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Effect of Anesthesia Gases on the Oxygen Reduction Reaction
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Water-Soluble 3D Covalent Organic Framework that Displays an Enhanced Enrichment Effect of Photosensitizers and Catalysts for the Reduction of Protons to H 2
Covalent organic frameworks (COFs) are emerging porous polymers that have 2D or 3D long-range ordering. Currently available COFs are typically insoluble or decompose upon dissolution, which remarkably restricts their practical implementations. For 3D COFs, the achievement of noninterpenetration, which maximizes their porosity-derived applications, also remains a challenge synthetically. Here, we report the synthesis of the first highly water-soluble 3D COF (sCOF-101) from irreversible polymerization of a preorganized supramolecular organic framework through cucurbit[8]uril (CB[8])-controlled [2 + 2] photodimerization. Synchrotron X-ray scattering and diffraction analyses confirm that sCOF-101 exhibits porosity periodicity, with a channel diameter of 2.3 nm, in both water and the solid state and retains the periodicity under both strongly acidic and basic conditions. As an ordered 3D polymer, sCOF-101 can enrich [Ru(bpy) 3 ] 2+ photosensitizers and redox-active polyoxometalates in water, which leads to remarkable increase of their photocatalytic activity for proton reduction to produce H2.
Effects of Surface Roughness on the Electrochemical Reduction of CO 2 over Cu
We have investigated the role of surface roughening on the CO 2 reduction reaction (CO 2 RR) over Cu. The activity and product selectivity of Cu surfaces roughened by plasma pretreatment in Ar, O 2 , or N 2 were compared with that of electrochemically polished Cu samples. Differences in total and product current densities, the ratio of current densities for HER (the hydrogen evolution reaction) to CO 2 RR, and the ratio of current densities for C 2+ to C 1 products depend on the electrochemically active surface and are nearly independent of plasma composition. Theoretical analysis of an electropolished and roughened Cu surface reveals a higher fraction of undercoordinated Cu sites on the roughened surface, sites that bind CO preferentially. Roughened surfaces also contain square sites similar to those on a Cu(100) surface but with neighboring step sites, which adsorb OC-COH, a precursor to C 2+ products. Here, these findings explain the increases in the formation of oxygenates and hydrocarbons relative to CO and the ratio of oxygenates to hydrocarbons observed with increasing surface roughness.
Oriented Electrostatic Effects on O 2 and CO 2 Reduction by a Polycationic Iron Porphyrin
Next-generation energy technologies require improved methods for rapid and efficient chemical-to-electrical energy transformations. One new approach has been to include atomically-positioned, electrostatic motifs in molecular catalysts to stabilize high-energy, charged intermediates. For example, an iron porphyrin bearing four cationic, ortho-N,N,N-trimethylanilinium groups (o-[N(CH 3 ) 3 ] + ) has recently been used to catalyze the complex, multi-step O 2 and CO 2 reduction reactions (ORR and CO 2 RR) with fast rates and at low overpotentials. The success of this catalyst is attributed, at least in part, to specific charge-charge interactions between the atomically-positioned o-[N(CH 3 ) 3 ] + groups and the bound substrate. However, by nature of the mono-ortho substitution pattern, there are four possible atropisomers of this metalloporphyrin and thus four unique electrostatic environments. This work reports that each of the four individual atropisomers catalyzes both the ORR and CO 2 RR with fast rates and low overpotentials. The maximum turnover frequencies (TOF max ) vary among the atropisomers, by a factor of 60 for the ORR and a factor of 5 for CO 2 RR. For the ORR, the αβαβ isomer is the fastest and has the highest overpotential, while for the CO 2 RR, the order is reversed and the αααα isomer is the fastest and has the highest overpotential. The role of charge-positioning is complex and can affect more than a single step such as CO 2 binding. These data offer a first-of-a-kind perspective on atomically positioned charge and highlight the significance of high charge density, rather than orientation, on the thermodynamics and kinetics of multistep molecular electrochemical transformations.
Tuning the Type 1 Reduction Potential of Multicopper Oxidases: Uncoupling the Effects of Electrostatics and H-Bonding to Histidine Ligands
In multicopper oxidases (MCOs), the type 1 (T1) Cu accepts electrons from the substrate and transfers these to the trinuclear Cu cluster (TNC) where O 2 is reduced to H 2 O. The T1 potential in MCOs varies from 340 to 780 mV, a range not explained by the existing literature. Here, this study focused on the ~350 mV difference in potential of the T1 center in Fet3p and Trametes versicolor laccase (TvL) that have the same 2His1Cys ligand set. A range of spectroscopies performed on the oxidized and reduced T1 sites in these MCOs shows that they have equivalent geometric and electronic structures. However, the two His ligands of the T1 Cu in Fet3p are H-bonded to carboxylate residues, while in TvL they are H-bonded to noncharged groups. Electron spin echo envelope modulation spectroscopy shows that there are significant differences in the second-sphere H-bonding interactions in the two T1 centers. Redox titrations on type 2-depleted derivatives of Fet3p and its D409A and E185A variants reveal that the two carboxylates (D409 and E185) lower the T1 potential by 110 and 255–285 mV, respectively. Density functional theory calculations uncouple the effects of the charge of the carboxylates and their difference in H-bonding interactions with the His ligands on the T1 potential, indicating 90–150 mV for anionic charge and ~100 mV for a strong H-bond. Finally, this study provides an explanation for the generally low potentials of metallooxidases relative to the wide range of potentials of the organic oxidases in terms of different oxidized states of their TNCs involved in catalytic turnover.
Threefold reduction of modeled uncertainty in direct radiative effects over biomass burning regions by constraining absorbing aerosols
Absorbing aerosols emitted from biomass burning (BB) greatly affect the radiation balance, cloudiness, and circulation over tropical regions. Assessments of these impacts rely heavily on the modeled aerosol absorption from poorly constrained global models and thus exhibit large uncertainties. By combining the AeroCom model ensemble with satellite and in situ observations, we provide constraints on the aerosol absorption optical depth (AAOD) over the Amazon and Africa. Our approach enables identification of error contributions from emission, lifetime, and MAC (mass absorption coefficient) per model, with MAC and emission dominating the AAOD errors over Amazon and Africa, respectively. In addition to primary emissions, our analysis suggests substantial formation of secondary organic aerosols over the Amazon but not over Africa. Furthermore, we find that differences in direct aerosol radiative effects between models decrease by threefold over the BB source and outflow regions after correcting the identified errors. This highlights the potential to greatly reduce the uncertainty in the most uncertain radiative forcing agent.
Effect of at-the-source noise reduction on performance and weights of a tilt-rotor aircraft
Reduction of far-field acoustic signature through modification of basic design parameters (tip speed, number of blades, disc loading and rotor blade area) was examined, using a tilt-rotor flight research aircraft as a baseline configuration. Of those design parameters, tip speed appeared as the most important. Next, preliminary design of two aircraft was performed, postulating the following reduction of noise level from that of the baseline machine, at 500 feet from the spot of OGE hover. In one aircraft, the PNL was lowered by 10 PNdB and in the other, OASPL decreased by 10 dB. The resulting weight and performance penalties were examined. Then, PNL and EPNL aspects of terminal operation were compared for the baseline and quieter aircraft.
Grain size reduction in granular flows of spheres - The effects of critical impact energy
Methods employed to derive recent kinetic theories for rapid noncomminuting granular flows are extended to homogeneous flows in which a fraction of the repeated collisions produce tiny fractures on the particles' peripheries and gradually reduce their effective diameters. The theory consists of balance equations for mass, momentum, and energy, as well as constitutive relations for the presence tensor and collisional rates of mass and energy lost. The work of Richman and Chou (1989) is improved by incorporating into the constitutive theory the critical impact energy below which no mass loss occurs in a binary collision. The theory is applied to granular shear flows and, for fixed shear rates, predicts the time variations of the solid fraction granular temperature, and induced stresses, as well as their extreme sensitivities to small changes in the critical impact energy.
Reduction of Non-uniform Beam Filling Effects by Vertical Decorrelation: Theory and Simulations
Algorithms for estimating precipitation rates from spaceborne radar observations of apparent radar reflectivity depend on attenuation correction procedures. The algorithm suite for the Ku-band precipitation radar aboard the Tropical Rainfall Measuring Mission satellite is one such example. The well-known problem of nonuniform beam filling is a source of error in the estimates, especially in regions where intense deep convection occurs. The error is caused by unresolved horizontal variability in precipitation characteristics such as specific attenuation, rain rate, and effective reflectivity factor. This paper proposes the use of vertical decorrelation for correcting the nonuniform beam filling error developed under the assumption of a perfect vertical correlation. Empirical tests conducted using ground-based radar observations in the current simulation study show that decorrelation effects are evident in tilted convective cells. However, the problem of obtaining reasonable estimates of a governing parameter from the satellite data remains unresolved.
Performance study of charcoal-based radon reduction systems for ultraclean rare event detectors
The continuous emanation of radon due to trace amounts of uranium and thorium in detector materials introduces radon to the active detection volume of low-background rare event search detectors. 222 Rn produces a particularly problematic background in the physics region of interest by the "naked" beta decay of its 214 Pb daughter nucleus. While charcoal-based adsorption traps are expected to be effective for radon reduction in auxiliary circulation loops that service the warm components of current ton-scale detectors at slow flow rates (0.5-2 SLPM), radon reduction in the entire circulation loop at high flow rates $\mathcal{O}$(100s SLPM) is necessary to reach high sensitivity in future generation experiments. In this article we explore radon dynamics with a charcoal-based radon reduction system in the main circulation loop of time projection chamber detectors. Here, we find that even for perfect radon traps, circulation speeds of 2,000 SLPM are needed to reduce radon concentration in a 10 ton detector by 90%. This is faster by a factor of four than the highest circulation speeds currently achieved in dark matter detectors. We further find that the effectiveness of vacuum swing adsorption systems, which have been employed very successfully at reducing atmospheric radon levels in clean-rooms, is limited by the intrinsic radon activity of the charcoal adsorbent in ultra-low radon environments. Adsorbents with significantly lower intrinsic radon activity than in currently available activated charcoals would be necessary to build effective vacuum swing adsorption systems operated at room temperature for rare event search experiments. If such VSA systems are cooled to about 190 K, this requirement relaxes drastically.
Impacts of corn intercropping with soybean, peanut and millet through different planting patterns on population dynamics and community diversity of insects under fertilizer reduction
Corn is one of the key grain crops in China and the excessive use of chemical fertilizers and pesticides seriously damages the ecological environment in fields. To explore a more scientific and reasonable way to plant corn and simultaneously reduce the overuse of chemical fertilizers and pesticides, the impact of corn intercropping with soybean, peanut, and millet, respectively, through five planting patterns, including three intercropping patterns (2 corn rows to 2, 3 and 4 rows of soybean/peanut or 2, 4 and 6 millet rows, respectively) and two monoculture patterns of corn and soybean, peanut or millet under normal (600 kg/ha) and reduced (375 kg/ha) levels of NPK (N:P 2 O 5 :K 2 O = 15:15:15) fertilization on the population abundance and community diversity of insects, leaf nutrients, and induced plant hormones jasmonic acid (JA) and salicylic acid (SA) was studied in 2018 and 2019. The results showed that the insect community indexes of the species number ( S ), the diversity index ( H ), and the uniformity index ( E ) generally increased under intercropping and were significantly higher than those under corn monoculture. The prevalence of Asian corn borer ( Ostrinia furnacalis ) on the intercropping corn plants decreased by based on the average of seven surveys per year for each treatment 2.9 to 17 heads per 30 plants compared with that on the monoculture corn plants. The number of natural enemy insect species on corn plants under intercropping was significantly higher than that under corn monoculture. That is, intercropping may decrease the population of Asian corn borers by increasing S , H , E , and natural enemy insect species (NEI). Moreover, intercropping type and fertilizer level significantly affected corn leaf nutrient contents. Compared with the normal fertilizer level, fertilizer reduction significantly reduced the foliar contents of amino acids, soluble protein, and soluble sugar in corn plants. In addition, corn–soybean and corn–peanut intercropping significantly increased the three nutrient contents in corn leaves compared with corn monoculture. In terms of corn nutrients, intercropping could compensate for the effects of fertilizer reduction. The foliar content of JA in corn–soybean intercropping was significantly higher than in corn monoculture. Under corn–soybean and corn–peanut intercropping, SA was significantly lower than under corn monoculture. Overall, intercropping, not fertilizer reduction, can significantly increase insect community diversity while reducing the population abundances of the key insect pest species on corn plants. Intercropping reduced the SA content, increased amino acids and thus reduced the susceptibility of corn to the pest insects.
Generation of Performance Model for the Aeolian Wind Tunnel (AWT) Rotor at Reduced Pressure
The NASA Jet Propulsion Laboratory (JPL) designed the Mars Helicopter (MH) in collaboration with AeroVironment Inc., NASA Ames Research Center, and NASA Langley Research Center to explore the possibility of a vertical takeoff and landing (VTOL) Unmanned Aerial Vehicle (UAV) for flight on Mars. A 40-inch-diameter Aeolian Wind Tunnel (AWT) rotor, roughly approximating the proposed MH design by JPL, was tested in forward flight at Mars atmospheric pressure at the NASA Ames Planetary Aeolian Laboratory (PAL) in support of MH research efforts. This report describes the generation of the rotor model used to correlate with that experimental effort as reported by Ament and Koning. The 40-inch-diameter rotor was 3D-scanned and transformed into an airfoil deck. The scanned rotor airfoil sections are analyzed using C81 Generator (C81Gen) to generate the sectional aerodynamic coefficients for comprehensive analyses. A mid-fidelity computational fluid dynamics (CFD) simulation using Rotorcraft CFD (RotCFD) is pursued to efficiently estimate rotor hover and forward flight performance. Simulations at two pressures, 7 mbar (approximate Martian atmospheric pressure) and 1018 mbar (1 atmosphere), are performed to gain an understanding of the performance differences and Reynolds number effects observed. Experimental 1-atmosphere thrust for single- and dual-rotor isolated hover cases correlate well with the modeled rotor. Performance results at reduced pressure (7 mbar) show a drastic decrease in lift for equivalent RPMs tested at 1 atmosphere. Although this is primarily due to pressure reduction, Reynolds number effects also contribute to this decrease, as airfoil lift and drag coefficients are affected when compared with 1-atmosphere results. Further, simulated rotor power coefficient shows drastic increases at reduced pressures, attributed to laminar boundary layer separation, as described in Koning et al. for the MH rotor analysis. PAL experimental Martian Surface Wind Tunnel (MARSWIT) results are presented in the paper by Ament and Koning. The very low Reynolds number range is currently not well understood and presents various challenges for both experimentation and simulation.
Nitrogen Dioxide Trend over the United States: the View from the Ground, the View from Space
Emissions of nitrogen oxides (NOx) are decreasing over the US due to environmental policies and technological change. We use observations of tropospheric nitrogen dioxide (NO2) columns from the Ozone Monitoring Instrument (OMI) satellite instrument and surface NO2 in-situ measurements from the air quality system (AQS) to quantify the trends, and to establish the relationship between the trends in tropospheric column and surface concentration. Both observations show substantial downward trends from 2005 to 2013, with an average reduction of 35 percent according to OMI and 38 percent according to AQS. The annual reduction rates are largest in 2005-2009: -6.2 percent per year and -7 percent per year observed by OMI and AQS, respectively. We examine various factors affecting the estimated trend in OMI NO2 columns and in-situ NO2 observations. An improved understanding of trend offers valuable insights about effectiveness of emission reduction regulations on state and federal level.
The design and development of an automatic control system for the in-duct cancellation of spinning modes of sound
The reduction is discussed of the discrete tones generated by jet engines which is essential for jet aircraft to meet present and proposed noise standards. The discrete tones generated by the blades and vanes propagate in the inlet and exhaust duct in the form of spiraling acoustic waves, or spinning modes. The reduction of these spinning modes by the cancellation effect of the combination of two acoustic fields was investigated. The spinning mode synthesizer provided the means for effective study of this noise reduction scheme. Two sets of electrical-acoustical transducers located in an equally-spaced circular array simultaneously generate a specified spinning mode and the cancelling mode. Analysis of the wave equation for the synthesizer established the optimum cancelling array acoustic parameters for maximum sound pressure level reduction. The parameter dependence of the frequency ranges of propagation of single, specified circumferential modes generated by a single array, and of effective cancellation of the modes generated by two arrays, was determined. Substantial sound pressure level reduction was obtained for modes within these limits.
Exploratory drag reduction studies in non-polar soap systems.
Concentration, flow rate and tube diameter effects on viscous drag reduction in nonpolar soap solutions, using pressure drop measurements to observe turbulent flow behavior