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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 19 records

The Role of Pendant Amines in the Breaking and Forming of Molecular Hydrogen Catalyzed by Nickel Complexes

We present the results of a comprehensive theoretical investigation of the role of pendant amine ligands in the oxidation of H2 and formation of H2 by [Ni(P2RN2R’)2]2+ electrocatalysts (where P2RN2R’ is the 1,5-R’-3,7-R derivative of 1,5-diaza-3,7-diphosphacyclooctane with R and R’ are aryl or alkyl groups). We focus our analysis on the thermolchemical part of the catalytic cycle, as it is known to be rate determining for both H2 oxidation and production. We find that the presence of pendant amine functional groups greatly facilitates the heterolytic H2 bond cleavage resulting in a protonated amine functional group and a Ni hydride. Only one single well-positioned pendant amine is required to serve this function. The pendant amine can also effectively shuttle protons to the active site making the redistribution of protons and the H2 evolution a very facile processes. An important requirement for the overall catalytic process is the positioning of at least one amine in close proximity to the metal center. Indeed, only protonation of the pendant amines on the metal center side (endo position) leads to catalytically active intermediates, whereas protonation on the opposite side of the metal center (exo position) leads to a variety of isomers, which are detrimental to catalysis. This material is based upon work supported as part of the Center for Molecular Electrocatalysis, an Energy Frontier Research Center funded by the US Department of Energy, Office of Science, Office of Basic Energy Sciences under FWP56073.

08 HYDROGEN↗

Fermi large area telescope detection of a break in the gamma-ray spectrum of the supernova remnant Cassiopeia A

We report on observations of the supernova remnant Cassiopeia A in the energy range from 100 MeV to 100 GeV using 44 months of observations from the Large Area Telescope on board the Fermi Gamma-Ray Space Telescope. We perform a detailed spectral analysis of this source and report on a low-energy break in the spectrum at 1.72{sub −0.89}{sup +1.35} GeV. By comparing the results with models for the gamma-ray emission, we find that hadronic emission is preferred for the GeV energy range.

79 ASTRONOMY AND ASTROPHYSICS↗

Symmetry breaking indication for supergravity inflation in light of the Planck 2015

Supergravity (SUGRA) theories with exact global U(1) symmetry or shift symmetry in Kähler potential provide natural frameworks for inflation. However, quadratic inflation is disfavoured by the new results on primordial tensor fluctuations from the Planck Collaboration. To be consistent with the new Planck data, we point out that the explicit symmetry breaking is needed, and study these two SUGRA inflation in detail. For SUGRA inflation with global U(1) symmetry, the symmetry breaking term leads to a trigonometric modulation on inflaton potential. Coefficient of the U(1) symmetry breaking term is of order 10{sup −2}, which is sufficient large to improve the inflationary predictions while its higher order corrections are negligible. Such models predict sizeable tensor fluctuations and highly agree with the Planck results. In particular, the model with a linear U(1) symmetry breaking term predicts the tensor-to-scalar ratio around r∼0.01 and running spectral index α{sub s∼} −0.004, which comfortably fit with the Planck observations. For SUGRA inflation with breaking shift symmetry, the inflaton potential is modulated by an exponential factor. The modulated linear and quadratic models are consistent with the Planck observations. In both types of models the tensor-to-scalar ratio can be of order 10{sup −2}, which will be tested by the near future observations.

79 ASTRONOMY AND ASTROPHYSICS↗

EARLY BUD-BREAK 1 and EARLY BUD-BREAK 3 control resumption of poplar growth after winter dormancy

Bud-break is an economically and environmentally important process in trees and shrubs from boreal and temperate latitudes, but its molecular mechanisms are poorly understood. Here, we show that two previously reported transcription factors, EARLY BUD BREAK 1 (EBB1) and SHORT VEGETATIVE PHASE-Like (SVL) directly interact to control bud-break. EBB1 is a positive regulator of bud-break, whereas SVL is a negative regulator of bud-break. EBB1 directly and negatively regulates SVL expression. We further report the identification and characterization of the EBB3 gene. EBB3 is a temperature-responsive, epigenetically-regulated, positive regulator of bud-break that provides a direct link to activation of the cell cycle during bud-break. EBB3 is an AP2/ERF transcription factor that positively and directly regulates CYCLIND3.1 gene. Our results reveal the architecture of a putative regulatory module that links temperature-mediated control of bud-break with activation of cell cycle.

54 ENVIRONMENTAL SCIENCES↗

Dynamics of Peccei-Quinn breaking field after inflation and axion isocurvature perturbations

The Peccei-Quinn mechanism suffers from the problem of the isocurvature perturbations. The isocurvature perturbations are suppressed if the Peccei-Quinn breaking scale is large during inflation. The oscillation of the Peccei-Quinn breaking field after inflation, however, leads to the formation of domain walls due to the parametric resonance effect. In this paper, we discuss the evolution of the Peccei-Quinn breaking field after inflation in detail, and propose a model where the parametric resonance is ineffective and hence domain walls are not formed. We also discuss consistency of our model with supersymmetric theory.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗

Breaking discrete symmetries in the effective field theory of inflation

We study the phenomenon of discrete symmetry breaking during the inflationary epoch, using a model-independent approach based on the effective field theory of inflation. We work in a context where both time reparameterization symmetry and spatial diffeomorphism invariance can be broken during inflation. We determine the leading derivative operators in the quadratic action for fluctuations that break parity and time-reversal. Within suitable approximations, we study their consequences for the dynamics of linearized fluctuations. Both in the scalar and tensor sectors, we show that such operators can lead to new direction-dependent phases for the modes involved. They do not affect the power spectra, but can have consequences for higher correlation functions. Moreover, a small quadrupole contribution to the sound speed can be generated.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗

Boost breaking in the EFT of inflation

If time-translations are spontaneously broken, so are boosts. This symmetry breaking pattern can be non-linearly realized by either just the Goldstone boson of time translations, or by four Goldstone bosons associated with time translations and boosts. Here in this paper we extend the Effective Field Theory of Multifield Inflation to consider the case in which the additional Goldstone bosons associated with boosts are light and coupled to the Goldstone boson of time translations. The symmetry breaking pattern forces a coupling to curvature so that the mass of the additional Goldstone bosons is predicted to be equal to √2H in the vast majority of the parameter space where they are light. This pattern therefore offers a natural way of generating self-interacting particles with Hubble mass during inflation. After constructing the general effective Lagrangian, we study how these particles mix and interact with the curvature fluctuations, generating potentially detectable non-Gaussian signals.

79 ASTRONOMY AND ASTROPHYSICS↗

SU-C-BRE-07: Sensitivity Analysis of the Threshold Energy for the Creation of Strand Breaks and of Single and Double Strand Break Clustering Conditions

Purpose: To analyse the sensitivity of the creation of strand breaks (SB) to the threshold energy (Eth) and thresholding method and to quantify the impact of clustering conditions on single strand break (SSB) and double strand break (DSB) yields. Methods: Monte Carlo simulations using Geant4-DNA were conducted for electron tracks of 280 eV to 220 keV in a geometrical DNA model composed of nucleosomes of 396 phospho-diester groups (PDGs) each. A strand break was created inside a PDG when the sum of all energy deposits (method 1) or energy transfers (method 2) was higher than Eth or when at least one interaction deposited (method 3) or transferred (method 4) an energy higher than Eth. SBs were then clustered into SSBs and DSBs using clustering scoring criteria from the literature and compared to our own. Results: The total number of SBs decreases as Eth is increased. In addition, thresholding on the energy transfers (methods 2 and 4) produces a higher SB count than when thresholding on energy deposits (methods 1 and 3). Method 2 produces a step-like function and should be avoided when attempting to optimize Eth. When SBs are grouped into damage patterns, clustering conditions can underestimated SSBs by up to 18 % and DSBs can be overestimated by up to 12 % compared to our own implementation. Conclusion: We show that two often underreported simulation parameters have a non-negligible effect on overall DNA damage yields. First more SBs are counted when using energy transfers to the PDG rather than energy deposits. Also, SBs grouped according to different clustering conditions can influence reported SSB and DSB by as much as 20%. Careful handling of these parameters is required when trying to compare DNA damage yields from different authors. Research funding from the governments of Canada and Quebec. PP acknowledges partial support by the CREATE Medical Physics Research Training Network grant of the Natural Sciences and Engineering Research Council (Grant number: 432290)

60 APPLIED LIFE SCIENCES↗

WIMP and SIMP dark matter from the spontaneous breaking of a global group

We propose and study a scalar extension of the Standard Model which respects a ℤ{sub 3} symmetry remnant of the spontaneous breaking of a global U(1){sub DM} symmetry. Consequently, this model has a natural dark matter candidate and a Goldstone boson in the physical spectrum. In addition, the Higgs boson properties are changed with respect to the Standard Model due to the mixing with a new particle. We explore regions in the parameter space taking into account bounds from the measured Higgs properties, dark matter direct detection as well as measurements of the effective number of neutrino species before recombination. The dark matter relic density is determined by three classes of processes: the usual self-annihilation, semi-annihilation and purely dark matter 3→2 processes. The latter has been subject of recent interest leading to the so-called ‘Strongly Interacting Massive Particle’ (SIMP) scenario. We show under which conditions our model can lead to a concrete realization of such scenario and study the possibility that the dark matter self-interactions could address the small scale structure problems. In particular, we find that in order for the SIMP scenario to work, the dark matter mass must be in the range 7−115 MeV, with the global symmetry energy breaking scale in the TeV range.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗

Base excision repair and double strand break repair cooperate to modulate the formation of unrepaired double strand breaks in mouse brain

Abstract We lack the fundamental information needed to understand how DNA damage in the brain is generated and how it is controlled over a lifetime in the absence of replication check points. To address these questions, here, we integrate cell-type and region-specific features of DNA repair activity in the normal brain. The brain has the same repair proteins as other tissues, but normal, canonical repair activity is unequal and is characterized by high base excision repair (BER) and low double strand break repair (DSBR). The natural imbalance creates conditions where single strand breaks (SSBs) can convert to double strand breaks (DSBs) and reversibly switch between states in response to oxidation both in vivo and in vitro. Our data suggest that, in a normal background of repair, SSBs and DSBs are in an equilibrium which is pushed or pulled by metabolic state. Interconversion of SSB to DSBs provides a physiological check point, which would allow the formation of unrepaired DSBs for productive functions, but would also restrict them from exceeding tolerable limits.

Science & Technology - Other Topics↗

Symmetry breaking charge transfer as a means to study electron transfer with no driving force

Symmetry breaking charge transfer (SBCT) is a process where a symmetrically disposed pair of identical chromophores forms a charge transfer excited state with the hole and electron on different chromophores, i.e. chr–chr + hν → chr + –chr – . Herein we explore this process in two dipyrrin-based bichromophoric systems. One of these bisdipyrrins involved a pair of BODIPY chromophores linked by a single bond at their meso-positions (compound 1) and the other involved two dipyrrin ligands coordinated in a tetrahedral geometry at the Zn 2+ ion (compound 2). Both compounds show rapid SBCT in polar solvents and only dipyrrin based emission in nonpolar solvents, the latter arising from a dipyrrin localized excited sate (LE). By “tuning” the solvent polarity the equilibrium between the LE and SBCT states can be shifted to favor either state. Ultrafast transient absorption spectroscopy (TA) was used to probe the kinetics of the charge transfer for 2 in solvents where the electron transfer is endergonic, exergonic and has a ΔG close to zero. Our TA derived rates were used to predict fluorescence efficiencies in each of the different solvent systems and showed a good correspondence to measured values. Detailed density functional theory (DFT) and time dependent DFT were used to model the ground states as well as the LE and SBCT states of 1 and 2, in both polar and nonpolar media. Lastly, the ground and LE excited states show small dipole moments, while the SBCT states show dipole moments of 16.4 and 20.3 D for 1 and 2, respectively.

14 SOLAR ENERGY↗