48,046 research outputs found
Modeling of secondary organic aerosol yields from laboratory chamber data
Laboratory chamber data serve as the basis for constraining models of secondary organic aerosol (SOA) formation. Current models fall into three categories: empirical two-product (Odum), product-specific, and volatility basis set. The product-specific and volatility basis set models are applied here to represent laboratory data on the ozonolysis of α-pinene under dry, dark, and low-NOx conditions in the presence of ammonium sulfate seed aerosol. Using five major identified products, the model is fit to the chamber data. From the optimal fitting, SOA oxygen-to-carbon (O/C) and hydrogen-to-carbon (H/C) ratios are modeled. The discrepancy between measured H/C ratios and those based on the oxidation products used in the model fitting suggests the potential importance of particle-phase reactions. Data fitting is also carried out using the volatility basis set, wherein oxidation products are parsed into volatility bins. The product-specific model is most likely hindered by lack of explicit inclusion of particle-phase accretion compounds. While prospects for identification of the majority of SOA products for major volatile organic compounds (VOCs) classes remain promising, for the near future empirical product or volatility basis set models remain the approaches of choice
Energetic Components of Cooperative Protein Folding
A new lattice protein model with a four-helix bundle ground state is analyzed
by a parameter-space Monte Carlo histogram technique to evaluate the effects of
an extensive variety of model potentials on folding thermodynamics. Cooperative
helical formation and contact energies based on a 5-letter alphabet are found
to be insufficient to satisfy calorimetric and other experimental criteria for
two-state folding. Such proteinlike behaviors are predicted, however, by models
with polypeptide-like local conformational restrictions and
environment-dependent hydrogen bonding-like interactions.Comment: 11 pages, 4 postscripts figures, Phys. Rev. Lett. (in press
Supercritical multicomponent solvent coal extraction
The yield of organic extract from the supercritical extraction of coal with larger diameter organic solvents such as toluene is increased by use of a minor amount of from 0.1 to 10% by weight of a second solvent such as methanol having a molecular diameter significantly smaller than the average pore diameter of the coal
Non-radial oscillations of anisotropic neutron stars in the Cowling approximation
One of the most common assumptions in the study of neutron star models and
their oscillations is that the pressure is isotopic, however there are
arguments that this may not be correct. Thus in the present paper we make a
first step towards studying the nonradial oscillations of neutron stars with an
anisotropic pressure. We adopt the so-called Cowling approximation where the
spacetime metric is kept fixed and the oscillation spectrum for the first few
fluid modes is obtained. The effect of the anisotropy on the frequencies is
apparent, although with the present results it might be hard to distinguish it
from the changes in the frequencies caused by different equations of state.Comment: 17 pages, 8 figures; title changed, comments adde
Role of aldehyde chemistry and NO_x concentrations in secondary organic aerosol formation
Aldehydes are an important class of products from atmospheric oxidation of hydrocarbons. Isoprene (2-methyl-1,3-butadiene), the most abundantly emitted atmospheric non-methane hydrocarbon, produces a significant amount of secondary organic aerosol (SOA) via methacrolein (a C_4-unsaturated aldehyde) under urban high-NO_x conditions. Previously, we have identified peroxy methacryloyl nitrate (MPAN) as the important intermediate to isoprene and methacrolein SOA in this NO_x regime. Here we show that as a result of this chemistry, NO_2 enhances SOA formation from methacrolein and two other α, β-unsaturated aldehydes, specifically acrolein and crotonaldehyde, a NO_x effect on SOA formation previously unrecognized. Oligoesters of dihydroxycarboxylic acids and hydroxynitrooxycarboxylic acids are observed to increase with increasing NO_2/NO ratio, and previous characterizations are confirmed by both online and offline high-resolution mass spectrometry techniques. Molecular structure also determines the amount of SOA formation, as the SOA mass yields are the highest for aldehydes that are α, β-unsaturated and contain an additional methyl group on the α-carbon. Aerosol formation from 2-methyl-3-buten-2-ol (MBO232) is insignificant, even under high-NO_2 conditions, as PAN (peroxy acyl nitrate, RC(O)OONO_2) formation is structurally unfavorable. At atmospherically relevant NO_2/NO ratios (3–8), the SOA yields from isoprene high-NO_x photooxidation are 3 times greater than previously measured at lower NO_2/NO ratios. At sufficiently high NO_2 concentrations, in systems of α, β-unsaturated aldehydes, SOA formation from subsequent oxidation of products from acyl peroxyl radicals+NO_2 can exceed that from RO_2+HO_2 reactions under the same inorganic seed conditions, making RO_2+NO_2 an important channel for SOA formation
Secondary organic aerosol formation from photooxidation of naphthalene and alkylnaphthalenes: implications for oxidation of intermediate volatility organic compounds (IVOCs)
Current atmospheric models do not include secondary
organic aerosol (SOA) production from gas-phase reactions
of polycyclic aromatic hydrocarbons (PAHs). Recent
studies have shown that primary emissions undergo oxidation
in the gas phase, leading to SOA formation. This
opens the possibility that low-volatility gas-phase precursors
are a potentially large source of SOA. In this work,
SOA formation from gas-phase photooxidation of naphthalene,
1-methylnaphthalene (1-MN), 2-methylnaphthalene (2-
MN), and 1,2-dimethylnaphthalene (1,2-DMN) is studied in
the Caltech dual 28-m^3 chambers. Under high-NO_x conditions
and aerosol mass loadings between 10 and 40μgm^(−3),
the SOA yields (mass of SOA per mass of hydrocarbon reacted)
ranged from 0.19 to 0.30 for naphthalene, 0.19 to 0.39
for 1-MN, 0.26 to 0.45 for 2-MN, and constant at 0.31 for
1,2-DMN. Under low-NO_x conditions, the SOA yields were
measured to be 0.73, 0.68, and 0.58, for naphthalene, 1-
MN, and 2-MN, respectively. The SOA was observed to be
semivolatile under high-NO_x conditions and essentially nonvolatile
under low-NO_x conditions, owing to the higher fraction
of ring-retaining products formed under low-NO_x conditions.
When applying these measured yields to estimate
SOA formation from primary emissions of diesel engines
and wood burning, PAHs are estimated to yield 3–5 times
more SOA than light aromatic compounds over photooxidation
timescales of less than 12 h. PAHs can also account for
up to 54% of the total SOA from oxidation of diesel emissions,
representing a potentially large source of urban SOA
Energy landscapes, supergraphs, and "folding funnels" in spin systems
Dynamical connectivity graphs, which describe dynamical transition rates
between local energy minima of a system, can be displayed against the
background of a disconnectivity graph which represents the energy landscape of
the system. The resulting supergraph describes both dynamics and statics of the
system in a unified coarse-grained sense. We give examples of the supergraphs
for several two dimensional spin and protein-related systems. We demonstrate
that disordered ferromagnets have supergraphs akin to those of model proteins
whereas spin glasses behave like random sequences of aminoacids which fold
badly.Comment: REVTeX, 9 pages, two-column, 13 EPS figures include
Constraining New Forces in the Casimir Regime Using the Isoelectronic Technique
We report the first isoelectronic differential force measurements between a
Au-coated probe and two Au-coated films, made out of Au and Ge. These
measurements, performed at submicron separations using soft
microelectromechanical torsional oscillators, eliminate the need for a detailed
understanding of the probe-film Casimir interaction. The observed differential
signal is directly converted into limits on the parameters and
which characterize Yukawa-like deviations from Newtonian gravity. We
find \alpha \lsim 10^{12} for nm, an improvement of
10 over previous limits.Comment: 10 pages, 4 figure
Error Voltage Components in Quantitative Voltage Contrast Measurement Systems
This paper presents the results of computer simulation studies into the respective contributions of the potential barrier, the off-normal incidence injection of secondary electrons (SEs) into the retarding field and analyser geometry on Types I and II local field error voltages for a practical 20 mm wide planar retarding field energy analyser. Results show that the error voltage component due to the off-normal incidence injection effect of SEs into the retarding field dominates the Type I local field error. For type II LFE, the error voltage component due to analyser geometry effect is the higher contributing factor. The presence of a neighbouring electrode voltage tends to draw SEs away from the central axis of the energy analyser, thus causing the electron trajectories to be more sensitive to the influence of the analyser geometry
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