth of 3.9 cm under prototypical vessel off-gas conditions. An iodine loading of 22 mg I/g AgAerogel was observed in the first 0.3 cm of the bed. Of the iodine delivered to the system, 48% could not be accounted for, and future efforts will investigate this concern. Direct calculation of the decontamination factor is not possible, as no iodine was observed to break through the sorbent beds. Continued studies on the adsorption of iodine from prototypical vessel off-gas streams by silver-based sorbents will attempt to resolve some of the questions raised here, both regarding mass balance and the effect of aging on iodine adsorption by AgAerogel from a dilute gas stream. Additionally, the adsorption of different iodine species, such as I 2 and C 12 H 25 I will be studied. Other variables that merit examination are the gas velocity of the test and the dependence of the observed results on the inlet iodine concentration. Finally, longer duration testing should be considered in an effort to determine the mass transfer zone associated with iodine adsorption by AgAerogel under prototypical vessel off-gas conditions. The estimation of mass transfer zone is required for any future industrial implementation.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Gravity, Body Mass and Composition, and Metabolic Rate

Metabolic rate and body composition as a function of sex and age were defined in 5 species of common laboratory mammals, the mouse, hamster, rat, guinea pig and rabbit. Oxygen consumption and carbon dioxide production rates were measured individually in 6 male and 6 female animals for each of 8 age cohorts ranging from 1 month to 2 years, and for each of the species. From the results it is evident that among these small mammals there is no indication of scaling of muscularity to body size, despite the 100-fold difference in body mass represented by the skeletal musculature seems to reach a pronounced peak value at age 2 to 3 months and then declines, the fraction of the fat-free body represented by other body components in older animals must increase complementarily. Under normal gravity conditions muscularity in small laboratory mammals displays large, systematic variation as a function both of species and age. This variation must be considered when such animals are subjects of experiments to study the effects of altered gravitational loading on the skeletal musculature of the mammal.

Nello Pace↗

Xylem embolism refilling and resilience against drought-induced mortality in woody plants: processes and trade-offs

Understanding which species are able to recover from drought, under what conditions, and the mechanistic processes involved, will facilitate predictions of plant mortality in response to global change. In response to drought, some species die because of embolism-induced hydraulic failure, whilst others are able to avoid mortality and recover, following rehydration. Several tree species have evolved strategies to avoid embolism, whereas others tolerate high embolism rates but can recover their hydraulic functioning upon drought relief. Here, we focus on structures and processes that might allow some plants to recover from drought stress via embolism reversal. We provide insights into how embolism repair may have evolved, anatomical and physiological features that facilitate this process, and describe possible trade-offs and related costs. Recent controversies on methods used for estimating embolism formation/repair are also discussed, providing some methodological suggestions. Although controversial, embolism repair processes are apparently based on the activity of phloem and ray/axial parenchyma. The mechanism is energetically demanding, and the costs to plants include metabolism and transport of soluble sugars, water and inorganic ions. We propose that embolism repair should be considered as a possible component of a ‘hydraulic efficiency-safety’ spectrum. We also advance a framework for vegetation models, describing how vulnerability curves may change in hydrodynamic model formulations for plants that recover from embolism.

54 ENVIRONMENTAL SCIENCES↗

Microbe-iron interactions control lignin decomposition in soil

Lignin decomposition is critically linked to terrestrial carbon (C) cycle due to the enormous C mass of lignin and its importance in controlling overall rates of litter decomposition. Interactions between lignin and iron (Fe) minerals have been increasingly recognized as key mediators of lignin decomposition in experimental studies. However, we still lack a quantitative understanding of how Fe minerals interact with microbes to control lignin decomposition. Here, we leveraged experimental results from an incubation of Fe-rich soil, in which lignin decomposition rates were measured at aerobic conditions after four levels of pre-treated O2 availability, to examine microbe-Fe (MiFe) interactions in lignin decomposition with a MiFe model. We quantified how Fe redox cycling interacted with microbial activities to control lignin decomposition via data-model integration. Our results showed that the MiFe model with time-dependent growth and mortality functions better represented CO2 release from lignin decomposition (R2 ranging from 0.96 to 0.97) than models assuming either first-order or Michaelis-Menten kinetics. Reduction of Fe(III) to Fe(II) after pre-treatments with lower O2 availability stimu-lated the Fenton reaction to break down macro-molecular lignin into small molecules available to microbes. The small molecules of lignin and necromass bounded with oxidized Fe and were protected from decomposition. After 1-year incubation, the model implied that most of C stabilized with Fe minerals was derived from small molecular lignin C. Our quantitative analysis of microbe-Fe interactions sheds new light on lignin decomposition and preservation and helps improve model prediction of soil C persistence under global change.

Liao, Cuijuan↗

Effects of root litter traits on soil organic matter dynamics depend on decay stage and root branching order

Decaying roots contribute disproportionately to soil organic carbon (SOC) stocks in many ecosystems, yet few studies have examined the afterlife effects of root trait variability on the formation, stability and mineralization of SOC. In order to assess how root functional class (absorptive vs. transport) and mycorrhizal association (ectomycorrhizal vs. arbuscular mycorrhizal fungi) affect both formation and loss of SOC, we decayed lower-order absorptive (orders 1–2) and higher-order transport (orders 3–4) roots from six arbuscular mycorrhizal (AM) and six ectomycorrhizal (EcM) associated hardwood tree species in an isotopically distinct soil under laboratory conditions. We found that root litter effects on SOC differed significantly among root functional classes and mycorrhizal types. AM absorptive and transport roots (high in nitrogen and soluble compounds) contributed more to the formation of new mineral-associated organic carbon (MAOC), but also contributed to higher mineralization of native SOC (via priming effects). Moreover, absorptive AM roots formed MAOC gradually and rates saturated, whereas ECM roots formed MAOC more quickly, despite slower decay (via greater formation efficiency). Altogether, these findings demonstrate how different combinations of root traits might contribute to soil C balance, and that failure to account for the chemical and morphological heterogeneity of roots, as well their interactions with microbes over time, may lead to incorrect projections of SOC stocks and turnover.

59 BASIC BIOLOGICAL SCIENCES↗

Tracking Local pH Dynamics during Water Electrolysis via In-Line Continuous Flow Raman Spectroscopy

The performance of electrochemical devices, which play a critical role in decarbonization efforts, is often governed by proton-coupled electron transfer reactions at the electrode–electrolyte interface. These reactions are highly sensitive to the complex and dynamic microenvironment present at the electrode surface. However, characterizing this environment─particularly monitoring interfacial pH and its evolution under reaction conditions─remains challenging, necessitating the development of advanced analytical tools. Here, in this study, we introduce in-line continuous flow Raman spectroscopy (CFRS) as a spectroelectrochemical platform for quantifying interfacial pH swings generated during water-splitting. By monitoring phosphate ion speciation and controlling the hydrodynamics with a flow cell, we measure pH swings as a function of current density, flow rate, and distance from the electrode. Comparison with theoretical models reveals the impact of bulk pH, boundary layer thickness, and bubble dynamics at high current densities. Collectively, these findings establish CFRS as a platform for quantitatively investigating pH dynamics, offering critical insights for advancing electrochemical energy conversion technologies.

Marquez, Raul A. [Univ. of Texas, Austin, TX (Unit↗

Deconvolution of mass gain and mass loss mechanisms during carbothermic reduction to nitridization reactions in the zirconium system through thermogravimetric analysis

A novel approach was used to understand the effects of processing conditions on the conversion of zirconium dioxide to zirconium carbonitride using a carbothermic reduction to nitridation process. The conversion process was studied through the use of thermogravimetric analysis, X-ray diffraction (XRD), and scanning electron microscopy, resulting in an understanding of the nature and progression of conversion. The rate of mass change as measured through thermogravimetric analysis was plotted as a function of reaction progression, guiding the use of XRD in further understanding the conversion process. This approach was then used to characterize the important effect of initial compact morphology on conversion. Coupled analysis techniques allow for advancement of a number of hypotheses regarding the rate-limiting factors along the various steps in the carbothermic reduction to nitridation process. These results demonstrate the value of the proposed approach to aid in deconstruction of competing reaction mechanisms as necessary to understand the system studied here or other systems of scientific and industrial relevance.

36 MATERIALS SCIENCE↗