Independent EEG Sources Are Dipolar

PubMed Central

Delorme, Arnaud; Palmer, Jason; Onton, Julie; Oostenveld, Robert; Makeig, Scott

2012-01-01

Independent component analysis (ICA) and blind source separation (BSS) methods are increasingly used to separate individual brain and non-brain source signals mixed by volume conduction in electroencephalographic (EEG) and other electrophysiological recordings. We compared results of decomposing thirteen 71-channel human scalp EEG datasets by 22 ICA and BSS algorithms, assessing the pairwise mutual information (PMI) in scalp channel pairs, the remaining PMI in component pairs, the overall mutual information reduction (MIR) effected by each decomposition, and decomposition ‘dipolarity’ defined as the number of component scalp maps matching the projection of a single equivalent dipole with less than a given residual variance. The least well-performing algorithm was principal component analysis (PCA); best performing were AMICA and other likelihood/mutual information based ICA methods. Though these and other commonly-used decomposition methods returned many similar components, across 18 ICA/BSS algorithms mean dipolarity varied linearly with both MIR and with PMI remaining between the resulting component time courses, a result compatible with an interpretation of many maximally independent EEG components as being volume-conducted projections of partially-synchronous local cortical field activity within single compact cortical domains. To encourage further method comparisons, the data and software used to prepare the results have been made available (http://sccn.ucsd.edu/wiki/BSSComparison). PMID:22355308

Market Competitiveness Evaluation of Mechanical Equipment with a Pairwise Comparisons Hierarchical Model.

PubMed

Hou, Fujun

2016-01-01

This paper provides a description of how market competitiveness evaluations concerning mechanical equipment can be made in the context of multi-criteria decision environments. It is assumed that, when we are evaluating the market competitiveness, there are limited number of candidates with some required qualifications, and the alternatives will be pairwise compared on a ratio scale. The qualifications are depicted as criteria in hierarchical structure. A hierarchical decision model called PCbHDM was used in this study based on an analysis of its desirable traits. Illustration and comparison shows that the PCbHDM provides a convenient and effective tool for evaluating the market competitiveness of mechanical equipment. The researchers and practitioners might use findings of this paper in application of PCbHDM.

Ab initio Kinetics and Thermal Decomposition Mechanism of Mononitrobiuret and 1,5-Dinitrobiuret

DTIC Science & Technology

2016-03-14

Journal Article 3. DATES COVERED (From - To) Feb 2015-May 2015 4. TITLE AND SUBTITLE Ab initio Kinetics and Thermal Decomposition Mechanism of 5a...tetrazole-free, nitrogen-rich, energetic compounds. For the first time, the thermal decomposition mechanisms of MNB and DNB have been investigated...potential energy surfaces for thermal decomposition of MNB and DNB were characterized at the RCCSD(T)/cc-pV∞Z//M06-2X/aug- cc-pVTZ level of theory

Dynamics of pairwise motions in the Cosmic Web

NASA Astrophysics Data System (ADS)

Hellwing, Wojciech A.

2016-10-01

We present results of analysis of the dark matter (DM) pairwise velocity statistics in different Cosmic Web environments. We use the DM velocity and density field from the Millennium 2 simulation together with the NEXUS+ algorithm to segment the simulation volume into voxels uniquely identifying one of the four possible environments: nodes, filaments, walls or cosmic voids. We show that the PDFs of the mean infall velocities v 12 as well as its spatial dependence together with the perpendicular and parallel velocity dispersions bear a significant signal of the large-scale structure environment in which DM particle pairs are embedded. The pairwise flows are notably colder and have smaller mean magnitude in wall and voids, when compared to much denser environments of filaments and nodes. We discuss on our results, indicating that they are consistent with a simple theoretical predictions for pairwise motions as induced by gravitational instability mechanism. Our results indicate that the Cosmic Web elements are coherent dynamical entities rather than just temporal geometrical associations. In addition it should be possible to observationally test various Cosmic Web finding algorithms by segmenting available peculiar velocity data and studying resulting pairwise velocity statistics.

Effects of defects on thermal decomposition of HMX via ReaxFF molecular dynamics simulations.

PubMed

Zhou, Ting-Ting; Huang, Feng-Lei

2011-01-20

Effects of molecular vacancies on the decomposition mechanisms and reaction dynamics of condensed-phase β-HMX at various temperatures were studied using ReaxFF molecular dynamics simulations. Results show that three primary initial decomposition mechanisms, namely, N-NO(2) bond dissociation, HONO elimination, and concerted ring fission, exist at both high and lower temperatures. The contribution of the three mechanisms to the initial decomposition of HMX is influenced by molecular vacancies, and the effects vary with temperature. At high temperature (2500 K), molecular vacancies remarkably promote N-N bond cleavage and concerted ring breaking but hinder HONO formation. N-N bond dissociation and HONO elimination are two primary competing reaction mechanisms, and the former is dominant in the initial decomposition. Concerted ring breaking of condensed-phase HMX is not favored at high temperature. At lower temperature (1500 K), the most preferential initial decomposition pathway is N-N bond dissociation followed by the formation of NO(3) (O migration), although all three mechanisms are promoted by molecular vacancies. The promotion effect on concerted ring breaking is considerable at lower temperature. Products resulting from concerted ring breaking appear in the defective system but not in the perfect crystal. The mechanism of HONO elimination is less important at lower temperature. We also estimated the reaction rate constant and activation barriers of initial decomposition with different vacancy concentrations. Molecular vacancies accelerate the decomposition of condensed-phase HMX by increasing the reaction rate constant and reducing activation barriers.

Effect of Copper Oxide, Titanium Dioxide, and Lithium Fluoride on the Thermal Behavior and Decomposition Kinetics of Ammonium Nitrate

NASA Astrophysics Data System (ADS)

Vargeese, Anuj A.; Mija, S. J.; Muralidharan, Krishnamurthi

2014-07-01

Ammonium nitrate (AN) is crystallized along with copper oxide, titanium dioxide, and lithium fluoride. Thermal kinetic constants for the decomposition reaction of the samples were calculated by model-free (Friedman's differential and Vyzovkins nonlinear integral) and model-fitting (Coats-Redfern) methods. To determine the decomposition mechanisms, 12 solid-state mechanisms were tested using the Coats-Redfern method. The results of the Coats-Redfern method show that the decomposition mechanism for all samples is the contracting cylinder mechanism. The phase behavior of the obtained samples was evaluated by differential scanning calorimetry (DSC), and structural properties were determined by X-ray powder diffraction (XRPD). The results indicate that copper oxide modifies the phase transition behavior and can catalyze AN decomposition, whereas LiF inhibits AN decomposition, and TiO2 shows no influence on the rate of decomposition. Possible explanations for these results are discussed. Supplementary materials are available for this article. Go to the publisher's online edition of the Journal of Energetic Materials to view the free supplemental file.

Statistical methods for change-point detection in surface temperature records

NASA Astrophysics Data System (ADS)

Pintar, A. L.; Possolo, A.; Zhang, N. F.

2013-09-01

We describe several statistical methods to detect possible change-points in a time series of values of surface temperature measured at a meteorological station, and to assess the statistical significance of such changes, taking into account the natural variability of the measured values, and the autocorrelations between them. These methods serve to determine whether the record may suffer from biases unrelated to the climate signal, hence whether there may be a need for adjustments as considered by M. J. Menne and C. N. Williams (2009) "Homogenization of Temperature Series via Pairwise Comparisons", Journal of Climate 22 (7), 1700-1717. We also review methods to characterize patterns of seasonality (seasonal decomposition using monthly medians or robust local regression), and explain the role they play in the imputation of missing values, and in enabling robust decompositions of the measured values into a seasonal component, a possible climate signal, and a station-specific remainder. The methods for change-point detection that we describe include statistical process control, wavelet multi-resolution analysis, adaptive weights smoothing, and a Bayesian procedure, all of which are applicable to single station records.

Pairwise-additive hydrophobic effect for alkanes in water

PubMed Central

Wu, Jianzhong; Prausnitz, John M.

2008-01-01

Pairwise additivity of the hydrophobic effect is indicated by reliable experimental Henry's constants for a large number of linear and branched low-molecular-weight alkanes in water. Pairwise additivity suggests that the hydrophobic effect is primarily a local phenomenon and that the hydrophobic interaction may be represented by a semiempirical force field. By representing the hydrophobic potential between two methane molecules as a linear function of the overlap volume of the hydration layers, we find that the contact value of the hydrophobic potential (−0.72 kcal/mol) is smaller than that from quantum mechanics simulations (−2.8 kcal/mol) but is close to that from classical molecular dynamics (−0.5∼−0.9 kcal/mol). PMID:18599448

Computing the non-Markovian coarse-grained interactions derived from the Mori-Zwanzig formalism in molecular systems: Application to polymer melts

NASA Astrophysics Data System (ADS)

Li, Zhen; Lee, Hee Sun; Darve, Eric; Karniadakis, George Em

2017-01-01

Memory effects are often introduced during coarse-graining of a complex dynamical system. In particular, a generalized Langevin equation (GLE) for the coarse-grained (CG) system arises in the context of Mori-Zwanzig formalism. Upon a pairwise decomposition, GLE can be reformulated into its pairwise version, i.e., non-Markovian dissipative particle dynamics (DPD). GLE models the dynamics of a single coarse particle, while DPD considers the dynamics of many interacting CG particles, with both CG systems governed by non-Markovian interactions. We compare two different methods for the practical implementation of the non-Markovian interactions in GLE and DPD systems. More specifically, a direct evaluation of the non-Markovian (NM) terms is performed in LE-NM and DPD-NM models, which requires the storage of historical information that significantly increases computational complexity. Alternatively, we use a few auxiliary variables in LE-AUX and DPD-AUX models to replace the non-Markovian dynamics with a Markovian dynamics in a higher dimensional space, leading to a much reduced memory footprint and computational cost. In our numerical benchmarks, the GLE and non-Markovian DPD models are constructed from molecular dynamics (MD) simulations of star-polymer melts. Results show that a Markovian dynamics with auxiliary variables successfully generates equivalent non-Markovian dynamics consistent with the reference MD system, while maintaining a tractable computational cost. Also, transient subdiffusion of the star-polymers observed in the MD system can be reproduced by the coarse-grained models. The non-interacting particle models, LE-NM/AUX, are computationally much cheaper than the interacting particle models, DPD-NM/AUX. However, the pairwise models with momentum conservation are more appropriate for correctly reproducing the long-time hydrodynamics characterised by an algebraic decay in the velocity autocorrelation function.

Decomposition mechanism of chromite in sulfuric acid-dichromic acid solution

NASA Astrophysics Data System (ADS)

Zhao, Qing; Liu, Cheng-jun; Li, Bao-kuan; Jiang, Mao-fa

2017-12-01

The sulfuric acid leaching process is regarded as a promising, cleaner method to prepare trivalent chromium products from chromite; however, the decomposition mechanism of the ore is poorly understood. In this work, binary spinels of Mg-Al, Mg-Fe, and Mg-Cr in the powdered and lump states were synthesized and used as raw materials to investigate the decomposition mechanism of chromite in sulfuric acid-dichromic acid solution. The leaching yields of metallic elements and the changes in morphology of the spinel were studied. The experimental results showed that the three spinels were stable in sulfuric acid solution and that dichromic acid had little influence on the decomposition behavior of the Mg-Al spinel and Mg-Fe spinel because Mg2+, Al3+, and Fe3+ in spinels cannot be oxidized by Cr6+. However, in the case of the Mg-Cr spinel, dichromic acid substantially promoted the decomposition efficiency and functioned as a catalyst. The decomposition mechanism of chromite in sulfuric acid-dichromic acid solution was illustrated on the basis of the findings of this study.

An ab initio molecular dynamics study of thermal decomposition of 3,6-di(azido)-1,2,4,5-tetrazine.

PubMed

Wu, Qiong; Zhu, Weihua; Xiao, Heming

2014-10-21

Ab initio molecular dynamics simulations were performed to study the thermal decomposition of isolated and crystal 3,6-di(azido)-1,2,4,5-tetrazine (DiAT). During unimolecular decomposition, the three different initiation mechanisms were observed to be N-N2 cleavage, ring opening, and isomerization, respectively. The preferential initial decomposition step is the homolysis of the N-N2 bond in the azido group. The release mechanisms of nitrogen gas are found to be very different in the early and later decomposition stages of crystal DiAT. In the early decomposition, DiAT decomposes very fast and drastically without forming any stable long-chains or heterocyclic clusters, and most of the nitrogen gases are released through rapid rupture of nitrogen-nitrogen and carbon-nitrogen bonds. But in the later decomposition stage, the release of nitrogen gas is inhibited due to low mobility, long distance from each other, and strong carbon-nitrogen bonds. To overcome the obstacles, the nitrogen gases are released through slow formation and disintegration of polycyclic networks. Our simulations suggest a new decomposition mechanism for the organic polyazido initial explosive at the atomistic level.

A density functional theory study of the decomposition mechanism of nitroglycerin.

PubMed

Pei, Liguan; Dong, Kehai; Tang, Yanhui; Zhang, Bo; Yu, Chang; Li, Wenzuo

2017-08-21

The detailed decomposition mechanism of nitroglycerin (NG) in the gas phase was studied by examining reaction pathways using density functional theory (DFT) and canonical variational transition state theory combined with a small-curvature tunneling correction (CVT/SCT). The mechanism of NG autocatalytic decomposition was investigated at the B3LYP/6-31G(d,p) level of theory. Five possible decomposition pathways involving NG were identified and the rate constants for the pathways at temperatures ranging from 200 to 1000 K were calculated using CVT/SCT. There was found to be a lower energy barrier to the β-H abstraction reaction than to the α-H abstraction reaction during the initial step in the autocatalytic decomposition of NG. The decomposition pathways for CHOCOCHONO 2 (a product obtained following the abstraction of three H atoms from NG by NO 2 ) include O-NO 2 cleavage or isomer production, meaning that the autocatalytic decomposition of NG has two reaction pathways, both of which are exothermic. The rate constants for these two reaction pathways are greater than the rate constants for the three pathways corresponding to unimolecular NG decomposition. The overall process of NG decomposition can be divided into two stages based on the NO 2 concentration, which affects the decomposition products and reactions. In the first stage, the reaction pathway corresponding to O-NO 2 cleavage is the main pathway, but the rates of the two autocatalytic decomposition pathways increase with increasing NO 2 concentration. However, when a threshold NO 2 concentration is reached, the NG decomposition process enters its second stage, with the two pathways for NG autocatalytic decomposition becoming the main and secondary reaction pathways.

Power independent EMG based gesture recognition for robotics.

PubMed

Li, Ling; Looney, David; Park, Cheolsoo; Rehman, Naveed U; Mandic, Danilo P

2011-01-01

A novel method for detecting muscle contraction is presented. This method is further developed for identifying four different gestures to facilitate a hand gesture controlled robot system. It is achieved based on surface Electromyograph (EMG) measurements of groups of arm muscles. The cross-information is preserved through a simultaneous processing of EMG channels using a recent multivariate extension of Empirical Mode Decomposition (EMD). Next, phase synchrony measures are employed to make the system robust to different power levels due to electrode placements and impedances. The multiple pairwise muscle synchronies are used as features of a discrete gesture space comprising four gestures (flexion, extension, pronation, supination). Simulations on real-time robot control illustrate the enhanced accuracy and robustness of the proposed methodology.

New mechanism for autocatalytic decomposition of H2CO3 in the vapor phase.

PubMed

Ghoshal, Sourav; Hazra, Montu K

2014-04-03

In this article, we present high level ab initio calculations investigating the energetics of a new autocatalytic decomposition mechanism for carbonic acid (H2CO3) in the vapor phase. The calculation have been performed at the MP2 level of theory in conjunction with aug-cc-pVDZ, aug-cc-pVTZ, and 6-311++G(3df,3pd) basis sets as well as at the CCSD(T)/aug-cc-pVTZ level. The present study suggests that this new decomposition mechanism is effectively a near-barrierless process at room temperature and makes vapor phase of H2CO3 unstable even in the absence of water molecules. Our calculation at the MP2/aug-cc-pVTZ level predicts that the effective barrier, defined as the difference between the zero-point vibrational energy (ZPE) corrected energy of the transition state and the total energy of the isolated starting reactants in terms of bimolecular encounters, is nearly zero for the autocatalytic decomposition mechanism. The results at the CCSD(T)/aug-cc-pVTZ level of calculations suggest that the effective barrier, as defined above, is sensitive to some extent to the levels of calculations used, nevertheless, we find that the effective barrier height predicted at the CCSD(T)/aug-cc-pVTZ level is very small or in other words the autocatalytic decomposition mechanism presented in this work is a near-barrierless process as mentioned above. Thus, we suggest that this new autocatalytic decomposition mechanism has to be considered as the primary mechanism for the decomposition of carbonic acid, especially at its source, where the vapor phase concentration of H2CO3 molecules reaches its highest levels.

A characterization of the two-step reaction mechanism of phenol decomposition by a Fenton reaction

NASA Astrophysics Data System (ADS)

Valdés, Cristian; Alzate-Morales, Jans; Osorio, Edison; Villaseñor, Jorge; Navarro-Retamal, Carlos

2015-11-01

Phenol is one of the worst contaminants at date, and its degradation has been a crucial task over years. Here, the decomposition process of phenol, in a Fenton reaction, is described. Using scavengers, it was observed that decomposition of phenol was mainly influenced by production of hydroxyl radicals. Experimental and theoretical activation energies (Ea) for phenol oxidation intermediates were calculated. According to these Ea, phenol decomposition is a two-step reaction mechanism mediated predominantly by hydroxyl radicals, producing a decomposition yield order given as hydroquinone > catechol > resorcinol. Furthermore, traces of reaction derived acids were detected by HPLC and GS-MS.

Theoretical study of the decomposition mechanism of environmentally friendly insulating medium C3F7CN in the presence of H2O in a discharge

NASA Astrophysics Data System (ADS)

Zhang, Xiaoxing; Li, Yi; Xiao, Song; Tian, Shuangshuang; Deng, Zaitao; Tang, Ju

2017-08-01

C3F7CN has been the focus of the alternative gas research field over the past two years because of its excellent insulation properties and environmental characteristics. Experimental studies on its insulation performance have made many achievements. However, few studies on the formation mechanism of the decomposition components exist. A discussion of the decomposition characteristics of insulating media will provide guidance for scientific experimental research and the work that must be completed before further engineering application. In this study, the decomposition mechanism of C3F7CN in the presence of trace H2O under discharge was calculated based on the density functional theory and transition state theory. The reaction heat, Gibbs free energy, and activation energy of different decomposition pathways were investigated. The ionization parameters and toxicity of C3F7CN and various decomposition products were analyzed from the molecular structure perspective. The formation mechanism of the C3F7CN discharge decomposition components and the influence of trace water were evaluated. This paper confirms that C3F7CN has excellent decomposition characteristics, which provide theoretical support for later experiments and related engineering applications. However, the existence of trace water has a negative impact on C3F7CN’s insulation performance. Thus, strict trace water content standards should be developed to ensure dielectric insulation and the safety of maintenance personnel.

Propensity-score matching in economic analyses: comparison with regression models, instrumental variables, residual inclusion, differences-in-differences, and decomposition methods.

PubMed

Crown, William H

2014-02-01

This paper examines the use of propensity score matching in economic analyses of observational data. Several excellent papers have previously reviewed practical aspects of propensity score estimation and other aspects of the propensity score literature. The purpose of this paper is to compare the conceptual foundation of propensity score models with alternative estimators of treatment effects. References are provided to empirical comparisons among methods that have appeared in the literature. These comparisons are available for a subset of the methods considered in this paper. However, in some cases, no pairwise comparisons of particular methods are yet available, and there are no examples of comparisons across all of the methods surveyed here. Irrespective of the availability of empirical comparisons, the goal of this paper is to provide some intuition about the relative merits of alternative estimators in health economic evaluations where nonlinearity, sample size, availability of pre/post data, heterogeneity, and missing variables can have important implications for choice of methodology. Also considered is the potential combination of propensity score matching with alternative methods such as differences-in-differences and decomposition methods that have not yet appeared in the empirical literature.

Viscosity effects on the thermal decomposition of bis(perfluoro-2-N-propoxypropionyl) peroxide in dense carbon dioxide and fluorinated solvents.

PubMed

Bunyard, W C; Kadla, J F; DeYoung, J; DeSimone, J M

2001-08-01

The thermal decomposition of the free-radical initiator bis(perfluoro-2-N-propoxyprionyl) peroxide (BPPP) was studied in dense carbon dioxide and a series of fluorinated solvents. For the fluorinated solvents, the observed first-order decomposition rate constants, k(obs), increased with decreasing solvent viscosity, suggesting a single-bond decomposition mechanism. The k(obs) values are comparatively larger in dense carbon dioxide and similar to the "zero-viscosity" rate constants extrapolated from the decomposition kinetics in the fluorinated solvents. The decomposition activation parameters demonstrate a compensation behavior of the activation enthalpy with the activation entropy upon change in solvent viscosity. Comparison of the change in activation parameter values upon change in solvent viscosity for BPPP with two additional initiators, acetyl peroxide (AP) and trifluoroacetyl peroxide (TFAP), further suggests that carbon dioxide exerts a very minimal influence on the decomposition mechanism of these initiators through solvent-cage effects.

Theoretical studies of the decomposition mechanisms of 1,2,4-butanetriol trinitrate.

PubMed

Pei, Liguan; Dong, Kehai; Tang, Yanhui; Zhang, Bo; Yu, Chang; Li, Wenzuo

2017-12-06

Density functional theory (DFT) and canonical variational transition-state theory combined with a small-curvature tunneling correction (CVT/SCT) were used to explore the decomposition mechanisms of 1,2,4-butanetriol trinitrate (BTTN) in detail. The results showed that the γ-H abstraction reaction is the initial pathway for autocatalytic BTTN decomposition. The three possible hydrogen atom abstraction reactions are all exothermic. The rate constants for autocatalytic BTTN decomposition are 3 to 10 40 times greater than the rate constants for the two unimolecular decomposition reactions (O-NO 2 cleavage and HONO elimination). The process of BTTN decomposition can be divided into two stages according to whether the NO 2 concentration is above a threshold value. HONO elimination is the main reaction channel during the first stage because autocatalytic decomposition requires NO 2 and the concentration of NO 2 is initially low. As the reaction proceeds, the concentration of NO 2 gradually increases; when it exceeds the threshold value, the second stage begins, with autocatalytic decomposition becoming the main reaction channel.

Nitrosonium-Catalyzed Decomposition of S-Nitrosothiols in Solution

PubMed Central

Zhao, Yi-Lei; McCarren, Patrick R.; Houk, K. N.; Choi, Bo Yoon; Toone, Eric J.

2008-01-01

The decomposition of S-nitrosothiols (RSNO) in solution under oxidative conditions is significantly faster than can be accounted for by homolysis of the S-N bond. Here we propose a cationic chain mechanism in which nitrosylation of nitrosothiol produces a nitrosylated cation that, in turn, reacts with a second nitrosothiol to produce disulfide and the NO dimer. Nitrosylated dimer acts as a source of nitrosonium for nitrosothiol nitrosylation, completing the catalytic cycle. The mechanism accounts for several unexplained facets of nitrosothiol chemistry in solution, including the observation that the decomposition of an RSNO is accelerated by O2, mixtures of O2 and NO, and other oxidants, that decomposition is inhibited by thiols and other antioxidants, that decomposition is dependent on sulfur substitution, and that decomposition often shows non-integral kinetic orders. PMID:16076198

Comorbidities in the diseasome are more apparent than real: What Bayesian filtering reveals about the comorbidities of depression

PubMed Central

Bolgar, Bence; Deakin, Bill

2017-01-01

Comorbidity patterns have become a major source of information to explore shared mechanisms of pathogenesis between disorders. In hypothesis-free exploration of comorbid conditions, disease-disease networks are usually identified by pairwise methods. However, interpretation of the results is hindered by several confounders. In particular a very large number of pairwise associations can arise indirectly through other comorbidity associations and they increase exponentially with the increasing breadth of the investigated diseases. To investigate and filter this effect, we computed and compared pairwise approaches with a systems-based method, which constructs a sparse Bayesian direct multimorbidity map (BDMM) by systematically eliminating disease-mediated comorbidity relations. Additionally, focusing on depression-related parts of the BDMM, we evaluated correspondence with results from logistic regression, text-mining and molecular-level measures for comorbidities such as genetic overlap and the interactome-based association score. We used a subset of the UK Biobank Resource, a cross-sectional dataset including 247 diseases and 117,392 participants who filled out a detailed questionnaire about mental health. The sparse comorbidity map confirmed that depressed patients frequently suffer from both psychiatric and somatic comorbid disorders. Notably, anxiety and obesity show strong and direct relationships with depression. The BDMM identified further directly co-morbid somatic disorders, e.g. irritable bowel syndrome, fibromyalgia, or migraine. Using the subnetwork of depression and metabolic disorders for functional analysis, the interactome-based system-level score showed the best agreement with the sparse disease network. This indicates that these epidemiologically strong disease-disease relations have improved correspondence with expected molecular-level mechanisms. The substantially fewer number of comorbidity relations in the BDMM compared to pairwise methods implies that biologically meaningful comorbid relations may be less frequent than earlier pairwise methods suggested. The computed interactive comprehensive multimorbidity views over the diseasome are available on the web at Co=MorNet: bioinformatics.mit.bme.hu/UKBNetworks. PMID:28644851

Interactions of Hydrazine and Blowby Gases

NASA Technical Reports Server (NTRS)

Meagher, Nancy E.

2003-01-01

The interactions between hydrazine and blowby gases from pyrovalves was explored in this research project. Investigating the decomposition chemistry of hydrazine through detailed chemical kinetic modeling is a project started last summer while participating in the Summer Faculty Fellowship program. During the 1999-2000 academic year, the chemical kinetic mechanism for hydrazine decomposition developed while a SFF at NASA's White Sands Test Facility was further revised and validated against the limited experimental data in the literature. This mechanism was then used in assessing the effects of blowby gas species on hydrazine decomposition. The combustion products introduced into the fuel line by pyrovalve actuation consist primarily of hydrogen gas. Hydrogen is also a product of the decomposition of hydrazine. Additional gaseous chemical species are introduced into the fuel, as well as metals and metal salts that deposit onto the walls of the fuel line. The deposition process is undoubtedly very rapid, and exothermic. Therefore, the major focus of this summer's work was examining the effects of hydrogen presence on hydrazine decomposition, with some representative calculations including the remaining gaseous species found to exist in blowby gases. Since hydrogen is a product of hydrazine decomposition, all reactions necessary to evaluate its effect on hydrazine decomposition chemistry were in the original mechanism developed. However, the mechanism needed to be considerably expanded to include the reactions of the other gaseous blowby species with hydrazine, all the intermediate species formed in its decomposition, and each other. The expanded mechanism consists of 70 species interacting via a network of 452 reactions. Calculations with molecular hydrogen introduced into hydrazine gas in an inert bath gas indicate that H2 presence as an initial reactant in substantial amounts can dramatically impact the decomposition process for hydrazine. The other gaseous blowby species (CO, CO2, H2O, CH4, O2, and N2) were found to have little effect compared to the inclusion of hydrogen itself as an initial reagent. This result is undoubtedly due, in part, to the fact that the blowby gas used in these calculations consisted of 94.6% H2. A more rigorous examination of the behavior of the full detailed mechanism under a variety of conditions was not performed.

Single-atom gold catalysis in the context of developments in parahydrogen-induced polarization.

PubMed

Corma, Avelino; Salnikov, Oleg G; Barskiy, Danila A; Kovtunov, Kirill V; Koptyug, Igor V

2015-05-04

A highly isolated monoatomic gold catalyst, with single gold atoms dispersed on multiwalled carbon nanotubes (MWCNTs), has been synthesized, characterized, and tested in heterogeneous hydrogenation of 1,3-butadiene and 1-butyne with parahydrogen to maximize the polarization level and the contribution of the pairwise hydrogen addition route. The Au/MWCNTs catalyst was found to be active and efficient in pairwise hydrogen addition and the estimated contributions from the pairwise hydrogen addition route are at least an order of magnitude higher than those for supported metal nanoparticle catalysts. Therefore, the use of the highly isolated monoatomic catalysts is very promising for production of hyperpolarized fluids that can be used for the significant enhancement of NMR signals. A mechanism of 1,3-butadiene hydrogenation with parahydrogen over the highly isolated monoatomic Au/MWCNTs catalyst is also proposed. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Study on US/O3 mechanism in p-chlorophenol decomposition

PubMed Central

Xu, Xian-wen; Xu, Xin-hua; Shi, Hui-xiang; Wang, Da-hui

2005-01-01

Study on the effects of sonolysis, ozonolysis and US/O3 system on the decomposition of p-chlorophenol in aqueous solutions indicated that in the cases of US/O3 system, individual ozonolysis and sonolysis, the decomposition rate of p-chlorophenol reached 78.78%, 56.20%, 2.79% after a 16-min reaction while its CODcr (chemical oxygen demand) removal rate was 97.02%, 62.17%, 3.67% after a 120-min reaction. The decomposition reaction of p-chlorophenol follows pseudo-first-order kinetics. The enhancement factors of p-chlorophenol and its CODcr under US/O3 system reached 63% and 237% respectively. The main intermediates during the decomposition include catechol, hydroquinone, p-benzoquinone, phenol, fumaric acid, maleic acid, oxalic acid and formic acid. The decomposition mechanism of p-chlorophenol was also discussed. PMID:15909343

Nitrosonium-catalyzed decomposition of s-nitrosothiols in solution: a theoretical and experimental study.

PubMed

Zhao, Yi-Lei; McCarren, Patrick R; Houk, K N; Choi, Bo Yoon; Toone, Eric J

2005-08-10

The decomposition of S-nitrosothiols (RSNO) in solution under oxidative conditions is significantly faster than can be accounted for by homolysis of the S-N bond. Here we propose a cationic chain mechanism in which nitrosation of nitrosothiol produces a nitrosated cation that, in turn, reacts with a second nitrosothiol to produce nitrosated disulfide and the NO dimer. The nitrosated disulfide acts as a source of nitrosonium for nitrosothiol nitrosation, completing the catalytic cycle. The mechanism accounts for several unexplained facets of nitrosothiol chemistry in solution, including the observation that the decomposition of an RSNO is accelerated by O(2), mixtures of O(2) and NO, and other oxidants, that decomposition is inhibited by thiols and other antioxidants, that decomposition is dependent on sulfur substitution, and that decomposition often shows nonintegral kinetic orders.

Density-dependent liquid nitromethane decomposition: molecular dynamics simulations based on ReaxFF.

PubMed

Rom, Naomi; Zybin, Sergey V; van Duin, Adri C T; Goddard, William A; Zeiri, Yehuda; Katz, Gil; Kosloff, Ronnie

2011-09-15

The decomposition mechanism of hot liquid nitromethane at various compressions was studied using reactive force field (ReaxFF) molecular dynamics simulations. A competition between two different initial thermal decomposition schemes is observed, depending on compression. At low densities, unimolecular C-N bond cleavage is the dominant route, producing CH(3) and NO(2) fragments. As density and pressure rise approaching the Chapman-Jouget detonation conditions (∼30% compression, >2500 K) the dominant mechanism switches to the formation of the CH(3)NO fragment via H-transfer and/or N-O bond rupture. The change in the decomposition mechanism of hot liquid NM leads to a different kinetic and energetic behavior, as well as products distribution. The calculated density dependence of the enthalpy change correlates with the change in initial decomposition reaction mechanism. It can be used as a convenient and useful global parameter for the detection of reaction dynamics. Atomic averaged local diffusion coefficients are shown to be sensitive to the reactions dynamics, and can be used to distinguish between time periods where chemical reactions occur and diffusion-dominated, nonreactive time periods. © 2011 American Chemical Society

Thermal Decomposition Mechanism of CL-20 at Different Temperatures by ReaxFF Reactive Molecular Dynamics Simulations.

PubMed

Wang, Fuping; Chen, Lang; Geng, Deshen; Wu, Junying; Lu, Jianying; Wang, Chen

2018-04-26

Hexanitrohexaazaisowurtzitane (CL-20) has a high detonation velocity and pressure, but its sensitivity is also high, which somewhat limits its applications. Therefore, it is important to understand the mechanism and characteristics of thermal decomposition of CL-20. In this study, a ε-CL-20 supercell was constructed and ReaxFF-lg reactive molecular dynamics simulations were performed to investigate thermal decomposition of ε-CL-20 at various temperatures (2000, 2500, 2750, 3000, 3250, and 3500 K). The mechanism of thermal decomposition of CL-20 was analyzed from the aspects of potential energy evolution, the primary reactions, and the intermediate and final product species. The effect of temperature on thermal decomposition of CL-20 is also discussed. The initial reaction path of thermal decomposition of CL-20 is N-NO 2 cleavage to form NO 2 , followed by C-N cleavage, leading to the destruction of the cage structure. A small number of clusters appear in the early reactions and disappear at the end of the reactions. The initial reaction path of CL-20 decomposition is the same at different temperatures. However, as the temperature increases, the decomposition rate of CL-20 increases and the cage structure is destroyed earlier. The temperature greatly affects the rate constants of H 2 O and N 2 , but it has little effect on the rate constants of CO 2 and H 2 .

Dynamics in the Decompositions Approach to Quantum Mechanics

NASA Astrophysics Data System (ADS)

Harding, John

2017-12-01

In Harding (Trans. Amer. Math. Soc. 348(5), 1839-1862 1996) it was shown that the direct product decompositions of any non-empty set, group, vector space, and topological space X form an orthomodular poset Fact X. This is the basis for a line of study in foundational quantum mechanics replacing Hilbert spaces with other types of structures. Here we develop dynamics and an abstract version of a time independent Schrödinger's equation in the setting of decompositions by considering representations of the group of real numbers in the automorphism group of the orthomodular poset Fact X of decompositions.

Thermal Decomposition Behavior of Hydroxytyrosol (HT) in Nitrogen Atmosphere Based on TG-FTIR Methods.

PubMed

Tu, Jun-Ling; Yuan, Jiao-Jiao

2018-02-13

The thermal decomposition behavior of olive hydroxytyrosol (HT) was first studied using thermogravimetry (TG). Cracked chemical bond and evolved gas analysis during the thermal decomposition process of HT were also investigated using thermogravimetry coupled with infrared spectroscopy (TG-FTIR). Thermogravimetry-Differential thermogravimetry (TG-DTG) curves revealed that the thermal decomposition of HT began at 262.8 °C and ended at 409.7 °C with a main mass loss. It was demonstrated that a high heating rate (over 20 K·min -1 ) restrained the thermal decomposition of HT, resulting in an obvious thermal hysteresis. Furthermore, a thermal decomposition kinetics investigation of HT indicated that the non-isothermal decomposition mechanism was one-dimensional diffusion (D1), integral form g ( x ) = x ², and differential form f ( x ) = 1/(2 x ). The four combined approaches were employed to calculate the activation energy ( E = 128.50 kJ·mol -1 ) and Arrhenius preexponential factor (ln A = 24.39 min -1 ). In addition, a tentative mechanism of HT thermal decomposition was further developed. The results provide a theoretical reference for the potential thermal stability of HT.

Dispersion- and Exchange-Corrected Density Functional Theory for Sodium Ion Hydration.

PubMed

Soniat, Marielle; Rogers, David M; Rempe, Susan B

2015-07-14

A challenge in density functional theory is developing functionals that simultaneously describe intermolecular electron correlation and electron delocalization. Recent exchange-correlation functionals address those two issues by adding corrections important at long ranges: an atom-centered pairwise dispersion term to account for correlation and a modified long-range component of the electron exchange term to correct for delocalization. Here we investigate how those corrections influence the accuracy of binding free energy predictions for sodium-water clusters. We find that the dual-corrected ωB97X-D functional gives cluster binding energies closest to high-level ab initio methods (CCSD(T)). Binding energy decomposition shows that the ωB97X-D functional predicts the smallest ion-water (pairwise) interaction energy and larger multibody contributions for a four-water cluster than most other functionals - a trend consistent with CCSD(T) results. Also, ωB97X-D produces the smallest amounts of charge transfer and the least polarizable waters of the density functionals studied, which mimics the lower polarizability of CCSD. When compared with experimental binding free energies, however, the exchange-corrected CAM-B3LYP functional performs best (error <1 kcal/mol), possibly because of its parametrization to experimental formation enthalpies. For clusters containing more than four waters, "split-shell" coordination must be considered to obtain accurate free energies in comparison with experiment.

Effect of Isomorphous Substitution on the Thermal Decomposition Mechanism of Hydrotalcites

PubMed Central

Crosby, Sergio; Tran, Doanh; Cocke, David; Duraia, El-Shazly M.; Beall, Gary W.

2014-01-01

Hydrotalcites have many important applications in catalysis, wastewater treatment, gene delivery and polymer stabilization, all depending on preparation history and treatment scenarios. In catalysis and polymer stabilization, thermal decomposition is of great importance. Hydrotalcites form easily with atmospheric carbon dioxide and often interfere with the study of other anion containing systems, particularly if formed at room temperature. The dehydroxylation and decomposition of carbonate occurs simultaneously, making it difficult to distinguish the dehydroxylation mechanisms directly. To date, the majority of work on understanding the decomposition mechanism has utilized hydrotalcite precipitated at room temperature. In this study, evolved gas analysis combined with thermal analysis has been used to show that CO2 contamination is problematic in materials being formed at RT that are poorly crystalline. This has led to some dispute as to the nature of the dehydroxylation mechanism. In this paper, data for the thermal decomposition of the chloride form of hydrotalcite are reported. In addition, carbonate-free hydrotalcites have been synthesized with different charge densities and at different growth temperatures. This combination of parameters has allowed a better understanding of the mechanism of dehydroxylation and the role that isomorphous substitution plays in these mechanisms to be delineated. In addition, the effect of anion type on thermal stability is also reported. A stepwise dehydroxylation model is proposed that is mediated by the level of aluminum substitution. PMID:28788231

In silico local structure approach: a case study on outer membrane proteins.

PubMed

Martin, Juliette; de Brevern, Alexandre G; Camproux, Anne-Claude

2008-04-01

The detection of Outer Membrane Proteins (OMP) in whole genomes is an actual question, their sequence characteristics have thus been intensively studied. This class of protein displays a common beta-barrel architecture, formed by adjacent antiparallel strands. However, due to the lack of available structures, few structural studies have been made on this class of proteins. Here we propose a novel OMP local structure investigation, based on a structural alphabet approach, i.e., the decomposition of 3D structures using a library of four-residue protein fragments. The optimal decomposition of structures using hidden Markov model results in a specific structural alphabet of 20 fragments, six of them dedicated to the decomposition of beta-strands. This optimal alphabet, called SA20-OMP, is analyzed in details, in terms of local structures and transitions between fragments. It highlights a particular and strong organization of beta-strands as series of regular canonical structural fragments. The comparison with alphabets learned on globular structures indicates that the internal organization of OMP structures is more constrained than in globular structures. The analysis of OMP structures using SA20-OMP reveals some recurrent structural patterns. The preferred location of fragments in the distinct regions of the membrane is investigated. The study of pairwise specificity of fragments reveals that some contacts between structural fragments in beta-sheets are clearly favored whereas others are avoided. This contact specificity is stronger in OMP than in globular structures. Moreover, SA20-OMP also captured sequential information. This can be integrated in a scoring function for structural model ranking with very promising results. (c) 2007 Wiley-Liss, Inc.

Distance-Based Functional Diversity Measures and Their Decomposition: A Framework Based on Hill Numbers

PubMed Central

Chiu, Chun-Huo; Chao, Anne

2014-01-01

Hill numbers (or the “effective number of species”) are increasingly used to characterize species diversity of an assemblage. This work extends Hill numbers to incorporate species pairwise functional distances calculated from species traits. We derive a parametric class of functional Hill numbers, which quantify “the effective number of equally abundant and (functionally) equally distinct species” in an assemblage. We also propose a class of mean functional diversity (per species), which quantifies the effective sum of functional distances between a fixed species to all other species. The product of the functional Hill number and the mean functional diversity thus quantifies the (total) functional diversity, i.e., the effective total distance between species of the assemblage. The three measures (functional Hill numbers, mean functional diversity and total functional diversity) quantify different aspects of species trait space, and all are based on species abundance and species pairwise functional distances. When all species are equally distinct, our functional Hill numbers reduce to ordinary Hill numbers. When species abundances are not considered or species are equally abundant, our total functional diversity reduces to the sum of all pairwise distances between species of an assemblage. The functional Hill numbers and the mean functional diversity both satisfy a replication principle, implying the total functional diversity satisfies a quadratic replication principle. When there are multiple assemblages defined by the investigator, each of the three measures of the pooled assemblage (gamma) can be multiplicatively decomposed into alpha and beta components, and the two components are independent. The resulting beta component measures pure functional differentiation among assemblages and can be further transformed to obtain several classes of normalized functional similarity (or differentiation) measures, including N-assemblage functional generalizations of the classic Jaccard, Sørensen, Horn and Morisita-Horn similarity indices. The proposed measures are applied to artificial and real data for illustration. PMID:25000299

Distance-based functional diversity measures and their decomposition: a framework based on Hill numbers.

PubMed

Chiu, Chun-Huo; Chao, Anne

2014-01-01

Hill numbers (or the "effective number of species") are increasingly used to characterize species diversity of an assemblage. This work extends Hill numbers to incorporate species pairwise functional distances calculated from species traits. We derive a parametric class of functional Hill numbers, which quantify "the effective number of equally abundant and (functionally) equally distinct species" in an assemblage. We also propose a class of mean functional diversity (per species), which quantifies the effective sum of functional distances between a fixed species to all other species. The product of the functional Hill number and the mean functional diversity thus quantifies the (total) functional diversity, i.e., the effective total distance between species of the assemblage. The three measures (functional Hill numbers, mean functional diversity and total functional diversity) quantify different aspects of species trait space, and all are based on species abundance and species pairwise functional distances. When all species are equally distinct, our functional Hill numbers reduce to ordinary Hill numbers. When species abundances are not considered or species are equally abundant, our total functional diversity reduces to the sum of all pairwise distances between species of an assemblage. The functional Hill numbers and the mean functional diversity both satisfy a replication principle, implying the total functional diversity satisfies a quadratic replication principle. When there are multiple assemblages defined by the investigator, each of the three measures of the pooled assemblage (gamma) can be multiplicatively decomposed into alpha and beta components, and the two components are independent. The resulting beta component measures pure functional differentiation among assemblages and can be further transformed to obtain several classes of normalized functional similarity (or differentiation) measures, including N-assemblage functional generalizations of the classic Jaccard, Sørensen, Horn and Morisita-Horn similarity indices. The proposed measures are applied to artificial and real data for illustration.

xEMD procedures as a data - Assisted filtering method

NASA Astrophysics Data System (ADS)

Machrowska, Anna; Jonak, Józef

2018-01-01

The article presents the possibility of using Empirical Mode Decomposition (EMD), Ensemble Empirical Mode Decomposition (EEMD), Complete Ensemble Empirical Mode Decomposition with Adaptive Noise (CEEMDAN) and Improved Complete Ensemble Empirical Mode Decomposition (ICEEMD) algorithms for mechanical system condition monitoring applications. There were presented the results of the xEMD procedures used for vibration signals of system in different states of wear.

Decomposition Mechanism and Decomposition Promoting Factors of Waste Hard Metal for Zinc Decomposition Process (ZDP)

NASA Astrophysics Data System (ADS)

Pee, J. H.; Kim, Y. J.; Kim, J. Y.; Seong, N. E.; Cho, W. S.; Kim, K. J.

2011-10-01

Decomposition promoting factors and decomposition mechanism in the zinc decomposition process of waste hard metals which are composed mostly of tungsten carbide and cobalt were evaluated. Zinc volatility amount was suppressed and zinc steam pressure was produced in the reaction graphite crucible inside an electric furnace for ZDP. Reaction was done for 2 hrs at 650 °C, which 100 % decomposed the waste hard metals that were over 30 mm thick. As for the separation-decomposition of waste hard metals, zinc melted alloy formed a liquid composed of a mixture of γ-β1 phase from the cobalt binder layer (reaction interface). The volume of reacted zone was expanded and the waste hard metal layer was decomposed-separated horizontally from the hard metal. Zinc used in the ZDP process was almost completely removed-collected by decantation and volatilization-collection process at 1000 °C. The small amount of zinc remaining in the tungsten carbide-cobalt powder which was completely decomposed was fully removed by using phosphate solution which had a slow cobalt dissolution speed.

Unraveling the physical meaning of the Jaffe-Manohar decomposition of the nucleon spin

NASA Astrophysics Data System (ADS)

Wakamatsu, M.

2016-09-01

A general consensus now is that there are two physically inequivalent complete decompositions of the nucleon spin, i.e. the decomposition of the canonical type and that of mechanical type. The well-known Jaffe-Manohar decomposition is of the former type. Unfortunately, there is a wide-spread misbelief that this decomposition matches the partonic picture, which states that motion of quarks in the nucleon is approximately free. In the present monograph, we reveal that this understanding is not necessarily correct and that the Jaffe-Manohar decomposition is not such a decomposition, which natively reflects the intrinsic (or static) orbital angular momentum structure of the nucleon.

In situ spectroscopic studies on vapor phase catalytic decomposition of dimethyl oxalate.

PubMed

Hegde, Shweta; Tharpa, Kalsang; Akuri, Satyanarayana Reddy; K, Rakesh; Kumar, Ajay; Deshpande, Raj; Nair, Sreejit A

2017-03-15

Dimethyl Oxalate (DMO) has recently gained prominence as a valuable intermediate for the production of compounds of commercial importance. The stability of DMO is poor and hence this can result in the decomposition of DMO under reaction conditions. The mechanism of DMO decomposition is however not reported and more so on catalytic surfaces. Insights into the mechanism of decomposition would help in designing catalysts for its effective molecular transformation. It is well known that DMO is sensitive to moisture, which can also be a factor contributing to its decomposition. The present work reports the results of decomposition of DMO on various catalytic materials. The materials studied consist of acidic (γ-Al 2 O 3 ), basic (MgO), weakly acidic (ZnAl 2 O 4 ) and neutral surfaces such as α-Al 2 O 3 and mesoporous precipitated SiO 2 . Infrared spectroscopy is used to identify the nature of adsorption of the molecule on the various surfaces. The spectroscopy study is done at a temperature of 200 °C, which is the onset of gas phase decomposition of DMO. The results indicate that the stability of DMO is lower than the corresponding acid, i.e. oxalic acid. It is also one of the products of decomposition. Spectroscopic data suggest that DMO decomposition is related to surface acidity and the extent of decomposition depends on the number of surface hydroxyl groups. Decomposition was also observed on α-Al 2 O 3 , which was attributed to the residual surface hydroxyl groups. DMO decomposition to oxalic acid was not observed on the basic surface (MgO).

The influence of arene-ring size on stacking interaction with canonical base pairs

NASA Astrophysics Data System (ADS)

Formánek, Martin; Burda, Jaroslav V.

2014-04-01

Stacking interactions between aromatic molecules (benzene, p-cymene, biphenyl, and di- and tetra-hydrogen anthracene) and G.C and A.T canonical Watson-Crick (WC) base pairs are explored. Two functionals with dispersion corrections: ω-B97XD and B3LYP-D3 are used. For a comparison also the MP2 and B3LYP-D3/PCM methods were used for the most stable p-cymene…WC geometries. It was found that the stacking interaction increases with the size of π-conjugation system. Its extent is in agreement with experimental finding on anticancer activity of Ru(II) piano-stool complexes where intercalation of these aromatic molecules should play an important role. The explored structures are considered as ternary system so that decomposition of the interaction energy to pairwise and non-additivity contributions is also examined.

Causal mechanisms of soil organic matter decomposition: Deconstructing salinity and flooding impacts in coastal wetlands

USGS Publications Warehouse

Stagg, Camille L.; Schoolmaster, Donald; Krauss, Ken W.; Cormier, Nicole; Conner, William H.

2017-01-01

Coastal wetlands significantly contribute to global carbon storage potential. Sea-level rise and other climate change-induced disturbances threaten coastal wetland sustainability and carbon storage capacity. It is critical that we understand the mechanisms controlling wetland carbon loss so that we can predict and manage these resources in anticipation of climate change. However, our current understanding of the mechanisms that control soil organic matter decomposition, in particular the impacts of elevated salinity, are limited, and literature reports are contradictory. In an attempt to improve our understanding of these complex processes, we measured root and rhizome decomposition and developed a causal model to identify and quantify the mechanisms that influence soil organic matter decomposition in coastal wetlands that are impacted by sea-level rise. We identified three causal pathways: 1) a direct pathway representing the effects of flooding on soil moisture, 2) a direct pathway representing the effects of salinity on decomposer microbial communities and soil biogeochemistry, and 3) an indirect pathway representing the effects of salinity on litter quality through changes in plant community composition over time. We used this model to test the effects of alternate scenarios on the response of tidal freshwater forested wetlands and oligohaline marshes to short- and long-term climate-induced disturbances of flooding and salinity. In tidal freshwater forested wetlands, the model predicted less decomposition in response to drought, hurricane salinity pulsing, and long-term sea-level rise. In contrast, in the oligohaline marsh, the model predicted no change in response to sea-level rise, and increased decomposition following a drought or a hurricane salinity pulse. Our results show that it is critical to consider the temporal scale of disturbance and the magnitude of exposure when assessing the effects of salinity intrusion on carbon mineralization in coastal wetlands. Here we identify three causal mechanisms that can reconcile disparities between long-term and short-term salinity impacts on organic matter decomposition.

Causal mechanisms of soil organic matter decomposition: deconstructing salinity and flooding impacts in coastal wetlands.

PubMed

Stagg, Camille L; Schoolmaster, Donald R; Krauss, Ken W; Cormier, Nicole; Conner, William H

2017-08-01

Coastal wetlands significantly contribute to global carbon storage potential. Sea-level rise and other climate-change-induced disturbances threaten coastal wetland sustainability and carbon storage capacity. It is critical that we understand the mechanisms controlling wetland carbon loss so that we can predict and manage these resources in anticipation of climate change. However, our current understanding of the mechanisms that control soil organic matter decomposition, in particular the impacts of elevated salinity, are limited, and literature reports are contradictory. In an attempt to improve our understanding of these complex processes, we measured root and rhizome decomposition and developed a causal model to identify and quantify the mechanisms that influence soil organic matter decomposition in coastal wetlands that are impacted by sea-level rise. We identified three causal pathways: (1) a direct pathway representing the effects of flooding on soil moisture, (2) a direct pathway representing the effects of salinity on decomposer microbial communities and soil biogeochemistry, and (3) an indirect pathway representing the effects of salinity on litter quality through changes in plant community composition over time. We used this model to test the effects of alternate scenarios on the response of tidal freshwater forested wetlands and oligohaline marshes to short- and long-term climate-induced disturbances of flooding and salinity. In tidal freshwater forested wetlands, the model predicted less decomposition in response to drought, hurricane salinity pulsing, and long-term sea-level rise. In contrast, in the oligohaline marsh, the model predicted no change in response to drought and sea-level rise, and increased decomposition following a hurricane salinity pulse. Our results show that it is critical to consider the temporal scale of disturbance and the magnitude of exposure when assessing the effects of salinity intrusion on carbon mineralization in coastal wetlands. Here, we identify three causal mechanisms that can reconcile disparities between long-term and short-term salinity impacts on organic matter decomposition. © 2017 by the Ecological Society of America.

Analysis of Decomposition for Structure I Methane Hydrate by Molecular Dynamics Simulation

NASA Astrophysics Data System (ADS)

Wei, Na; Sun, Wan-Tong; Meng, Ying-Feng; Liu, An-Qi; Zhou, Shou-Wei; Guo, Ping; Fu, Qiang; Lv, Xin

2018-05-01

Under multi-nodes of temperatures and pressures, microscopic decomposition mechanisms of structure I methane hydrate in contact with bulk water molecules have been studied through LAMMPS software by molecular dynamics simulation. Simulation system consists of 482 methane molecules in hydrate and 3027 randomly distributed bulk water molecules. Through analyses of simulation results, decomposition number of hydrate cages, density of methane molecules, radial distribution function for oxygen atoms, mean square displacement and coefficient of diffusion of methane molecules have been studied. A significant result shows that structure I methane hydrate decomposes from hydrate-bulk water interface to hydrate interior. As temperature rises and pressure drops, the stabilization of hydrate will weaken, decomposition extent will go deep, and mean square displacement and coefficient of diffusion of methane molecules will increase. The studies can provide important meanings for the microscopic decomposition mechanisms analyses of methane hydrate.

[Progress in Raman spectroscopic measurement of methane hydrate].

PubMed

Xu, Feng; Zhu, Li-hua; Wu, Qiang; Xu, Long-jun

2009-09-01

Complex thermodynamics and kinetics problems are involved in the methane hydrate formation and decomposition, and these problems are crucial to understanding the mechanisms of hydrate formation and hydrate decomposition. However, it was difficult to accurately obtain such information due to the difficulty of measurement since methane hydrate is only stable under low temperature and high pressure condition, and until recent years, methane hydrate has been measured in situ using Raman spectroscopy. Raman spectroscopy, a non-destructive and non-invasive technique, is used to study vibrational modes of molecules. Studies of methane hydrate using Raman spectroscopy have been developed over the last decade. The Raman spectra of CH4 in vapor phase and in hydrate phase are presented in this paper. The progress in the research on methane hydrate formation thermodynamics, formation kinetics, decomposition kinetics and decomposition mechanism based on Raman spectroscopic measurements in the laboratory and deep sea are reviewed. Formation thermodynamic studies, including in situ observation of formation condition of methane hydrate, analysis of structure, and determination of hydrate cage occupancy and hydration numbers by using Raman spectroscopy, are emphasized. In the aspect of formation kinetics, research on variation in hydrate cage amount and methane concentration in water during the growth of hydrate using Raman spectroscopy is also introduced. For the methane hydrate decomposition, the investigation associated with decomposition mechanism, the mutative law of cage occupancy ratio and the formulation of decomposition rate in porous media are described. The important aspects for future hydrate research based on Raman spectroscopy are discussed.

Remarkable sequence conservation of the last intron in the PKD1 gene.

PubMed

Rodova, Marianna; Islam, M Rafiq; Peterson, Kenneth R; Calvet, James P

2003-10-01

The last intron of the PKD1 gene (intron 45) was found to have exceptionally high sequence conservation across four mammalian species: human, mouse, rat, and dog. This conservation did not extend to the comparable intron in pufferfish. Pairwise comparisons for intron 45 showed 91% identity (human vs. dog) to 100% identity (mouse vs. rat) for an average for all four species of 94% identity. In contrast, introns 43 and 44 of the PKD1 gene had average pairwise identities of 57% and 54%, and exons 43, 44, and 45 and the coding region of exon 46 had average pairwise identities of 80%, 84%, 82%, and 80%. Intron 45 is 90 to 95 bp in length, with the major region of sequence divergence being in a central 4-bp to 9-bp variable region. RNA secondary structure analysis of intron 45 predicts a branching stem-loop structure in which the central variable region lies in one loop and the putative branch point sequence lies in another loop, suggesting that the intron adopts a specific stem-loop structure that may be important for its removal. Although intron 45 appears to conform to the class of small, G-triplet-containing introns that are spliced by a mechanism utilizing intron definition, its high sequence conservation may be a reflection of constraints imposed by a unique mechanism that coordinates splicing of this last PKD1 intron with polyadenylation.

ChIP-PIT: Enhancing the Analysis of ChIP-Seq Data Using Convex-Relaxed Pair-Wise Interaction Tensor Decomposition.

PubMed

Zhu, Lin; Guo, Wei-Li; Deng, Su-Ping; Huang, De-Shuang

2016-01-01

In recent years, thanks to the efforts of individual scientists and research consortiums, a huge amount of chromatin immunoprecipitation followed by high-throughput sequencing (ChIP-seq) experimental data have been accumulated. Instead of investigating them independently, several recent studies have convincingly demonstrated that a wealth of scientific insights can be gained by integrative analysis of these ChIP-seq data. However, when used for the purpose of integrative analysis, a serious drawback of current ChIP-seq technique is that it is still expensive and time-consuming to generate ChIP-seq datasets of high standard. Most researchers are therefore unable to obtain complete ChIP-seq data for several TFs in a wide variety of cell lines, which considerably limits the understanding of transcriptional regulation pattern. In this paper, we propose a novel method called ChIP-PIT to overcome the aforementioned limitation. In ChIP-PIT, ChIP-seq data corresponding to a diverse collection of cell types, TFs and genes are fused together using the three-mode pair-wise interaction tensor (PIT) model, and the prediction of unperformed ChIP-seq experimental results is formulated as a tensor completion problem. Computationally, we propose efficient first-order method based on extensions of coordinate descent method to learn the optimal solution of ChIP-PIT, which makes it particularly suitable for the analysis of massive scale ChIP-seq data. Experimental evaluation the ENCODE data illustrate the usefulness of the proposed model.

Initial mechanisms for the unimolecular decomposition of electronically excited bisfuroxan based energetic materials.

PubMed

Yuan, Bing; Bernstein, Elliot R

2017-01-07

Unimolecular decomposition of energetic molecules, 3,3'-diamino-4,4'-bisfuroxan (labeled as A) and 4,4'-diamino-3,3'-bisfuroxan (labeled as B), has been explored via 226/236 nm single photon laser excitation/decomposition. These two energetic molecules, subsequent to UV excitation, create NO as an initial decomposition product at the nanosecond excitation energies (5.0-5.5 eV) with warm vibrational temperature (1170 ± 50 K for A, 1400 ± 50 K for B) and cold rotational temperature (<55 K). Initial decomposition mechanisms for these two electronically excited, isolated molecules are explored at the complete active space self-consistent field (CASSCF(12,12)/6-31G(d)) level with and without MP2 correction. Potential energy surface calculations illustrate that conical intersections play an essential role in the calculated decomposition mechanisms. Based on experimental observations and theoretical calculations, NO product is released through opening of the furoxan ring: ring opening can occur either on the S 1 excited or S 0 ground electronic state. The reaction path with the lowest energetic barrier is that for which the furoxan ring opens on the S 1 state via the breaking of the N1-O1 bond. Subsequently, the molecule moves to the ground S 0 state through related ring-opening conical intersections, and an NO product is formed on the ground state surface with little rotational excitation at the last NO dissociation step. For the ground state ring opening decomposition mechanism, the N-O bond and C-N bond break together in order to generate dissociated NO. With the MP2 correction for the CASSCF(12,12) surface, the potential energies of molecules with dissociated NO product are in the range from 2.04 to 3.14 eV, close to the theoretical result for the density functional theory (B3LYP) and MP2 methods. The CASMP2(12,12) corrected approach is essential in order to obtain a reasonable potential energy surface that corresponds to the observed decomposition behavior of these molecules. Apparently, highly excited states are essential for an accurate representation of the kinetics and dynamics of excited state decomposition of both of these bisfuroxan energetic molecules. The experimental vibrational temperatures of NO products of A and B are about 800-1000 K lower than previously studied energetic molecules with NO as a decomposition product.

Effect of aging temperature on phase decomposition and mechanical properties in cast duplex stainless steels

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mburu, Sarah; Kolli, R. Prakash; Perea, Daniel E.

The microstructure and mechanical properties in unaged and thermally aged (at 280 °C, 320 °C, 360 °C, and 400 °C to 4300 h) CF–3 and CF–8 cast duplex stainless steels (CDSS) are investigated. The unaged CF–8 steel has Cr-rich M 23C 6 carbides located at the δ–ferrite/γ–austenite heterophase interfaces that were not observed in the CF–3 steel and this corresponds to a difference in mechanical properties. Both unaged steels exhibit incipient spinodal decomposition into Fe-rich α–domains and Cr-rich α’–domains. During aging, spinodal decomposition progresses and the mean wavelength (MW) and mean amplitude (MA) of the compositional fluctuations increase as amore » function of aging temperature. Additionally, G–phase precipitates form between the spinodal decomposition domains in CF–3 at 360 °C and 400 °C and in CF–8 at 400 °C. Finally, the microstructural evolution is correlated to changes in mechanical properties.« less

Effect of aging temperature on phase decomposition and mechanical properties in cast duplex stainless steels

DOE PAGES

Mburu, Sarah; Kolli, R. Prakash; Perea, Daniel E.; ...

2017-03-06

The microstructure and mechanical properties in unaged and thermally aged (at 280 °C, 320 °C, 360 °C, and 400 °C to 4300 h) CF–3 and CF–8 cast duplex stainless steels (CDSS) are investigated. The unaged CF–8 steel has Cr-rich M 23C 6 carbides located at the δ–ferrite/γ–austenite heterophase interfaces that were not observed in the CF–3 steel and this corresponds to a difference in mechanical properties. Both unaged steels exhibit incipient spinodal decomposition into Fe-rich α–domains and Cr-rich α’–domains. During aging, spinodal decomposition progresses and the mean wavelength (MW) and mean amplitude (MA) of the compositional fluctuations increase as amore » function of aging temperature. Additionally, G–phase precipitates form between the spinodal decomposition domains in CF–3 at 360 °C and 400 °C and in CF–8 at 400 °C. Finally, the microstructural evolution is correlated to changes in mechanical properties.« less

Effect of aging temperature on phase decomposition and mechanical properties in cast duplex stainless steels

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mburu, Sarah; Kolli, R. Prakash; Perea, Daniel E.

The microstructure and mechanical properties in unaged and thermally aged (at 280 oC, 320 oC, 360 oC, and 400 oC to 4300 h) CF–3 and CF–8 cast duplex stainless steels (CDSS) are investigated. The unaged CF–8 steel has Cr-rich M23C6 carbides located at the δ–ferrite/γ– austenite heterophase interfaces that were not observed in the CF–3 steel and this corresponds to a difference in mechanical properties. Both unaged steels exhibit incipient spinodal decomposition into Fe-rich α–domains and Cr-rich α’–domains. During aging, spinodal decomposition progresses and the mean wavelength (MW) and mean amplitude (MA) of the compositional fluctuations increase as a functionmore » of aging temperature. Additionally, G–phase precipitates form between the spinodal decomposition domains in CF–3 at 360 oC and 400 oC and in CF–8 at 400 oC. The microstructural evolution is correlated to changes in mechanical properties.« less

Experimental and DFT simulation study of a novel felodipine cocrystal: Characterization, dissolving properties and thermal decomposition kinetics.

PubMed

Yang, Caiqin; Guo, Wei; Lin, Yulong; Lin, Qianqian; Wang, Jiaojiao; Wang, Jing; Zeng, Yanli

2018-05-30

In this study, a new cocrystal of felodipine (Fel) and glutaric acid (Glu) with a high dissolution rate was developed using the solvent ultrasonic method. The prepared cocrystal was characterized using X-ray powder diffraction, differential scanning calorimetry, thermogravimetric (TG) analysis, and infrared (IR) spectroscopy. To provide basic information about the optimization of pharmaceutical preparations of Fel-based cocrystals, this work investigated the thermal decomposition kinetics of the Fel-Glu cocrystal through non-isothermal thermogravimetry. Density functional theory (DFT) simulations were also performed on the Fel monomer and the trimolecular cocrystal compound for exploring the mechanisms underlying hydrogen bonding formation and thermal decomposition. Combined results of IR spectroscopy and DFT simulation verified that the Fel-Glu cocrystal formed via the NH⋯OC and CO⋯HO hydrogen bonds between Fel and Glu at the ratio of 1:2. The TG/derivative TG curves indicated that the thermal decomposition of the Fel-Glu cocrystal underwent a two-step process. The apparent activation energy (E a ) and pre-exponential factor (A) of the thermal decomposition for the first stage were 84.90 kJ mol -1 and 7.03 × 10 7  min -1 , respectively. The mechanism underlying thermal decomposition possibly involved nucleation and growth, with the integral mechanism function G(α) of α 3/2 . DFT calculation revealed that the hydrogen bonding between Fel and Glu weakened the terminal methoxyl, methyl, and ethyl groups in the Fel molecule. As a result, these groups were lost along with the Glu molecule in the first thermal decomposition. In conclusion, the formed cocrystal exhibited different thermal decomposition kinetics and showed different E a , A, and shelf life from the intact active pharmaceutical ingredient. Copyright © 2018 Elsevier B.V. All rights reserved.

Molecular dynamics simulations of methane hydrate decomposition.

PubMed

Myshakin, Evgeniy M; Jiang, Hao; Warzinski, Robert P; Jordan, Kenneth D

2009-03-12

Molecular dynamics simulations have been carried out to study decomposition of methane hydrate at different cage occupancies. The decomposition rate is found to depend sensitively on the hydration number. The rate of the destruction of the cages displays Arrhenius behavior, consistent with an activated mechanism. During the simulations, reversible formation of partial water cages around methane molecules in the liquid was observed at the interface at temperatures above the computed hydrate decomposition temperature.

Mechanism of thermal decomposition of K2FeO4 and BaFeO4: A review

NASA Astrophysics Data System (ADS)

Sharma, Virender K.; Machala, Libor

2016-12-01

This paper presents thermal decomposition of potassium ferrate(VI) (K2FeO4) and barium ferrate(VI) (BaFeO4) in air and nitrogen atmosphere. Mössbauer spectroscopy and nuclear forward scattering (NFS) synchrotron radiation approaches are reviewed to advance understanding of electron-transfer processes involved in reduction of ferrate(VI) to Fe(III) phases. Direct evidences of Fe V and Fe IV as intermediate iron species using the applied techniques are given. Thermal decomposition of K2FeO4 involved Fe V, Fe IV, and K3FeO3 as intermediate species while BaFeO3 (i.e. Fe IV) was the only intermediate species during the decomposition of BaFeO4. Nature of ferrite species, formed as final Fe(III) species, of thermal decomposition of K2FeO4 and BaFeO4 under different conditions are evaluated. Steps of the mechanisms of thermal decomposition of ferrate(VI), which reasonably explained experimental observations of applied approaches in conjunction with thermal and surface techniques, are summarized.

Spectroscopic and Computational Investigation of Room-Temperature Decomposition of a Chemical Warfare Agent Simulant on Polycrystalline Cupric Oxide

DOE PAGES

Trotochaud, Lena; Tsyshevsky, Roman; Holdren, Scott; ...

2017-08-21

Certain organophosphorus molecules are infamous due to their use as highly toxic nerve agents. The filtration materials currently in common use for protection against chemical warfare agents were designed before organophosphorus compounds were used as chemical weapons. A better understanding of the surface chemistry between simulant molecules and the individual filtration-material components is a critical precursor to the development of more effective materials for filtration, destruction, decontamination, and/or sensing of nerve agents. Here, we report on the surface adsorption and reactions of a sarin simulant molecule, dimethyl methylphosphonate (DMMP), with cupric oxide surfaces. In situ ambient pressure X-ray photoelectron andmore » infrared spectroscopies are coupled with density functional calculations to propose mechanisms for DMMP decomposition on CuO. We find extensive room temperature decomposition of DMMP on CuO, with the majority of decomposition fragments bound to the CuO surface. We observe breaking of PO-CH3, P-OCH3, and P-CH3bonds at room temperature. On the basis of these results, we identify specific DMMP decomposition mechanisms not seen on other metal oxides. Participation of lattice oxygen in the decomposition mechanism leads to significant changes in chemical and electronic surface environment, which are manifest in the spectroscopic and computational data. This study establishes a computational baseline for the study of highly toxic organophosphorous compounds on metal oxide surfaces.« less

Spectroscopic and Computational Investigation of Room-Temperature Decomposition of a Chemical Warfare Agent Simulant on Polycrystalline Cupric Oxide

DOE Office of Scientific and Technical Information (OSTI.GOV)

Trotochaud, Lena; Tsyshevsky, Roman; Holdren, Scott

Certain organophosphorus molecules are infamous due to their use as highly toxic nerve agents. The filtration materials currently in common use for protection against chemical warfare agents were designed before organophosphorus compounds were used as chemical weapons. A better understanding of the surface chemistry between simulant molecules and the individual filtration-material components is a critical precursor to the development of more effective materials for filtration, destruction, decontamination, and/or sensing of nerve agents. Here, we report on the surface adsorption and reactions of a sarin simulant molecule, dimethyl methylphosphonate (DMMP), with cupric oxide surfaces. In situ ambient pressure X-ray photoelectron andmore » infrared spectroscopies are coupled with density functional calculations to propose mechanisms for DMMP decomposition on CuO. We find extensive room temperature decomposition of DMMP on CuO, with the majority of decomposition fragments bound to the CuO surface. We observe breaking of PO-CH3, P-OCH3, and P-CH3bonds at room temperature. On the basis of these results, we identify specific DMMP decomposition mechanisms not seen on other metal oxides. Participation of lattice oxygen in the decomposition mechanism leads to significant changes in chemical and electronic surface environment, which are manifest in the spectroscopic and computational data. This study establishes a computational baseline for the study of highly toxic organophosphorous compounds on metal oxide surfaces.« less

Theoretical evidence of the observed kinetic order dependence on temperature during the N(2)O decomposition over Fe-ZSM-5.

PubMed

Guesmi, Hazar; Berthomieu, Dorothee; Bromley, Bryan; Coq, Bernard; Kiwi-Minsker, Lioubov

2010-03-28

The characterization of Fe/ZSM5 zeolite materials, the nature of Fe-sites active in N(2)O direct decomposition, as well as the rate limiting step are still a matter of debate. The mechanism of N(2)O decomposition on the binuclear oxo-hydroxo bridged extraframework iron core site [Fe(II)(mu-O)(mu-OH)Fe(II)](+) inside the ZSM-5 zeolite has been studied by combining theoretical and experimental approaches. The overall calculated path of N(2)O decomposition involves the oxidation of binuclear Fe(II) core sites by N(2)O (atomic alpha-oxygen formation) and the recombination of two surface alpha-oxygen atoms leading to the formation of molecular oxygen. Rate parameters computed using standard statistical mechanics and transition state theory reveal that elementary catalytic steps involved into N(2)O decomposition are strongly dependent on the temperature. This theoretical result was compared to the experimentally observed steady state kinetics of the N(2)O decomposition and temperature-programmed desorption (TPD) experiments. A switch of the reaction order with respect to N(2)O pressure from zero to one occurs at around 800 K suggesting a change of the rate determining step from the alpha-oxygen recombination to alpha-oxygen formation. The TPD results on the molecular oxygen desorption confirmed the mechanism proposed.

Photodegradation at day, microbial decomposition at night - decomposition in arid lands

NASA Astrophysics Data System (ADS)

Gliksman, Daniel; Gruenzweig, Jose

2014-05-01

Our current knowledge of decomposition in dry seasons and its role in carbon turnover is fragmentary. So far, decomposition during dry seasons was mostly attributed to abiotic mechanisms, mainly photochemical and thermal degradation, while the contribution of microorganisms to the decay process was excluded. We asked whether microbial decomposition occurs during the dry season and explored its interaction with photochemical degradation under Mediterranean climate. We conducted a litter bag experiment with local plant litter and manipulated litter exposure to radiation using radiation filters. We found notable rates of CO2 fluxes from litter which were related to microbial activity mainly during night-time throughout the dry season. This activity was correlated with litter moisture content and high levels of air humidity and dew. Day-time CO2 fluxes were related to solar radiation, and radiation manipulation suggested photodegradation as the underlying mechanism. In addition, a decline in microbial activity was followed by a reduction in photodegradation-related CO2 fluxes. The levels of microbial decomposition and photodegradation in the dry season were likely the factors influencing carbon mineralization during the subsequent wet season. This study showed that microbial decomposition can be a dominant contributor to CO2 emissions and mass loss in the dry season and it suggests a regulating effect of microbial activity on photodegradation. Microbial decomposition is an important contributor to the dry season decomposition and impacts the annual litter turn-over rates in dry regions. Global warming may lead to reduced moisture availability and dew deposition, which may greatly influence not only microbial decomposition of plant litter, but also photodegradation.

Influence of gamma-irradiation on the non-isothermal decomposition of calcium-gadolinium oxalate

NASA Astrophysics Data System (ADS)

Moharana, S. C.; Praharaj, J.; Bhatta, D.

Thermal decomposition of co-precipitated unirradiated and irradiated Ca-Gd oxalate has been studied by adopting differential thermal analysis (DTA) and thermogravimetric (TG) techniques. The reaction occurs through two stages corresponding to the decomposition of gadolinium oxalate (Gd-Ox) followed by that of calcium oxalate (Ca-Ox). The kinetic parameters for both the stages are calculated by using solid state reaction models and Coats-Redfern's equation. The co-precipitation as well as irradiation alter the DTA peak temperatures and the kinetic parameters of Ca-Ox. The decomposition of Gd-Ox follows the two dimensional Contracting area (R-2) mechanism, while that of Ca-Ox follows the Avrami-Erofeev (A(2)) mechanism (n =2), which are also exhibited by the co-precipitated and irradiated samples. Co-precipitation decreases the energy of activation and the pre-exponential factor of the individual components but the reverse phenomenon takes place upon irradiation of the co-precipitate. The mechanisms underlying the phenomena are explored.

Nano or micro? A mechanism on thermal decomposition of ammonium perchlorate catalyzed by cobalt oxalate.

PubMed

Zou, Min; Jiang, Xiaohong; Lu, Lude; Wang, Xin

2012-07-30

Micrometer-sized cobalt oxalates with different morphologies have been prepared in the presence of surfactants. The effect of catalysts morphology on the thermal decomposition of ammonium perchlorate (AP) was evaluated by differential thermal analysis (DSC). Remarkably, contrary to the well-accepted concepts, no direct relationship between the morphologies of catalysts and their activities has been observed. Based on the structural and morphological variation of the catalysts during the reaction, a catalytic mechanism on thermal decomposition of ammonium perchlorate catalyzed by cobalt oxalate is proposed. We believe that it is the "self-crushing and self-distributed" occurred within the reaction that really works for the improvement of the overall catalytic activities. In this process, both catalysts and reactants have been crashed and distributed uniformly in an automatic way. This work provides an in-depth insight into the thermal decomposition mechanism of AP as catalyzed by oxalates. Copyright © 2012 Elsevier B.V. All rights reserved.

Development of Novel Decontamination and Inerting Techniques for Explosives Contaminated Facilities. Phase 1. Identification and Evaluation of Novel Decontamination Concepts. Volume 1

DTIC Science & Technology

1983-07-01

the decomposition reaction (Leider, 1981; Kageyama, 1973; Wolfrom, 1956), 2) Hydrolysis of linkages between glucose units (Urbanski, 1964), 3... dehydration ), 2) Acceleration period (to 50 percent decomposition ), 3) First order reaction rate period. The products of thermal decomposition of...simple mechanism to clean an entire building at once. o Depending on the contaminant, thermal decomposition and or hydrolysis may occur. o May be

Determination of the thermal stability of perfluoropolyalkyl ethers by tensimetry

NASA Technical Reports Server (NTRS)

Helmick, Larry A.; Jones, William R., Jr.

1992-01-01

The thermal decomposition temperatures of several perfluoropolyalkyl ether fluids were determined with a computerized tensimeter. In general, the decomposition temperatures of the commercial fluids were all similar and significantly higher than those for noncommercial fluids. Correlation of the decomposition temperatures with the molecular structures of the primary components of the commercial fluids revealed that the stability of the fluids was not affected by carbon chain length, branching, or adjacent difluoroformal groups. Instead, stability was limited by the presence of small quantities of thermally unstable material and/or chlorine-containing material arising from the use of chlorine containing solvents during synthesis. Finally, correlation of decomposition temperatures with molecular weights for two fluids supports a chain cleavage reaction mechanism for one and an unzipping reaction mechanism for the other.

Explosive decomposition of hydrazine by rapid compression of a gas volume

NASA Technical Reports Server (NTRS)

Bunker, R. L.; Baker, D. L.; Lee, J. H. S.

1991-01-01

In the present investigation of the initiation mechanism and the explosion mode of hydrazine decomposition, a 20 cm-long column of liquid hydrazine was accelerated into a column of gaseous nitrogen, from which it was separated by a thin Teflon diaphragm, in a close-ended cylindrical chamber. Video data obtained reveal the formation of a froth generated by the acceleration of hydrazine into nitrogen at the liquid hydrazine-gaseous nitrogen interface. The explosive hydrazine decomposition had as its initiation mechanism the formation of a froth at a critical temperature; the explosion mode of hydrazine is a confined thermal runaway reaction.

Darwin v. 2.0: an interpreted computer language for the biosciences.

PubMed

Gonnet, G H; Hallett, M T; Korostensky, C; Bernardin, L

2000-02-01

We announce the availability of the second release of Darwin v. 2.0, an interpreted computer language especially tailored to researchers in the biosciences. The system is a general tool applicable to a wide range of problems. This second release improves Darwin version 1.6 in several ways: it now contains (1) a larger set of libraries touching most of the classical problems from computational biology (pairwise alignment, all versus all alignments, tree construction, multiple sequence alignment), (2) an expanded set of general purpose algorithms (search algorithms for discrete problems, matrix decomposition routines, complex/long integer arithmetic operations), (3) an improved language with a cleaner syntax, (4) better on-line help, and (5) a number of fixes to user-reported bugs. Darwin is made available for most operating systems free of char ge from the Computational Biochemistry Research Group (CBRG), reachable at http://chrg.inf.ethz.ch. darwin@inf.ethz.ch

Evolutionary relationships can be more important than abiotic conditions in predicting the outcome of plant-plant interactions

PubMed Central

Soliveres, Santiago; Torices, Rubén; Maestre, Fernando T.

2015-01-01

Positive and negative plant-plant interactions are major processes shaping plant communities. They are affected by environmental conditions and evolutionary relationships among the interacting plants. However, the generality of these factors as drivers of pairwise plant interactions and their combined effects remain virtually unknown. We conducted an observational study to assess how environmental conditions (altitude, temperature, irradiance and rainfall), the dispersal mechanism of beneficiary species and evolutionary relationships affected the co-occurrence of pairwise interactions in 11 Stipa tenacissima steppes located along an environmental gradient in Spain. We studied 197 pairwise plant-plant interactions involving the two major nurse plants (the resprouting shrub Quercus coccifera and the tussock grass S. tenacissima) found in these communities. The relative importance of the studied factors varied with the nurse species considered. None of the factors studied were good predictors of the co-ocurrence between S. tenacissima and its neighbours. However, both the dispersal mechanism of the beneficiary species and the phylogenetic distance between interacting species were crucial factors affecting the co-occurrence between Q. coccifera and its neighbours, while climatic conditions (irradiance) played a secondary role. Values of phylogenetic distance between 207-272.8 Myr led to competition, while values outside this range or fleshy-fruitness in the beneficiary species led to positive interactions. The low importance of environmental conditions as a general driver of pairwise interactions was caused by the species-specific response to changes in either rainfall or radiation. This result suggests that factors other than climatic conditions must be included in theoretical models aimed to generally predict the outcome of plant-plant interactions. Our study helps to improve current theory on plant-plant interactions and to understand how these interactions can respond to expected modifications in species composition and climate associated to ongoing global environmental change. PMID:25914426

Resolving Some Paradoxes in the Thermal Decomposition Mechanism of Acetaldehyde

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sivaramakrishnan, Raghu; Michael, Joe V.; Harding, Lawrence B.

2015-07-16

The mechanism for the thermal decomposition of acetaldehyde has been revisited with an analysis of literature kinetics experiments using theoretical kinetics. The present modeling study was motivated by recent observations, with very sensitive diagnostics, of some unexpected products in high temperature micro-tubular reactor experiments on the thermal decomposition of CH3CHO and its deuterated analogs, CH3CDO, CD3CHO, and CD3CDO. The observations of these products prompted the authors of these studies to suggest that the enol tautomer, CH2CHOH (vinyl alcohol), is a primary intermediate in the thermal decomposition of acetaldehyde. The present modeling efforts on acetaldehyde decomposition incorporate a master equation re-analysismore » of the CH3CHO potential energy surface (PES). The lowest energy process on this PES is an isomerization of CH3CHO to CH2CHOH. However, the subsequent product channels for CH2CHOH are substantially higher in energy, and the only unimolecular process that can be thermally accessed is a re-isomerization to CH3CHO. The incorporation of these new theoretical kinetics predictions into models for selected literature experiments on CH3CHO thermal decomposition confirms our earlier experiment and theory based conclusions that the dominant decomposition process in CH3CHO at high temperatures is C-C bond fission with a minor contribution (~10-20%) from the roaming mechanism to form CH4 and CO. The present modeling efforts also incorporate a master-equation analysis of the H + CH2CHOH potential energy surface. This bimolecular reaction is the primary mechanism for removal of CH2CHOH, which can accumulate to minor amounts at high temperatures, T > 1000 K, in most lab-scale experiments that use large initial concentrations of CH3CHO. Our modeling efforts indicate that the observation of ketene, water and acetylene in the recent micro-tubular experiments are primarily due to bimolecular reactions of CH3CHO and CH2CHOH with H-atoms, and have no bearing on the unimolecular decomposition mechanism of CH3CHO. The present simulations also indicate that experiments using these micro-tubular reactors when interpreted with the aid of high-level theoretical calculations and kinetics modeling can offer insights into the chemistry of elusive intermediates in high temperature pyrolysis of organic molecules.« less

Molecular Mechanisms in the shock induced decomposition of FOX-7

NASA Astrophysics Data System (ADS)

Mishra, Ankit; Tiwari, Subodh C.; Nakano, Aiichiro; Vashishta, Priya; Kalia, Rajiv; CACS Team

Experimental and first principle computational studies on FOX 7 have either involved a very small system consisting of a few atoms or they did not take into account the decomposition mechanisms under extreme conditions of temperature and pressure. We have performed a large-scale reactive MD simulation using ReaxFF-lg force field to study the shock decomposition of FOX 7. The chemical composition of the principal decomposition products correlates well with experimental observations. Furthermore, we observed that the production of N2 and H2O was inter molecular in nature and was through different chemical pathways. Moreover, the production of CO and CO2 was delayed due to production of large stable C,O atoms cluster. These critical insights into the initial processes involved in the shock induced decomposition of FOX-7 will greatly help in understanding the factors playing an important role in the insensitiveness of this high energy material. This research is supported by AFOSR Award No. FA9550-16-1-0042.

Multivariate modelling of endophenotypes associated with the metabolic syndrome in Chinese twins.

PubMed

Pang, Z; Zhang, D; Li, S; Duan, H; Hjelmborg, J; Kruse, T A; Kyvik, K O; Christensen, K; Tan, Q

2010-12-01

The common genetic and environmental effects on endophenotypes related to the metabolic syndrome have been investigated using bivariate and multivariate twin models. This paper extends the pairwise analysis approach by introducing independent and common pathway models to Chinese twin data. The aim was to explore the common genetic architecture in the development of these phenotypes in the Chinese population. Three multivariate models including the full saturated Cholesky decomposition model, the common factor independent pathway model and the common factor common pathway model were fitted to 695 pairs of Chinese twins representing six phenotypes including BMI, total cholesterol, total triacylglycerol, fasting glucose, HDL and LDL. Performances of the nested models were compared with that of the full Cholesky model. Cross-phenotype correlation coefficients gave clear indication of common genetic or environmental backgrounds in the phenotypes. Decomposition of phenotypic correlation by the Cholesky model revealed that the observed phenotypic correlation among lipid phenotypes had genetic and unique environmental backgrounds. Both pathway models suggest a common genetic architecture for lipid phenotypes, which is distinct from that of the non-lipid phenotypes. The declining performance with model restriction indicates biological heterogeneity in development among some of these phenotypes. Our multivariate analyses revealed common genetic and environmental backgrounds for the studied lipid phenotypes in Chinese twins. Model performance showed that physiologically distinct endophenotypes may follow different genetic regulations.

Initial decomposition mechanism for the energy release from electronically excited energetic materials: FOX-7 (1,1-diamino-2,2-dinitroethene, C{sub 2}H{sub 4}N{sub 4}O{sub 4})

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yuan, Bing; Yu, Zijun; Bernstein, Elliot R., E-mail: erb@lamar.Colostate.edu

Decomposition of the energetic material FOX-7 (1,1-diamino-2,2-dinitroethylene, C{sub 2}H{sub 4}N{sub 4}O{sub 4}) is investigated both theoretically and experimentally. The NO molecule is observed as an initial decomposition product subsequent to electronic excitation. The observed NO product is rotationally cold (<35 K) and vibrationally hot (2800 K). The initial decomposition mechanism is explored at the complete active space self-consistent field (CASSCF) level. Potential energy surface calculations at the CASSCF(12,8)/6-31G(d) level illustrate that conical intersections play an essential role in the decomposition mechanism. Electronically excited S{sub 2} FOX-7 can radiationlessly relax to lower electronic states through (S{sub 2}/S{sub 1}){sub CI} and (S{submore » 1}/S{sub 0}){sub CI} conical intersections and undergo a nitro-nitrite isomerization to generate NO product on the S{sub 0} state. The theoretically predicted mechanism is consistent with the experimental results. As FOX-7 decomposes on the ground electronic state, thus, the vibrational energy of the NO product from FOX-7 is high. The observed rotational energy distribution for NO is consistent with the final transition state structure on the S{sub 0} state. Ground state FOX-7 decomposition agrees with previous work: the nitro-nitrite isomerization has the lowest average energy barrier, the C–NH{sub 2} bond cleavage is unlikely under the given excitation conditions, and HONO formation on the ground state surface is energy accessible but not the main process.« less

Information-geometric measures estimate neural interactions during oscillatory brain states

PubMed Central

Nie, Yimin; Fellous, Jean-Marc; Tatsuno, Masami

2014-01-01

The characterization of functional network structures among multiple neurons is essential to understanding neural information processing. Information geometry (IG), a theory developed for investigating a space of probability distributions has recently been applied to spike-train analysis and has provided robust estimations of neural interactions. Although neural firing in the equilibrium state is often assumed in these studies, in reality, neural activity is non-stationary. The brain exhibits various oscillations depending on cognitive demands or when an animal is asleep. Therefore, the investigation of the IG measures during oscillatory network states is important for testing how the IG method can be applied to real neural data. Using model networks of binary neurons or more realistic spiking neurons, we studied how the single- and pairwise-IG measures were influenced by oscillatory neural activity. Two general oscillatory mechanisms, externally driven oscillations and internally induced oscillations, were considered. In both mechanisms, we found that the single-IG measure was linearly related to the magnitude of the external input, and that the pairwise-IG measure was linearly related to the sum of connection strengths between two neurons. We also observed that the pairwise-IG measure was not dependent on the oscillation frequency. These results are consistent with the previous findings that were obtained under the equilibrium conditions. Therefore, we demonstrate that the IG method provides useful insights into neural interactions under the oscillatory condition that can often be observed in the real brain. PMID:24605089

Information-geometric measures estimate neural interactions during oscillatory brain states.

PubMed

Nie, Yimin; Fellous, Jean-Marc; Tatsuno, Masami

2014-01-01

The characterization of functional network structures among multiple neurons is essential to understanding neural information processing. Information geometry (IG), a theory developed for investigating a space of probability distributions has recently been applied to spike-train analysis and has provided robust estimations of neural interactions. Although neural firing in the equilibrium state is often assumed in these studies, in reality, neural activity is non-stationary. The brain exhibits various oscillations depending on cognitive demands or when an animal is asleep. Therefore, the investigation of the IG measures during oscillatory network states is important for testing how the IG method can be applied to real neural data. Using model networks of binary neurons or more realistic spiking neurons, we studied how the single- and pairwise-IG measures were influenced by oscillatory neural activity. Two general oscillatory mechanisms, externally driven oscillations and internally induced oscillations, were considered. In both mechanisms, we found that the single-IG measure was linearly related to the magnitude of the external input, and that the pairwise-IG measure was linearly related to the sum of connection strengths between two neurons. We also observed that the pairwise-IG measure was not dependent on the oscillation frequency. These results are consistent with the previous findings that were obtained under the equilibrium conditions. Therefore, we demonstrate that the IG method provides useful insights into neural interactions under the oscillatory condition that can often be observed in the real brain.

NDMA formation by chloramination of ranitidine: kinetics and mechanism.

PubMed

Roux, Julien Le; Gallard, Hervé; Croué, Jean-Philippe; Papot, Sébastien; Deborde, Marie

2012-10-16

The kinetics of decomposition of the pharmaceutical ranitidine (a major precursor of NDMA) during chloramination was investigated and some decomposition byproducts were identified by using high performance liquid chromatography coupled with mass spectrometry (HPLC-MS). The reaction between monochloramine and ranitidine followed second order kinetics and was acid-catalyzed. Decomposition of ranitidine formed different byproducts depending on the applied monochloramine concentration. Most identified products were chlorinated and hydroxylated analogues of ranitidine. In excess of monochloramine, nucleophilic substitution between ranitidine and monochloramine led to byproducts that are critical intermediates involved in the formation of NDMA, for example, a carbocation formed from the decomposition of the methylfuran moiety of ranitidine. A complete mechanism is proposed to explain the high formation yield of NDMA from chloramination of ranitidine. These results are of great importance to understand the formation of NDMA by chloramination of tertiary amines.

An ab initio molecular orbital study of the mechanism for the gas-phase water-mediated decomposition and the formation of hydrates of peroxyacetyl nitrate (PAN).

PubMed

Li, Yumin; Francisco, Joseph S

2005-08-31

There is uncertainty in the mechanism for the hydrolysis of peroxyacetyl nitrate (PAN), and experimental attempts to detect products of the direct reaction have been unsuccessful. Ab initio calculations are used to examine the energetics of water-mediated decomposition of gas-phase PAN into acetic acid and peroxynitric acid. On the basis of ab initio calculations, an alternative reaction mechanism for the decomposition of PAN is proposed. The calculations indicate that the barrier for one water addition to PAN is large. However, including additional water molecules reveals a substantially lower energy route. The calculations suggest that the formation of PAN hydrate complexes are energetically favorable and stable. Additional waters are increasingly efficient at stabilizing hydrated PAN.

The implications of microbial and substrate limitation for the fates of carbon in different organic soil horizon types of boreal forest ecosystems: a mechanistically based model analysis

USGS Publications Warehouse

He, Y.; Zhuang, Q.; Harden, Jennifer W.; McGuire, A. David; Fan, Z.; Liu, Y.; Wickland, Kimberly P.

2014-01-01

The large amount of soil carbon in boreal forest ecosystems has the potential to influence the climate system if released in large quantities in response to warming. Thus, there is a need to better understand and represent the environmental sensitivity of soil carbon decomposition. Most soil carbon decomposition models rely on empirical relationships omitting key biogeochemical mechanisms and their response to climate change is highly uncertain. In this study, we developed a multi-layer microbial explicit soil decomposition model framework for boreal forest ecosystems. A thorough sensitivity analysis was conducted to identify dominating biogeochemical processes and to highlight structural limitations. Our results indicate that substrate availability (limited by soil water diffusion and substrate quality) is likely to be a major constraint on soil decomposition in the fibrous horizon (40–60% of soil organic carbon (SOC) pool size variation), while energy limited microbial activity in the amorphous horizon exerts a predominant control on soil decomposition (>70% of SOC pool size variation). Elevated temperature alleviated the energy constraint of microbial activity most notably in amorphous soils, whereas moisture only exhibited a marginal effect on dissolved substrate supply and microbial activity. Our study highlights the different decomposition properties and underlying mechanisms of soil dynamics between fibrous and amorphous soil horizons. Soil decomposition models should consider explicitly representing different boreal soil horizons and soil–microbial interactions to better characterize biogeochemical processes in boreal forest ecosystems. A more comprehensive representation of critical biogeochemical mechanisms of soil moisture effects may be required to improve the performance of the soil model we analyzed in this study.

Lotka-Volterra pairwise modeling fails to capture diverse pairwise microbial interactions

PubMed Central

Momeni, Babak; Xie, Li; Shou, Wenying

2017-01-01

Pairwise models are commonly used to describe many-species communities. In these models, an individual receives additive fitness effects from pairwise interactions with each species in the community ('additivity assumption'). All pairwise interactions are typically represented by a single equation where parameters reflect signs and strengths of fitness effects ('universality assumption'). Here, we show that a single equation fails to qualitatively capture diverse pairwise microbial interactions. We build mechanistic reference models for two microbial species engaging in commonly-found chemical-mediated interactions, and attempt to derive pairwise models. Different equations are appropriate depending on whether a mediator is consumable or reusable, whether an interaction is mediated by one or more mediators, and sometimes even on quantitative details of the community (e.g. relative fitness of the two species, initial conditions). Our results, combined with potential violation of the additivity assumption in many-species communities, suggest that pairwise modeling will often fail to predict microbial dynamics. DOI: http://dx.doi.org/10.7554/eLife.25051.001 PMID:28350295

Does increasing pressure always accelerate the condensed material decay initiated through bimolecular reactions? A case of the thermal decomposition of TKX-50 at high pressures.

PubMed

Lu, Zhipeng; Zeng, Qun; Xue, Xianggui; Zhang, Zengming; Nie, Fude; Zhang, Chaoyang

2017-08-30

Performances and behaviors under high temperature-high pressure conditions are fundamentals for many materials. We study in the present work the pressure effect on the thermal decomposition of a new energetic ionic salt (EIS), TKX-50, by confining samples in a diamond anvil cell, using Raman spectroscopy measurements and ab initio simulations. As a result, we find a quadratic increase in decomposition temperature (T d ) of TKX-50 with increasing pressure (P) (T d = 6.28P 2 + 12.94P + 493.33, T d and P in K and GPa, respectively, and R 2 = 0.995) and the decomposition under various pressures initiated by an intermolecular H-transfer reaction (a bimolecular reaction). Surprisingly, this finding is contrary to a general observation about the pressure effect on the decomposition of common energetic materials (EMs) composed of neutral molecules: increasing pressure will impede the decomposition if it starts from a bimolecular reaction. Our results also demonstrate that increasing pressure impedes the H-transfer via the enhanced long-range electrostatic repulsion of H +δ H +δ of neighboring NH 3 OH + , with blue shifts of the intermolecular H-bonds. And the subsequent decomposition of the H-transferred intermediates is also suppressed, because the decomposition proceeds from a bimolecular reaction to a unimolecular one, which is generally prevented by compression. These two factors are the basic root for which the decomposition retarded with increasing pressure of TKX-50. Therefore, our finding breaks through the previously proposed concept that, for the condensed materials, increasing pressure will accelerate the thermal decomposition initiated by bimolecular reactions, and reveals a distinct mechanism of the pressure effect on thermal decomposition. That is to say, increasing pressure does not always promote the condensed material decay initiated through bimolecular reactions. Moreover, such a mechanism may be feasible to other EISs due to the similar intermolecular interactions.

Double Bounce Component in Cross-Polarimetric SAR from a New Scattering Target Decomposition

NASA Astrophysics Data System (ADS)

Hong, Sang-Hoon; Wdowinski, Shimon

2013-08-01

Common vegetation scattering theories assume that the Synthetic Aperture Radar (SAR) cross-polarization (cross-pol) signal represents solely volume scattering. We found this assumption incorrect based on SAR phase measurements acquired over the south Florida Everglades wetlands indicating that the cross-pol radar signal often samples the water surface beneath the vegetation. Based on these new observations, we propose that the cross-pol measurement consists of both volume scattering and double bounce components. The simplest multi-bounce scattering mechanism that generates cross-pol signal occurs by rotated dihedrals. Thus, we use the rotated dihedral mechanism with probability density function to revise some of the vegetation scattering theories and develop a three- component decomposition algorithm with single bounce, double bounce from both co-pol and cross-pol, and volume scattering components. We applied the new decomposition analysis to both urban and rural environments using Radarsat-2 quad-pol datasets. The decomposition of the San Francisco's urban area shows higher double bounce scattering and reduced volume scattering compared to other common three-component decomposition. The decomposition of the rural Everglades area shows that the relations between volume and cross-pol double bounce depend on the vegetation density. The new decomposition can be useful to better understand vegetation scattering behavior over the various surfaces and the estimation of above ground biomass using SAR observations.

Determination of the thermal stability of perfluoroalkylethers

NASA Technical Reports Server (NTRS)

Helmick, Larry S.; Jones, William R., Jr.

1990-01-01

The thermal decomposition temperatures of several commercial and custom synthesized perfluoroalkylether fluids were determined with a computerized tensimeter. In general, the decomposition temperatures of the commercial fluids were all similar and significantly higher than those for custom synthesized fluids. Correlation of the decomposition temperatures with the molecular structures of the primary components of the commercial fluids revealed that the stability of the fluids is not affected by intrinsic factors such as carbon chain length, branching, or cumulated difluoroformal groups. Instead, correlation with extrinsic factors revealed that the stability may be limited by the presence of small quantities of thermally unstable material and/or chlorine-containing material arising from the use of chlorine-containing solvents during synthesis. Finally, correlation of decomposition temperatures with molecular weights for Demnum and Krytox fluids supports a chain cleavage reaction mechanism for Demnum fluids and an unzipping reaction mechanism for Krytox fluids.

The correlation between elongation at break and thermal decomposition of aged EPDM cable polymer

NASA Astrophysics Data System (ADS)

Šarac, T.; Devaux, J.; Quiévy, N.; Gusarov, A.; Konstantinović, M. J.

2017-03-01

The effect of simultaneous thermal and gamma irradiation ageing on the mechanical and physicochemical properties of industrial EPDM was investigated. Accelerated ageing, covering a wide range of dose rates, doses and temperatures, was preformed in stagnant air on EPDM polymer samples extracted from the cables in use in the Belgian nuclear power plants. The mechanical properties, ultimate tensile stress and elongation at break, are found to exhibit the strong dependence on the dose, ageing temperature and dose rate. The thermal decomposition of aged polymer is observed to be the dose dependent when thermogravimetry test is performed under air atmosphere. No dose dependence is observed when thermal decomposition is performed under nitrogen atmosphere. The thermal decomposition rates are found to fully mimic the reduction of elongation at break for all dose rates and ageing temperatures. This effect is argued to be the result of thermal and radiation mediated oxidation degradation process.

Random walk in generalized quantum theory

NASA Astrophysics Data System (ADS)

Martin, Xavier; O'Connor, Denjoe; Sorkin, Rafael D.

2005-01-01

One can view quantum mechanics as a generalization of classical probability theory that provides for pairwise interference among alternatives. Adopting this perspective, we “quantize” the classical random walk by finding, subject to a certain condition of “strong positivity”, the most general Markovian, translationally invariant “decoherence functional” with nearest neighbor transitions.

Metal-porphyrin: a potential catalyst for direct decomposition of N(2)O by theoretical reaction mechanism investigation.

PubMed

Maitarad, Phornphimon; Namuangruk, Supawadee; Zhang, Dengsong; Shi, Liyi; Li, Hongrui; Huang, Lei; Boekfa, Bundet; Ehara, Masahiro

2014-06-17

The adsorption of nitrous oxide (N2O) on metal-porphyrins (metal: Ti, Cr, Fe, Co, Ni, Cu, or Zn) has been theoretically investigated using density functional theory with the M06L functional to explore their use as potential catalysts for the direct decomposition of N2O. Among these metal-porphyrins, Ti-porphyrin is the most active for N2O adsorption in the triplet ground state with the strongest adsorption energy (-13.32 kcal/mol). Ti-porphyrin was then assessed for the direct decomposition of N2O. For the overall reaction mechanism of three N2O molecules on Ti-porphyrin, two plausible catalytic cycles are proposed. Cycle 1 involves the consecutive decomposition of the first two N2O molecules, while cycle 2 is the decomposition of the third N2O molecule. For cycle 1, the activation energies of the first and second N2O decompositions are computed to be 3.77 and 49.99 kcal/mol, respectively. The activation energy for the third N2O decomposition in cycle 2 is 47.79 kcal/mol, which is slightly lower than that of the second activation energy of the first cycle. O2 molecules are released in cycles 1 and 2 as the products of the reaction, which requires endothermic energies of 102.96 and 3.63 kcal/mol, respectively. Therefore, the O2 desorption is mainly released in catalytic cycle 2 of a TiO3-porphyrin intermediate catalyst. In conclusion, regarding the O2 desorption step for the direct decomposition of N2O, the findings would be very useful to guide the search for potential N2O decomposition catalysts in new directions.

Nitrations Conference Held at Menlo Park, California on 27-29 July 1983.

DTIC Science & Technology

1983-09-01

MECHANISM OF HOMOGENEOUS GAS-PHASE DECOMPOSITION OF NITROTOLUENES" D. F. McMillen, C. W. Larson, and D. M. Golden...NITROAROMATICS. THE MECHANISM OF HOMOGENEOUS GAS-PHASE DECOMPOSITION OF NITROTOLUENES" i 6:00 Wine Tasting 7:00 Banquet, International Dining Room THURSDAY, JULY...which undergo hydrolysis or oxidations in strong acid solutions can he easily nitrated. Aryl nitriles, which could not be dinitrated without

An optimized ensemble local mean decomposition method for fault detection of mechanical components

NASA Astrophysics Data System (ADS)

Zhang, Chao; Li, Zhixiong; Hu, Chao; Chen, Shuai; Wang, Jianguo; Zhang, Xiaogang

2017-03-01

Mechanical transmission systems have been widely adopted in most of industrial applications, and issues related to the maintenance of these systems have attracted considerable attention in the past few decades. The recently developed ensemble local mean decomposition (ELMD) method shows satisfactory performance in fault detection of mechanical components for preventing catastrophic failures and reducing maintenance costs. However, the performance of ELMD often heavily depends on proper selection of its model parameters. To this end, this paper proposes an optimized ensemble local mean decomposition (OELMD) method to determinate an optimum set of ELMD parameters for vibration signal analysis. In OELMD, an error index termed the relative root-mean-square error (Relative RMSE) is used to evaluate the decomposition performance of ELMD with a certain amplitude of the added white noise. Once a maximum Relative RMSE, corresponding to an optimal noise amplitude, is determined, OELMD then identifies optimal noise bandwidth and ensemble number based on the Relative RMSE and signal-to-noise ratio (SNR), respectively. Thus, all three critical parameters of ELMD (i.e. noise amplitude and bandwidth, and ensemble number) are optimized by OELMD. The effectiveness of OELMD was evaluated using experimental vibration signals measured from three different mechanical components (i.e. the rolling bearing, gear and diesel engine) under faulty operation conditions.

Dominant modal decomposition method

NASA Astrophysics Data System (ADS)

Dombovari, Zoltan

2017-03-01

The paper deals with the automatic decomposition of experimental frequency response functions (FRF's) of mechanical structures. The decomposition of FRF's is based on the Green function representation of free vibratory systems. After the determination of the impulse dynamic subspace, the system matrix is formulated and the poles are calculated directly. By means of the corresponding eigenvectors, the contribution of each element of the impulse dynamic subspace is determined and the sufficient decomposition of the corresponding FRF is carried out. With the presented dominant modal decomposition (DMD) method, the mode shapes, the modal participation vectors and the modal scaling factors are identified using the decomposed FRF's. Analytical example is presented along with experimental case studies taken from machine tool industry.

Network reciprocity by coexisting learning and teaching strategies

NASA Astrophysics Data System (ADS)

Tanimoto, Jun; Brede, Markus; Yamauchi, Atsuo

2012-03-01

We propose a network reciprocity model in which an agent probabilistically adopts learning or teaching strategies. In the learning adaptation mechanism, an agent may copy a neighbor's strategy through Fermi pairwise comparison. The teaching adaptation mechanism involves an agent imposing its strategy on a neighbor. Our simulations reveal that the reciprocity is significantly affected by the frequency with which learning and teaching agents coexist in a network and by the structure of the network itself.

Decomposition of standing litter in arid grasslands: Interactions between sunlight, non-rainfall moisture, microbes, and plant traits

NASA Astrophysics Data System (ADS)

Logan, J. R. V.; Jacobson, P. J.; Jacobson, K. M.; Evans, S.

2017-12-01

Although arid lands make up 40% of the Earth's land surface, we still lack a strong understanding of carbon cycling and plant decomposition in these systems. One reason for this is that field studies typically only focus on decomposition at or below the ground surface even though standing dead litter (material that has not yet fallen to the ground) accounts for more than 50% of total necromass in many of these systems. While recent work has begun to recognize the important and unique aspects of standing litter decomposition, few studies have investigated specific mechanisms controlling rates of mass loss. We hypothesized that initial photodegradation of the outer plant cuticle of standing litter is an important determinant of litter decomposition because this process increases moisture absorption and subsequent opportunities for biological decomposition. Our preliminary results offer support for this hypothesis. We found that standing grass stems with their cuticles artificially removed had greater water absorbance and more than 400% greater mass loss over a 6-month period relative to controls with intact cuticles. Additionally, spectroscopic measurements of cuticle integrity showed damage to the litter surface after a period of extended photodegradation, allowing increased moisture uptake during simulated fog/dew events. These findings are especially important in the context of recent work by us and others showing that non-rainfall moisture (fog, dew, and water vapor) plays a much larger role in arid land decomposition than previously thought. Improving our understanding of the mechanisms driving decomposition of standing litter will enable us to develop a more predictive understanding of carbon storage in arid lands.

Thermal Decomposition Mechanism of Butyraldehyde

NASA Astrophysics Data System (ADS)

Hatten, Courtney D.; Warner, Brian; Wright, Emily; Kaskey, Kevin; McCunn, Laura R.

2013-06-01

The thermal decomposition of butyraldehyde, CH_3CH_2CH_2C(O)H, has been studied in a resistively heated SiC tubular reactor. Products of pyrolysis were identified via matrix-isolation FTIR spectroscopy and photoionization mass spectrometry in separate experiments. Carbon monoxide, ethene, acetylene, water and ethylketene were among the products detected. To unravel the mechanism of decomposition, pyrolysis of a partially deuterated sample of butyraldehyde was studied. Also, the concentration of butyraldehyde in the carrier gas was varied in experiments to determine the presence of bimolecular reactions. The results of these experiments can be compared to the dissociation pathways observed in similar aldehydes and are relevant to the processing of biomass, foods, and tobacco.

Resonance-Based Sparse Signal Decomposition and its Application in Mechanical Fault Diagnosis: A Review.

PubMed

Huang, Wentao; Sun, Hongjian; Wang, Weijie

2017-06-03

Mechanical equipment is the heart of industry. For this reason, mechanical fault diagnosis has drawn considerable attention. In terms of the rich information hidden in fault vibration signals, the processing and analysis techniques of vibration signals have become a crucial research issue in the field of mechanical fault diagnosis. Based on the theory of sparse decomposition, Selesnick proposed a novel nonlinear signal processing method: resonance-based sparse signal decomposition (RSSD). Since being put forward, RSSD has become widely recognized, and many RSSD-based methods have been developed to guide mechanical fault diagnosis. This paper attempts to summarize and review the theoretical developments and application advances of RSSD in mechanical fault diagnosis, and to provide a more comprehensive reference for those interested in RSSD and mechanical fault diagnosis. Followed by a brief introduction of RSSD's theoretical foundation, based on different optimization directions, applications of RSSD in mechanical fault diagnosis are categorized into five aspects: original RSSD, parameter optimized RSSD, subband optimized RSSD, integrated optimized RSSD, and RSSD combined with other methods. On this basis, outstanding issues in current RSSD study are also pointed out, as well as corresponding instructional solutions. We hope this review will provide an insightful reference for researchers and readers who are interested in RSSD and mechanical fault diagnosis.

Resonance-Based Sparse Signal Decomposition and Its Application in Mechanical Fault Diagnosis: A Review

PubMed Central

Huang, Wentao; Sun, Hongjian; Wang, Weijie

2017-01-01

Mechanical equipment is the heart of industry. For this reason, mechanical fault diagnosis has drawn considerable attention. In terms of the rich information hidden in fault vibration signals, the processing and analysis techniques of vibration signals have become a crucial research issue in the field of mechanical fault diagnosis. Based on the theory of sparse decomposition, Selesnick proposed a novel nonlinear signal processing method: resonance-based sparse signal decomposition (RSSD). Since being put forward, RSSD has become widely recognized, and many RSSD-based methods have been developed to guide mechanical fault diagnosis. This paper attempts to summarize and review the theoretical developments and application advances of RSSD in mechanical fault diagnosis, and to provide a more comprehensive reference for those interested in RSSD and mechanical fault diagnosis. Followed by a brief introduction of RSSD’s theoretical foundation, based on different optimization directions, applications of RSSD in mechanical fault diagnosis are categorized into five aspects: original RSSD, parameter optimized RSSD, subband optimized RSSD, integrated optimized RSSD, and RSSD combined with other methods. On this basis, outstanding issues in current RSSD study are also pointed out, as well as corresponding instructional solutions. We hope this review will provide an insightful reference for researchers and readers who are interested in RSSD and mechanical fault diagnosis. PMID:28587198

An enhanced Petri-net model to predict synergistic effects of pairwise drug combinations from gene microarray data.

PubMed

Jin, Guangxu; Zhao, Hong; Zhou, Xiaobo; Wong, Stephen T C

2011-07-01

Prediction of synergistic effects of drug combinations has traditionally been relied on phenotypic response data. However, such methods cannot be used to identify molecular signaling mechanisms of synergistic drug combinations. In this article, we propose an enhanced Petri-Net (EPN) model to recognize the synergistic effects of drug combinations from the molecular response profiles, i.e. drug-treated microarray data. We addressed the downstream signaling network of the targets for the two individual drugs used in the pairwise combinations and applied EPN to the identified targeted signaling network. In EPN, drugs and signaling molecules are assigned to different types of places, while drug doses and molecular expressions are denoted by color tokens. The changes of molecular expressions caused by treatments of drugs are simulated by two actions of EPN: firing and blasting. Firing is to transit the drug and molecule tokens from one node or place to another, and blasting is to reduce the number of molecule tokens by drug tokens in a molecule node. The goal of EPN is to mediate the state characterized by control condition without any treatment to that of treatment and to depict the drug effects on molecules by the drug tokens. We applied EPN to our generated pairwise drug combination microarray data. The synergistic predictions using EPN are consistent with those predicted using phenotypic response data. The molecules responsible for the synergistic effects with their associated feedback loops display the mechanisms of synergism. The software implemented in Python 2.7 programming language is available from request. stwong@tmhs.org.

The decomposition of fine and coarse roots: their global patterns and controlling factors

PubMed Central

Zhang, Xinyue; Wang, Wei

2015-01-01

Fine root decomposition represents a large carbon (C) cost to plants, and serves as a potential soil C source, as well as a substantial proportion of net primary productivity. Coarse roots differ markedly from fine roots in morphology, nutrient concentrations, functions, and decomposition mechanisms. Still poorly understood is whether a consistent global pattern exists between the decomposition of fine (<2 mm root diameter) and coarse (≥2 mm) roots. A comprehensive terrestrial root decomposition dataset, including 530 observations from 71 sampling sites, was thus used to compare global patterns of decomposition of fine and coarse roots. Fine roots decomposed significantly faster than coarse roots in middle latitude areas, but their decomposition in low latitude regions was not significantly different from that of coarse roots. Coarse root decomposition showed more dependence on climate, especially mean annual temperature (MAT), than did fine roots. Initial litter lignin content was the most important predictor of fine root decomposition, while lignin to nitrogen ratios, MAT, and mean annual precipitation were the most important predictors of coarse root decomposition. Our study emphasizes the necessity of separating fine roots and coarse roots when predicting the response of belowground C release to future climate changes. PMID:25942391

Calvin Mukarakate | NREL

Science.gov Websites

for the Symposium on Thermal and Catalytic Sciences for Biofuels and Biobased Products. He is also a ;Unimolecular Thermal Decomposition of Dimethoxybenzenes," Journal of Chemical Physics (2014) "Real ," Green Chemistry (2014) "Biomass Pyrolysis: Thermal Decomposition Mechanisms of Furfural and

DincRNA: a comprehensive web-based bioinformatics toolkit for exploring disease associations and ncRNA function.

PubMed

Cheng, Liang; Hu, Yang; Sun, Jie; Zhou, Meng; Jiang, Qinghua

2018-06-01

DincRNA aims to provide a comprehensive web-based bioinformatics toolkit to elucidate the entangled relationships among diseases and non-coding RNAs (ncRNAs) from the perspective of disease similarity. The quantitative way to illustrate relationships of pair-wise diseases always depends on their molecular mechanisms, and structures of the directed acyclic graph of Disease Ontology (DO). Corresponding methods for calculating similarity of pair-wise diseases involve Resnik's, Lin's, Wang's, PSB and SemFunSim methods. Recently, disease similarity was validated suitable for calculating functional similarities of ncRNAs and prioritizing ncRNA-disease pairs, and it has been widely applied for predicting the ncRNA function due to the limited biological knowledge from wet lab experiments of these RNAs. For this purpose, a large number of algorithms and priori knowledge need to be integrated. e.g. 'pair-wise best, pairs-average' (PBPA) and 'pair-wise all, pairs-maximum' (PAPM) methods for calculating functional similarities of ncRNAs, and random walk with restart (RWR) method for prioritizing ncRNA-disease pairs. To facilitate the exploration of disease associations and ncRNA function, DincRNA implemented all of the above eight algorithms based on DO and disease-related genes. Currently, it provides the function to query disease similarity scores, miRNA and lncRNA functional similarity scores, and the prioritization scores of lncRNA-disease and miRNA-disease pairs. http://bio-annotation.cn:18080/DincRNAClient/. biofomeng@hotmail.com or qhjiang@hit.edu.cn. Supplementary data are available at Bioinformatics online.

Perfluoropolyalkylether decomposition on catalytic aluminas

NASA Technical Reports Server (NTRS)

Morales, Wilfredo

1994-01-01

The decomposition of Fomblin Z25, a commercial perfluoropolyalkylether liquid lubricant, was studied using the Penn State Micro-oxidation Test, and a thermal gravimetric/differential scanning calorimetry unit. The micro-oxidation test was conducted using 440C stainless steel and pure iron metal catalyst specimens, whereas the thermal gravimetric/differential scanning calorimetry tests were conducted using catalytic alumina pellets. Analysis of the thermal data, high pressure liquid chromatography data, and x-ray photoelectron spectroscopy data support evidence that there are two different decomposition mechanisms for Fomblin Z25, and that reductive sites on the catalytic surfaces are responsible for the decomposition of Fomblin Z25.

Kinetics of gas phase formic acid decomposition on platinum single crystal and polycrystalline surfaces

NASA Astrophysics Data System (ADS)

Detwiler, Michael D.; Milligan, Cory A.; Zemlyanov, Dmitry Y.; Delgass, W. Nicholas; Ribeiro, Fabio H.

2016-06-01

Formic acid dehydrogenation turnover rates (TORs) were measured on Pt(111), Pt(100), and polycrystalline Pt foil surfaces at a total pressure of 800 Torr between 413 and 513 K in a batch reactor connected to an ultra-high vacuum (UHV) system. The TORs, apparent activation energies, and reaction orders are not sensitive to the structure of the Pt surface, within the precision of the measurements. CO introduced into the batch reactor depressed the formic acid dehydrogenation TOR and increased the reaction's apparent activation energies on Pt(111) and Pt(100), consistent with behavior predicted by the Temkin equation. Two reaction mechanisms were explored which explain the formic acid decomposition mechanism on Pt, both of which include dissociative adsorption of formic acid, rate limiting formate decomposition, and quasi-equilibrated hydrogen recombination and CO adsorption. No evidence was found that catalytic supports used in previous studies altered the reaction kinetics or mechanism.

Tautomerism and thermal decomposition of tetrazole: high-level ab initio study.

PubMed

Kiselev, Vitaly G; Cheblakov, Pavel B; Gritsan, Nina P

2011-03-10

The mutual interconversion and decomposition reactions of four tetrazole isomers (1H-TZ, 2H-TZ, 5H-TZ, and an N-heterocyclic carbene 14H) have been studied theoretically using the W1 high-level procedure. Computations allowed resolution of the existing discrepancies in the mechanism and key intermediates of TZ thermolysis. The tautomeric equilibria between 1H-TZ, 2H-TZ, and 14H turned out to play a very important role in the mechanism of thermal decomposition. Although the barriers of monomolecular tautomeric transformations were found to be high (∼50-70 kcal/mol), the concerted double H atom transfer reactions in the H-bonded complexes of TZ tautomers have profoundly lower barriers (∼18-28 kcal/mol). These reactions lead to fast interconversion between 1H-TZ, 2H-TZ, and 14H. The carbene 14H has never been considered before; however, it was predicted to be a key intermediate in the mechanism of thermal decomposition of TZ. For all species considered, the unimolecular reactions of N(2) elimination were predicted to dominate over the elimination of hydrazoic acid. In agreement with existing experimental data, the effective activation energy of thermolysis was calculated to be 36.2 kcal/mol.

Kinetics and mechanism of solid decompositions — From basic discoveries by atomic absorption spectrometry and quadrupole mass spectroscopy to thorough thermogravimetric analysis

NASA Astrophysics Data System (ADS)

L'vov, Boris V.

2008-02-01

This paper sums up the evolution of thermochemical approach to the interpretation of solid decompositions for the past 25 years. This period includes two stages related to decomposition studies by different techniques: by ET AAS and QMS in 1981-2001 and by TG in 2002-2007. As a result of ET AAS and QMS investigations, the method for determination of absolute rates of solid decompositions was developed and the mechanism of decompositions through the congruent dissociative vaporization was discovered. On this basis, in the period from 1997 to 2001, the decomposition mechanisms of several classes of reactants were interpreted and some unusual effects observed in TA were explained. However, the thermochemical approach has not received any support by other TA researchers. One of the potential reasons of this distrust was the unreliability of the E values measured by the traditional Arrhenius plot method. The theoretical analysis and comparison of metrological features of different methods used in the determinations of thermochemical quantities permitted to conclude that in comparison with the Arrhenius plot and second-law methods, the third-law method is to be very much preferred. However, this method cannot be used in the kinetic studies by the Arrhenius approach because its use suggests the measuring of the equilibrium pressures of decomposition products. On the contrary, the method of absolute rates is ideally suitable for this purpose. As a result of much higher precision of the third-law method, some quantitative conclusions that follow from the theory were confirmed, and several new effects, which were invisible in the framework of the Arrhenius approach, have been revealed. In spite of great progress reached in the development of reliable methodology, based on the third-law method, the thermochemical approach remains unclaimed as before.

Assessing many-body contributions to intermolecular interactions of the AMOEBA force field using energy decomposition analysis of electronic structure calculations.

PubMed

Demerdash, Omar; Mao, Yuezhi; Liu, Tianyi; Head-Gordon, Martin; Head-Gordon, Teresa

2017-10-28

In this work, we evaluate the accuracy of the classical AMOEBA model for representing many-body interactions, such as polarization, charge transfer, and Pauli repulsion and dispersion, through comparison against an energy decomposition method based on absolutely localized molecular orbitals (ALMO-EDA) for the water trimer and a variety of ion-water systems. When the 2- and 3-body contributions according to the many-body expansion are analyzed for the ion-water trimer systems examined here, the 3-body contributions to Pauli repulsion and dispersion are found to be negligible under ALMO-EDA, thereby supporting the validity of the pairwise-additive approximation in AMOEBA's 14-7 van der Waals term. However AMOEBA shows imperfect cancellation of errors for the missing effects of charge transfer and incorrectness in the distance dependence for polarization when compared with the corresponding ALMO-EDA terms. We trace the larger 2-body followed by 3-body polarization errors to the Thole damping scheme used in AMOEBA, and although the width parameter in Thole damping can be changed to improve agreement with the ALMO-EDA polarization for points about equilibrium, the correct profile of polarization as a function of intermolecular distance cannot be reproduced. The results suggest that there is a need for re-examining the damping and polarization model used in the AMOEBA force field and provide further insights into the formulations of polarizable force fields in general.

Assessing many-body contributions to intermolecular interactions of the AMOEBA force field using energy decomposition analysis of electronic structure calculations

NASA Astrophysics Data System (ADS)

Demerdash, Omar; Mao, Yuezhi; Liu, Tianyi; Head-Gordon, Martin; Head-Gordon, Teresa

2017-10-01

In this work, we evaluate the accuracy of the classical AMOEBA model for representing many-body interactions, such as polarization, charge transfer, and Pauli repulsion and dispersion, through comparison against an energy decomposition method based on absolutely localized molecular orbitals (ALMO-EDA) for the water trimer and a variety of ion-water systems. When the 2- and 3-body contributions according to the many-body expansion are analyzed for the ion-water trimer systems examined here, the 3-body contributions to Pauli repulsion and dispersion are found to be negligible under ALMO-EDA, thereby supporting the validity of the pairwise-additive approximation in AMOEBA's 14-7 van der Waals term. However AMOEBA shows imperfect cancellation of errors for the missing effects of charge transfer and incorrectness in the distance dependence for polarization when compared with the corresponding ALMO-EDA terms. We trace the larger 2-body followed by 3-body polarization errors to the Thole damping scheme used in AMOEBA, and although the width parameter in Thole damping can be changed to improve agreement with the ALMO-EDA polarization for points about equilibrium, the correct profile of polarization as a function of intermolecular distance cannot be reproduced. The results suggest that there is a need for re-examining the damping and polarization model used in the AMOEBA force field and provide further insights into the formulations of polarizable force fields in general.

Application of the Interacting Quantum Atoms Approach to the S66 and Ionic-Hydrogen-Bond Datasets for Noncovalent Interactions.

PubMed

Suárez, Dimas; Díaz, Natalia; Francisco, Evelio; Martín Pendás, Angel

2018-04-17

The interacting quantum atoms (IQA) method can assess, systematically and in great detail, the strength and physics of both covalent and noncovalent interactions. The lack of a pair density in density functional theory (DFT), which precludes the direct IQA decomposition of the characteristic exchange-correlation energy, has been recently overcome by means of a scaling technique, which can largely expand the applicability of the method. To better assess the utility of the augmented IQA methodology to derive quantum chemical decompositions at the atomic and molecular levels, we report the results of Hartree-Fock (HF) and DFT calculations on the complexes included in the S66 and the ionic H-bond databases of benchmark geometry and binding energies. For all structures, we perform single-point and geometry optimizations using HF and selected DFT methods with triple-ζ basis sets followed by full IQA calculations. Pairwise dispersion energies are accounted for by the D3 method. We analyze the goodness of the HF-D3 and DFT-D3 binding energies, the magnitude of numerical errors, the fragment and atomic distribution of formation energies, etc. It is shown that fragment-based IQA decomposes the formation energies in comparable terms to those of perturbative approaches and that the atomic IQA energies hold the promise of rigorously quantifying atomic and group energy contributions in larger biomolecular systems. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Thermochemistry, Tautomerism, and Thermal Decomposition of 1,5-Diaminotetrazole: A High-Level ab Initio Study.

PubMed

Shakhova, Margarita V; Muravyev, Nikita V; Gritsan, Nina P; Kiselev, Vitaly G

2018-04-19

Thermochemistry, kinetics, and mechanism of thermal decomposition of 1,5-diaminotetrazole (DAT), a widely used "building block" of nitrogen-rich energetic compounds, were studied theoretically at a high and reliable level of theory (viz., using the explicitly correlated CCSD(T)-F12/aug-cc-pVTZ procedure). Quantum chemical calculations provided detailed insight into the thermolysis mechanism of DAT missing in the existing literature. Moreover, several contradictory assumptions on the mechanism and key intermediates of thermolysis were resolved. The unimolecular primary decomposition reactions of the seven isomers of DAT were studied in the gas phase and in the melt using a simplified model of the latter. The two-step reaction of N 2 elimination from the diamino tautomer was found to be the primary decomposition process of DAT in the gas phase and melt. The effective Arrhenius parameters of this process were calculated to be E a = 43.4 kcal mol -1 and log( A/s -1 ) = 15.2 in a good agreement with the experimental values. Contrary to the existing literature data, all other decomposition channels of DAT isomers turned out to be kinetically unimportant. Apart from this, a new primary decomposition channel yielding N 2 , cyanamide, and 1,1-diazene was found for some H-bonded dimers of DAT. We also determined a reliable and mutually consistent set of thermochemical values for DAT (Δ f H solid 0 = 74.5 ± 1.5 kcal·mol -1 ) by combining theoretically calculated (W1 multilevel procedure along with an isodesmic reaction) gas phase enthalpy of formation (Δ f H gas 0 = 100.7 ± 1.0 kcal·mol -1 ) and experimentally measured sublimation enthalpy (Δ sub H 0 = 26.2 ± 0.5 kcal·mol -1 ).

Decomposition of amino diazeniumdiolates (NONOates): molecular mechanisms.

PubMed

Shaikh, Nizamuddin; Valiev, Marat; Lymar, Sergei V

2014-12-01

Although diazeniumdiolates (X[N(O)NO](-)) are extensively used in biochemical, physiological, and pharmacological studies due to their ability to release NO and/or its congeneric nitroxyl, the mechanisms of these processes remain obscure. In this work, we used a combination of spectroscopic, kinetic, and computational techniques to arrive at a quantitatively consistent molecular mechanism for decomposition of amino diazeniumdiolates (amino NONOates: R2N[N(O)NO](-), where R=N(C2H5)2 (1), N(C3H4NH2)2 (2), or N(C2H4NH2)2 (3)). Decomposition of these NONOates is triggered by protonation of their [NN(O)NO](-) group with the apparent pKa and decomposition rate constants of 4.6 and 1 s(-1) for 1; 3.5 and 0.083 s(-1) for 2; and 3.8 and 0.0033 s(-1) for 3. Although protonation occurs mainly on the O atoms of the functional group, only the minor R2N(H)N(O)NO tautomer (population ~10(-7), for 1) undergoes the NN heterolytic bond cleavage (kd~10(7) s(-1) for 1) leading to amine and NO. Decompositions of protonated amino NONOates are strongly temperature-dependent; activation enthalpies are 20.4 and 19.4 kcal/mol for 1 and 2, respectively, which includes contributions from both the tautomerization and bond cleavage. The bond cleavage rates exhibit exceptional sensitivity to the nature of R substituents which strongly modulate activation entropy. At pH<2, decompositions of all three NONOates that have been investigated are subject to additional acid catalysis that occurs through di-protonation of the [NN(O)NO](-) group. Copyright © 2014 Elsevier Inc. All rights reserved.

Decomposition of amino diazeniumdiolates (NONOates): Molecular mechanisms

DOE PAGES

Shaikh, Nizamuddin; Valiev, Marat; Lymar, Sergei V.

2014-08-23

Although diazeniumdiolates (X[N(O)NO] -) are extensively used in biochemical, physiological, and pharmacological studies due to their ability to release NO and/or its congeneric nitroxyl, the mechanisms of these processes remain obscure. In this work, we used a combination of spectroscopic, kinetic, and computational techniques to arrive at a quantitatively consistent molecular mechanism for decomposition of amino diazeniumdiolates (amino NONOates: R 2N[N(O)NO] -, where R = —N(C 2H 5) 2(1), —N(C 3H 4NH 2) 2(2), or —N(C 2H 4NH 2) 2(3)). Decomposition of these NONOates is triggered by protonation of their [NN(O)NO] - group with the apparent pKa and decomposition ratemore » constants of 4.6 and 1 s -1 for 1; 3.5 and 0.083 s -1 for 2; and 3.8 and 0.0033 s -1 for 3. Although protonation occurs mainly on the O atoms of the functional group, only the minor R 2N(H)N(O)NO tautomer (population ~ 10 -7, for 1) undergoes the N—N heterolytic bond cleavage (k d ~ 107 s -1 for 1) leading to amine and NO. Decompositions of protonated amino NONOates are strongly temperature-dependent; activation enthalpies are 20.4 and 19.4 kcal/mol for 1 and 2, respectively, which includes contributions from both the tautomerization and bond cleavage. Thus, the bond cleavage rates exhibit exceptional sensitivity to the nature of R substituents which strongly modulate activation entropy. At pH < 2, decompositions of all three NONOates that have been investigated are subject to additional acid catalysis that occurs through di-protonation of the [NN(O)NO] - group.« less

Pyrolysis and Matrix-Isolation FTIR of Acetoin

NASA Astrophysics Data System (ADS)

Cole, Sarah; Ellis, Martha; Sowards, John; McCunn, Laura R.

2017-06-01

Acetoin, CH_3C(O)CH(OH)CH_3, is an additive used in foods and cigarettes as well as a common component of biomass pyrolysate during the production of biofuels, yet little is known about its thermal decomposition mechanism. In order to identify thermal decomposition products of acetoin, a gas-phase mixture of approximately 0.3% acetoin in argon was subject to pyrolysis in a resistively heated SiC microtubular reactor at 1100-1500 K. Matrix-isolation FTIR spectroscopy was used to identify pyrolysis products. Many products were observed in analysis of the spectra, including acetylene, propyne, ethylene, and vinyl alcohol. These results provide clues to the overall mechanism of thermal decomposition and are important for predicting emissions from many industrial and residential processes.

Excited electronic state decomposition mechanisms and dynamics of nitramine energetic materials and model systems

NASA Astrophysics Data System (ADS)

Greenfield, Margo

Energetic materials play an important role in aeronautics, the weapon industry, and the propellant industry due to their broad applications as explosives and fuels. RDX (1,3,5-trinitrohexahydro-s-triazine), HMX (octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine), and CL-20 (2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane) are compounds which contain high energy density. Although RDX and HMX have been studied extensively over the past several decades a complete understanding of their decomposition mechanisms and dynamics is unknown. Time of flight mass spectroscopy (TOFMS) UV photodissociation (ns) experiments of gas phase RDX, HMX, and CL-20 generate the NO molecule as the initial decomposition product. Four different vibronic transitions of the initial decomposition product, the NO molecule, are observed: A2Sigma(upsilon'=0)←X 2pi(upsilon"=0,1,2,3). Simulations of the rovibronic intensities for the A←X transitions demonstrate that NO dissociated from RDX, HMX, and CL-20 is rotationally cold (˜20 K) and vibrationally hot (˜1800 K). Conversely, experiments on the five model systems (nitromethane, dimethylnitramine (DMNA), nitropyrrolidine, nitropiperidine and dinitropiperazine) produce rotationally hot and vibrationally cold spectra. Laser induced fluorescence (LIF) experiments are performed to rule out the possible decomposition product OH, generated along with NO, perhaps from the suggested HONO elimination mechanism. The OH radical is not observed in the fluorescence experiments, indicating the HONO decomposition intermediate is not an important pathway for the excited electronic state decomposition of cyclic nitramines. The NO molecule is also employed to measure the dynamics of the excited state decomposition. A 226 nm, 180 fs light pulse is utilized to photodissociate the gas phase systems. Stable ion states of DMNA and nitropyrrolidine are observed while the energetic materials and remaining model systems present the NO molecule as the only observed product. Pump-probe transients of the resonant A←X (0-0) transition of the NO molecule show a constant signal indicating these materials decompose faster than the time duration of the 226 nm laser light. Calculational results together with the experimental results indicate the energetic materials decompose through an internal conversion to very highly excited (˜5 eV of vibrational energy) vibrational states of their ground electronic state, while the model systems follow an excited electronic state decomposition pathway.

Time-resolved spectroscopic measurements of shock-wave induced decomposition in cyclotrimethylene trinitramine (RDX) crystals: anisotropic response.

PubMed

Dang, Nhan C; Dreger, Zbigniew A; Gupta, Yogendra M; Hooks, Daniel E

2010-11-04

Plate impact experiments on the (210), (100), and (111) planes were performed to examine the role of crystalline anisotropy on the shock-induced decomposition of cyclotrimethylenetrinitramine (RDX) crystals. Time-resolved emission spectroscopy was used to probe the decomposition of single crystals shocked to peak stresses ranging between 7 and 20 GPa. Emission produced by decomposition intermediates was analyzed in terms of induction time to emission, emission intensity, and the emission spectra shapes as a function of stress and time. Utilizing these features, we found that the shock-induced decomposition of RDX crystals exhibits considerable anisotropy. Crystals shocked on the (210) and (100) planes were more sensitive to decomposition than crystals shocked on the (111) plane. The possible sources of the observed anisotropy are discussed with regard to the inelastic deformation mechanisms of shocked RDX. Our results suggest that, despite the anisotropy observed for shock initiation, decomposition pathways for all three orientations are similar.

Ozone decomposition

PubMed Central

Batakliev, Todor; Georgiev, Vladimir; Anachkov, Metody; Rakovsky, Slavcho

2014-01-01

Catalytic ozone decomposition is of great significance because ozone is a toxic substance commonly found or generated in human environments (aircraft cabins, offices with photocopiers, laser printers, sterilizers). Considerable work has been done on ozone decomposition reported in the literature. This review provides a comprehensive summary of the literature, concentrating on analysis of the physico-chemical properties, synthesis and catalytic decomposition of ozone. This is supplemented by a review on kinetics and catalyst characterization which ties together the previously reported results. Noble metals and oxides of transition metals have been found to be the most active substances for ozone decomposition. The high price of precious metals stimulated the use of metal oxide catalysts and particularly the catalysts based on manganese oxide. It has been determined that the kinetics of ozone decomposition is of first order importance. A mechanism of the reaction of catalytic ozone decomposition is discussed, based on detailed spectroscopic investigations of the catalytic surface, showing the existence of peroxide and superoxide surface intermediates. PMID:26109880

Experimental characterization of pairwise correlations from triple quantum correlated beams generated by cascaded four-wave mixing processes

NASA Astrophysics Data System (ADS)

Wang, Wei; Cao, Leiming; Lou, Yanbo; Du, Jinjian; Jing, Jietai

2018-01-01

We theoretically and experimentally characterize the performance of the pairwise correlations from triple quantum correlated beams based on the cascaded four-wave mixing (FWM) processes. The pairwise correlations between any two of the beams are theoretically calculated and experimentally measured. The experimental and theoretical results are in good agreement. We find that two of the three pairwise correlations can be in the quantum regime. The other pairwise correlation is always in the classical regime. In addition, we also measure the triple-beam correlation which is always in the quantum regime. Such unbalanced and controllable pairwise correlation structures may be taken as advantages in practical quantum communications, for example, hierarchical quantum secret sharing. Our results also open the way for the classification and application of quantum states generated from the cascaded FWM processes.

Thermal Decomposition Mechanisms of Alkylimidazolium Ionic Liquids with CN-containing Anions

DTIC Science & Technology

2014-11-01

anion calculated at the M06/6-31+G(d,p) level of theory and using the generic ionic liquid (GIL) model to simulate the condensed phase methyl...decomposition mechanisms of alkylimidazolium ionic liquids with CN-containing anions 5b. GRANT NUMBER 5c. PROGRAM ELEMENT NUMBER 6. AUTHOR(S) 5d...perform, display, or disclose the work. 14. ABSTRACT Due to the unusually high heats of vaporization of room-temperature ionic liquids (RTILs

Changes in bacterial and eukaryotic communities during sewage decomposition in Mississippi River water

EPA Science Inventory

Microbial decay processes are one of the mechanisms whereby sewage contamination is reduced in the environment. This decomposition process involves a highly complex array of bacterial and eukaryotic communities from both sewage and ambient waters. However, relatively little is kn...

Azole energetic materials: Initial mechanisms for the energy release from electronical excited nitropyrazoles

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yuan, Bing; Yu, Zijun; Bernstein, Elliot R., E-mail: erb@lamar.Colostate.edu

2014-01-21

Decomposition of energetic material 3,4-dinitropyrazole (DNP) and two model molecules 4-nitropyrazole and 1-nitropyrazole is investigated both theoretically and experimentally. The initial decomposition mechanisms for these three nitropyrazoles are explored with complete active space self-consistent field (CASSCF) level. The NO molecule is observed as an initial decomposition product from all three materials subsequent to UV excitation. Observed NO products are rotationally cold (<50 K) for all three systems. The vibrational temperature of the NO product from DNP is (3850 ± 50) K, 1350 K hotter than that of the two model species. Potential energy surface calculations at the CASSCF(12,8)/6-31+G(d) level illustratemore » that conical intersections plays an essential role in the decomposition mechanism. Electronically excited S{sub 2} nitropyraozles can nonradiatively relax to lower electronic states through (S{sub 2}/S{sub 1}){sub CI} and (S{sub 1}/S{sub 0}){sub CI} conical intersection and undergo a nitro-nitrite isomerization to generate NO product either in the S{sub 1} state or S{sub 0} state. In model systems, NO is generated in the S{sub 1} state, while in the energetic material DNP, NO is produced on the ground state surface, as the S{sub 1} decomposition pathway is energetically unavailable. The theoretically predicted mechanism is consistent with the experimental results, as DNP decomposes in a lower electronic state than do the model systems and thus the vibrational energy in the NO product from DNP should be hotter than from the model systems. The observed rotational energy distributions for NO are consistent with the final structures of the respective transition states for each molecule.« less

Molecular mechanism of metal-independent decomposition of lipid hydroperoxide 13-HPODE by halogenated quinoid carcinogens.

PubMed

Qin, Hao; Huang, Chun-Hua; Mao, Li; Xia, Hai-Ying; Kalyanaraman, Balaraman; Shao, Jie; Shan, Guo-Qiang; Zhu, Ben-Zhan

2013-10-01

Halogenated quinones are a class of carcinogenic intermediates and newly identified chlorination disinfection by-products in drinking water. 13-Hydroperoxy-9,11-octadecadienoic acid (13-HPODE) is the most extensively studied endogenous lipid hydroperoxide. Although it is well known that the decomposition of 13-HPODE can be catalyzed by transition metal ions, it is not clear whether halogenated quinones could enhance its decomposition independent of metal ions and, if so, what the unique characteristics and similarities are. Here we show that 2,5-dichloro-1,4-benzoquinone (DCBQ) could markedly enhance the decomposition of 13-HPODE and formation of reactive lipid alkyl radicals such as pentyl and 7-carboxyheptyl radicals, and the genotoxic 4-hydroxy-2-nonenal (HNE), through the complementary application of ESR spin trapping, HPLC-MS, and GC-MS methods. Interestingly, two chloroquinone-lipid alkoxyl conjugates were also detected and identified from the reaction between DCBQ and 13-HPODE. Analogous results were observed with other halogenated quinones. This represents the first report that halogenated quinoid carcinogens can enhance the decomposition of the endogenous lipid hydroperoxide 13-HPODE and formation of reactive lipid alkyl radicals and genotoxic HNE via a novel metal-independent nucleophilic substitution coupled with homolytic decomposition mechanism, which may partly explain their potential genotoxicity and carcinogenicity. Copyright © 2013 Elsevier Inc. All rights reserved.

Ab initio kinetics and thermal decomposition mechanism of mononitrobiuret and 1,5-dinitrobiuret

NASA Astrophysics Data System (ADS)

Sun, Hongyan; Vaghjiani, Ghanshyam L.

2015-05-01

Mononitrobiuret (MNB) and 1,5-dinitrobiuret (DNB) are tetrazole-free, nitrogen-rich, energetic compounds. For the first time, a comprehensive ab initio kinetics study on the thermal decomposition mechanisms of MNB and DNB is reported here. In particular, the intramolecular interactions of amine H-atom with electronegative nitro O-atom and carbonyl O-atom have been analyzed for biuret, MNB, and DNB at the M06-2X/aug-cc-pVTZ level of theory. The results show that the MNB and DNB molecules are stabilized through six-member-ring moieties via intramolecular H-bonding with interatomic distances between 1.8 and 2.0 Å, due to electrostatic as well as polarization and dispersion interactions. Furthermore, it was found that the stable molecules in the solid state have the smallest dipole moment amongst all the conformers in the nitrobiuret series of compounds, thus revealing a simple way for evaluating reactivity of fuel conformers. The potential energy surface for thermal decomposition of MNB was characterized by spin restricted coupled cluster theory at the RCCSD(T)/cc-pV∞ Z//M06-2X/aug-cc-pVTZ level. It was found that the thermal decomposition of MNB is initiated by the elimination of HNCO and HNN(O)OH intermediates. Intramolecular transfer of a H-atom, respectively, from the terminal NH2 group to the adjacent carbonyl O-atom via a six-member-ring transition state eliminates HNCO with an energy barrier of 35 kcal/mol and from the central NH group to the adjacent nitro O-atom eliminates HNN(O)OH with an energy barrier of 34 kcal/mol. Elimination of HNN(O)OH is also the primary process involved in the thermal decomposition of DNB, which processes C2v symmetry. The rate coefficients for the primary decomposition channels for MNB and DNB were quantified as functions of temperature and pressure. In addition, the thermal decomposition of HNN(O)OH was analyzed via Rice-Ramsperger-Kassel-Marcus/multi-well master equation simulations, the results of which reveal the formation of (NO2 + H2O) to be the major decomposition path. Furthermore, we provide fundamental interpretations for the experimental results of Klapötke et al. [Combust. Flame 139, 358-366 (2004)] regarding the thermal stability of MNB and DNB, and their decomposition products. Notably, a fundamental understanding of fuel stability, decomposition mechanism, and key reactions leading to ignition is essential in the design and manipulation of molecular systems for the development of new energetic materials for advanced propulsion applications.

Ab Initio Kinetics and Thermal Decomposition Mechanism of Mononitrobiuret and 1,5- Dinitrobiuret

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sun, Hongyan; Vaghjiani, Ghanshyam G.

2015-05-26

Mononitrobiuret (MNB) and 1,5-dinitrobiuret (DNB) are tetrazole-free, nitrogen-rich, energetic compounds. For the first time, a comprehensive ab initio kinetics study on the thermal decomposition mechanisms of MNB and DNB is reported here. In particular, the intramolecular interactions of amine H-atom with electronegative nitro O-atom and carbonyl O-atom have been analyzed for biuret, MNB, and DNB at the M06-2X/aug-cc-pVTZ level of theory. The results show that the MNB and DNB molecules are stabilized through six-member-ring moieties via intramolecular H-bonding with interatomic distances between 1.8 and 2.0 Å, due to electrostatic as well as polarization and dispersion interactions. Furthermore, it was foundmore » that the stable molecules in the solid state have the smallest dipole moment amongst all the conformers in the nitrobiuret series of compounds, thus revealing a simple way for evaluating reactivity of fuel conformers. The potential energy surface for thermal decomposition of MNB was characterized by spin restricted coupled cluster theory at the RCCSD(T)/cc-pV∞ Z//M06-2X/aug-cc-pVTZ level. It was found that the thermal decomposition of MNB is initiated by the elimination of HNCO and HNN(O)OH intermediates. Intramolecular transfer of a H-atom, respectively, from the terminal NH2 group to the adjacent carbonyl O-atom via a six-member-ring transition state eliminates HNCO with an energy barrier of 35 kcal/mol and from the central NH group to the adjacent nitro O-atom eliminates HNN(O)OH with an energy barrier of 34 kcal/mol. Elimination of HNN(O)OH is also the primary process involved in the thermal decomposition of DNB, which processes C2v symmetry. The rate coefficients for the primary decomposition channels for MNB and DNB were quantified as functions of temperature and pressure. In addition, the thermal decomposition of HNN(O)OH was analyzed via Rice–Ramsperger–Kassel–Marcus/multi-well master equation simulations, the results of which reveal the formation of (NO2 + H2O) to be the major decomposition path. Furthermore, we provide fundamental interpretations for the experimental results of Klapötke et al. [Combust. Flame 139, 358–366 (2004)] regarding the thermal stability of MNB and DNB, and their decomposition products. Notably, a fundamental understanding of fuel stability, decomposition mechanism, and key reactions leading to ignition is essential in the design and manipulation of molecular systems for the development of new energetic materials for advanced propulsion applications.« less

Ab initio kinetics and thermal decomposition mechanism of mononitrobiuret and 1,5-dinitrobiuret.

PubMed

Sun, Hongyan; Vaghjiani, Ghanshyam L

2015-05-28

Mononitrobiuret (MNB) and 1,5-dinitrobiuret (DNB) are tetrazole-free, nitrogen-rich, energetic compounds. For the first time, a comprehensive ab initio kinetics study on the thermal decomposition mechanisms of MNB and DNB is reported here. In particular, the intramolecular interactions of amine H-atom with electronegative nitro O-atom and carbonyl O-atom have been analyzed for biuret, MNB, and DNB at the M06-2X/aug-cc-pVTZ level of theory. The results show that the MNB and DNB molecules are stabilized through six-member-ring moieties via intramolecular H-bonding with interatomic distances between 1.8 and 2.0 Å, due to electrostatic as well as polarization and dispersion interactions. Furthermore, it was found that the stable molecules in the solid state have the smallest dipole moment amongst all the conformers in the nitrobiuret series of compounds, thus revealing a simple way for evaluating reactivity of fuel conformers. The potential energy surface for thermal decomposition of MNB was characterized by spin restricted coupled cluster theory at the RCCSD(T)/cc-pV∞ Z//M06-2X/aug-cc-pVTZ level. It was found that the thermal decomposition of MNB is initiated by the elimination of HNCO and HNN(O)OH intermediates. Intramolecular transfer of a H-atom, respectively, from the terminal NH2 group to the adjacent carbonyl O-atom via a six-member-ring transition state eliminates HNCO with an energy barrier of 35 kcal/mol and from the central NH group to the adjacent nitro O-atom eliminates HNN(O)OH with an energy barrier of 34 kcal/mol. Elimination of HNN(O)OH is also the primary process involved in the thermal decomposition of DNB, which processes C2v symmetry. The rate coefficients for the primary decomposition channels for MNB and DNB were quantified as functions of temperature and pressure. In addition, the thermal decomposition of HNN(O)OH was analyzed via Rice-Ramsperger-Kassel-Marcus/multi-well master equation simulations, the results of which reveal the formation of (NO2 + H2O) to be the major decomposition path. Furthermore, we provide fundamental interpretations for the experimental results of Klapötke et al. [Combust. Flame 139, 358-366 (2004)] regarding the thermal stability of MNB and DNB, and their decomposition products. Notably, a fundamental understanding of fuel stability, decomposition mechanism, and key reactions leading to ignition is essential in the design and manipulation of molecular systems for the development of new energetic materials for advanced propulsion applications.

Matrix multiplication operations using pair-wise load and splat operations

DOE Office of Scientific and Technical Information (OSTI.GOV)

Eichenberger, Alexandre E.; Gschwind, Michael K.; Gunnels, John A.

Mechanisms for performing a matrix multiplication operation are provided. A vector load operation is performed to load a first vector operand of the matrix multiplication operation to a first target vector register. A pair-wise load and splat operation is performed to load a pair of scalar values of a second vector operand and replicate the pair of scalar values within a second target vector register. An operation is performed on elements of the first target vector register and elements of the second target vector register to generate a partial product of the matrix multiplication operation. The partial product is accumulatedmore » with other partial products and a resulting accumulated partial product is stored. This operation may be repeated for a second pair of scalar values of the second vector operand.« less

cDF Theory Software for mesoscopic modeling of equilibrium and transport phenomena

DOE Office of Scientific and Technical Information (OSTI.GOV)

2015-12-01

The approach is based on classical Density Functional Theory ((cDFT) coupled with the Poisson-Nernst-Planck (PNP) transport kinetics model and quantum mechanical description of short-range interaction and elementary transport processes. The model we proposed and implemented is fully atomistic, taking into account pairwise short-range and manybody long-range interactions. But in contrast to standard molecular dynamics (MD) simulations, where long-range manybody interactions are evaluated as a sum of pair-wise atom-atom contributions, we include them analytically based on wellestablished theories of electrostatic and excluded volume interactions in multicomponent systems. This feature of the PNP/cDFT approach allows us to reach well beyond the length-scalesmore » accessible to MD simulations, while retaining the essential physics of interatomic interactions from first principles and in a parameter-free fashion.« less

Sparse approximation of currents for statistics on curves and surfaces.

PubMed

Durrleman, Stanley; Pennec, Xavier; Trouvé, Alain; Ayache, Nicholas

2008-01-01

Computing, processing, visualizing statistics on shapes like curves or surfaces is a real challenge with many applications ranging from medical image analysis to computational geometry. Modelling such geometrical primitives with currents avoids feature-based approach as well as point-correspondence method. This framework has been proved to be powerful to register brain surfaces or to measure geometrical invariants. However, if the state-of-the-art methods perform efficiently pairwise registrations, new numerical schemes are required to process groupwise statistics due to an increasing complexity when the size of the database is growing. Statistics such as mean and principal modes of a set of shapes often have a heavy and highly redundant representation. We propose therefore to find an adapted basis on which mean and principal modes have a sparse decomposition. Besides the computational improvement, this sparse representation offers a way to visualize and interpret statistics on currents. Experiments show the relevance of the approach on 34 sets of 70 sulcal lines and on 50 sets of 10 meshes of deep brain structures.

Nonlocal van der Waals functionals: The case of rare-gas dimers and solids

NASA Astrophysics Data System (ADS)

Tran, Fabien; Hutter, Jürg

2013-05-01

Recently, the nonlocal van der Waals (vdW) density functionals [M. Dion, H. Rydberg, E. Schröder, D. C. Langreth, and B. I. Lundqvist, Phys. Rev. Lett. 92, 246401 (2004), 10.1103/PhysRevLett.92.246401] have attracted considerable attention due to their good performance for systems where weak interactions are important. Since the physics of dispersion is included in these functionals, they are usually more accurate and show less erratic behavior than the semilocal and hybrid methods. In this work, several variants of the vdW functionals have been tested on rare-gas dimers (from He2 to Kr2) and solids (Ne, Ar, and Kr) and their accuracy compared to standard semilocal approximations, supplemented or not by an atom-pairwise dispersion correction [S. Grimme, J. Antony, S. Ehrlich, and H. Krieg, J. Chem. Phys. 132, 154104 (2010), 10.1063/1.3382344]. An analysis of the results in terms of energy decomposition is also provided.

Precoded spatial multiplexing MIMO system with spatial component interleaver.

PubMed

Gao, Xiang; Wu, Zhanji

In this paper, the performance of precoded bit-interleaved coded modulation (BICM) spatial multiplexing multiple-input multiple-output (MIMO) system with spatial component interleaver is investigated. For the ideal precoded spatial multiplexing MIMO system with spatial component interleaver based on singular value decomposition (SVD) of the MIMO channel, the average pairwise error probability (PEP) of coded bits is derived. Based on the PEP analysis, the optimum spatial Q-component interleaver design criterion is provided to achieve the minimum error probability. For the limited feedback precoded proposed scheme with linear zero forcing (ZF) receiver, in order to minimize a bound on the average probability of a symbol vector error, a novel effective signal-to-noise ratio (SNR)-based precoding matrix selection criterion and a simplified criterion are proposed. Based on the average mutual information (AMI)-maximization criterion, the optimal constellation rotation angles are investigated. Simulation results indicate that the optimized spatial multiplexing MIMO system with spatial component interleaver can achieve significant performance advantages compared to the conventional spatial multiplexing MIMO system.

On orbital allotments for geostationary satellites

NASA Technical Reports Server (NTRS)

Gonsalvez, David J. A.; Reilly, Charles H.; Mount-Campbell, Clark A.

1986-01-01

The following satellite synthesis problem is addressed: communication satellites are to be allotted positions on the geostationary arc so that interference does not exceed a given acceptable level by enforcing conservative pairwise satellite separation. A desired location is specified for each satellite, and the objective is to minimize the sum of the deviations between the satellites' prescribed and desired locations. Two mixed integer programming models for the satellite synthesis problem are presented. Four solution strategies, branch-and-bound, Benders' decomposition, linear programming with restricted basis entry, and a switching heuristic, are used to find solutions to example synthesis problems. Computational results indicate the switching algorithm yields solutions of good quality in reasonable execution times when compared to the other solution methods. It is demonstrated that the switching algorithm can be applied to synthesis problems with the objective of minimizing the largest deviation between a prescribed location and the corresponding desired location. Furthermore, it is shown that the switching heuristic can use no conservative, location-dependent satellite separations in order to satisfy interference criteria.

Development of rate expressions for the thermal decomposition of RDX

DOE Office of Scientific and Technical Information (OSTI.GOV)

Erickson, K.L.; Behrens, R. Jr.; Bulusu, S.

Decomposition and combustion of energetic materials involve processes in both condensed and gas phases. Development of reliable models for design, performance, stability, and hazard analyses requires detailed understanding of the mechanisms for both the initial condensed phase decomposition of the energetic material and the subsequent reaction of the decomposition species to form the ultimate reaction products. Those mechanisms must be described in terms of constitutive rate expressions that can be incorporated into mathematical models. The thermal decomposition of RDX has been studied by Behrens and Bulusu using Simultaneous Thermogravimetric Modulated Beam Mass Spectrometry (STMBMS). Their work provides a basis formore » developing some of the constitutive rate expressions that are needed in models for design, performance, stability and hazard analyses involving RDX. Behrens and Bulusu have identified four primary reaction pathways that control the liquid-phase decomposition of RDX at temperatures between 200 and 215{degrees}C, and one that controls solid-phase decomposition at temperatures below 200{degrees}C. Two of the liquid-phase pathways appear to be first order in RDX. Arrhenius parameters for the first-order rate constants were evaluated from data reported by Behrens and Bulusu. Reaction rates extrapolated to temperatures between 370 and 450{degrees}C are in good agreement with global reaction rates observed by Trott et al. using high-speed photography and laser-heated thin-film samples. Furthermore, the STMBMS results of Behrens and Bulusu appear to be consistent with condensed-phase infrared results reported by Trott et al. and Erickson et al.« less

Development of rate expressions for the thermal decomposition of RDX

DOE Office of Scientific and Technical Information (OSTI.GOV)

Erickson, K.L.; Behrens, R. Jr.; Bulusu, S.

Decomposition and combustion of energetic materials involve processes in both condensed and gas phases. Development of reliable models for design, performance, stability, and hazard analyses requires detailed understanding of the mechanisms for both the initial condensed phase decomposition of the energetic material and the subsequent reaction of the decomposition species to form the ultimate reaction products. Those mechanisms must be described in terms of constitutive rate expressions that can be incorporated into mathematical models. The thermal decomposition of RDX has been studied by Behrens and Bulusu using Simultaneous Thermogravimetric Modulated Beam Mass Spectrometry (STMBMS). Their work provides a basis formore » developing some of the constitutive rate expressions that are needed in models for design, performance, stability and hazard analyses involving RDX. Behrens and Bulusu have identified four primary reaction pathways that control the liquid-phase decomposition of RDX at temperatures between 200 and 215[degrees]C, and one that controls solid-phase decomposition at temperatures below 200[degrees]C. Two of the liquid-phase pathways appear to be first order in RDX. Arrhenius parameters for the first-order rate constants were evaluated from data reported by Behrens and Bulusu. Reaction rates extrapolated to temperatures between 370 and 450[degrees]C are in good agreement with global reaction rates observed by Trott et al. using high-speed photography and laser-heated thin-film samples. Furthermore, the STMBMS results of Behrens and Bulusu appear to be consistent with condensed-phase infrared results reported by Trott et al. and Erickson et al.« less

In situ chemical oxidation of contaminated groundwater by persulfate: decomposition by Fe(III)- and Mn(IV)-containing oxides and aquifer materials.

PubMed

Liu, Haizhou; Bruton, Thomas A; Doyle, Fiona M; Sedlak, David L

2014-09-02

Persulfate (S2O8(2-)) is being used increasingly for in situ chemical oxidation (ISCO) of organic contaminants in groundwater, despite an incomplete understanding of the mechanism through which it is converted into reactive species. In particular, the decomposition of persulfate by naturally occurring mineral surfaces has not been studied in detail. To gain insight into the reaction rates and mechanism of persulfate decomposition in the subsurface, and to identify possible approaches for improving its efficacy, the decomposition of persulfate was investigated in the presence of pure metal oxides, clays, and representative aquifer solids collected from field sites in the presence and absence of benzene. Under conditions typical of groundwater, Fe(III)- and Mn(IV)-oxides catalytically converted persulfate into sulfate radical (SO4(•-)) and hydroxyl radical (HO(•)) over time scales of several weeks at rates that were 2-20 times faster than those observed in metal-free systems. Amorphous ferrihydrite was the most reactive iron mineral with respect to persulfate decomposition, with reaction rates proportional to solid mass and surface area. As a result of radical chain reactions, the rate of persulfate decomposition increased by as much as 100 times when benzene concentrations exceeded 0.1 mM. Due to its relatively slow rate of decomposition in the subsurface, it can be advantageous to inject persulfate into groundwater, allowing it to migrate to zones of low hydraulic conductivity where clays, metal oxides, and contaminants will accelerate its conversion into reactive oxidants.

In Situ Chemical Oxidation of Contaminated Groundwater by Persulfate: Decomposition by Fe(III)- and Mn(IV)-Containing Oxides and Aquifer Materials

PubMed Central

2015-01-01

Persulfate (S2O82–) is being used increasingly for in situ chemical oxidation (ISCO) of organic contaminants in groundwater, despite an incomplete understanding of the mechanism through which it is converted into reactive species. In particular, the decomposition of persulfate by naturally occurring mineral surfaces has not been studied in detail. To gain insight into the reaction rates and mechanism of persulfate decomposition in the subsurface, and to identify possible approaches for improving its efficacy, the decomposition of persulfate was investigated in the presence of pure metal oxides, clays, and representative aquifer solids collected from field sites in the presence and absence of benzene. Under conditions typical of groundwater, Fe(III)- and Mn(IV)-oxides catalytically converted persulfate into sulfate radical (SO4•–) and hydroxyl radical (HO•) over time scales of several weeks at rates that were 2–20 times faster than those observed in metal-free systems. Amorphous ferrihydrite was the most reactive iron mineral with respect to persulfate decomposition, with reaction rates proportional to solid mass and surface area. As a result of radical chain reactions, the rate of persulfate decomposition increased by as much as 100 times when benzene concentrations exceeded 0.1 mM. Due to its relatively slow rate of decomposition in the subsurface, it can be advantageous to inject persulfate into groundwater, allowing it to migrate to zones of low hydraulic conductivity where clays, metal oxides, and contaminants will accelerate its conversion into reactive oxidants. PMID:25133603

Sythesis of MCMC and Belief Propagation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ahn, Sungsoo; Chertkov, Michael; Shin, Jinwoo

Markov Chain Monte Carlo (MCMC) and Belief Propagation (BP) are the most popular algorithms for computational inference in Graphical Models (GM). In principle, MCMC is an exact probabilistic method which, however, often suffers from exponentially slow mixing. In contrast, BP is a deterministic method, which is typically fast, empirically very successful, however in general lacking control of accuracy over loopy graphs. In this paper, we introduce MCMC algorithms correcting the approximation error of BP, i.e., we provide a way to compensate for BP errors via a consecutive BP-aware MCMC. Our framework is based on the Loop Calculus (LC) approach whichmore » allows to express the BP error as a sum of weighted generalized loops. Although the full series is computationally intractable, it is known that a truncated series, summing up all 2-regular loops, is computable in polynomial-time for planar pair-wise binary GMs and it also provides a highly accurate approximation empirically. Motivated by this, we first propose a polynomial-time approximation MCMC scheme for the truncated series of general (non-planar) pair-wise binary models. Our main idea here is to use the Worm algorithm, known to provide fast mixing in other (related) problems, and then design an appropriate rejection scheme to sample 2-regular loops. Furthermore, we also design an efficient rejection-free MCMC scheme for approximating the full series. The main novelty underlying our design is in utilizing the concept of cycle basis, which provides an efficient decomposition of the generalized loops. In essence, the proposed MCMC schemes run on transformed GM built upon the non-trivial BP solution, and our experiments show that this synthesis of BP and MCMC outperforms both direct MCMC and bare BP schemes.« less

Thermal decomposition of pyrazole to vinylcarbene + N 2: A first principles/RRKM study

NASA Astrophysics Data System (ADS)

da Silva, Gabriel

2009-05-01

Thermal decomposition of pyrazole, a five-membered nitrogen-containing heterocycle, has been studied using ab initio G3X theory and RRKM rate theory. The decomposition mechanism involves an intramolecular hydrogen shift to 3 H-pyrazole, followed by ring opening to 3-diazo-1-propene and dissociation to vinylcarbene (CH 2CHCH) + N 2. At 1 atm the calculated rate equation k [s -1] = 1.26 × 10 50T-10.699e -41200/T is obtained, which agrees with the results of flash vacuum pyrolysis experiments. The pyrazole decomposition product vinylcarbene is expected to rearrange to propyne, making pyrazole decomposition essentially thermoneutral. It is hypothesized that at high concentrations vinylcarbene could undergo a self-reaction to 1,3- and 1,4-cyclohexadiene.

The spinodal decomposition in 17-4PH stainless steel subjected to long-term aging at 350 deg. C

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wang Jun; Zou Hong; Li Cong

2008-05-15

The influence of aging time on the microstructure evolution of 17-4 PH martensitic stainless steel was studied by transmission electron microscopy (TEM). Results showed that the martensite decomposed by a spinodal decomposition mechanism after the alloy was subjected to long-term aging at 350 deg. C. The fine scale spinodal decomposition of {alpha}-ferrite brought about a Cr-enriched bright stripe and a Fe-enriched dark stripe, i.e., {alpha}' and {alpha} phases, separately, which were perpendicular to the grain boundary. The spinodal decomposition started at the grain boundary. Then with prolonged aging time, the decomposition microstructure expanded from the grain boundary to interior. Themore » wavelength of the spinodally decomposed microstructure changed little with extended aging time.« less

Manipulation of Karyotype in Caenorhabditis elegans Reveals Multiple Inputs Driving Pairwise Chromosome Synapsis During Meiosis

PubMed Central

Roelens, Baptiste; Schvarzstein, Mara; Villeneuve, Anne M.

2015-01-01

Meiotic chromosome segregation requires pairwise association between homologs, stabilized by the synaptonemal complex (SC). Here, we investigate factors contributing to pairwise synapsis by investigating meiosis in polyploid worms. We devised a strategy, based on transient inhibition of cohesin function, to generate polyploid derivatives of virtually any Caenorhabditis elegans strain. We exploited this strategy to investigate the contribution of recombination to pairwise synapsis in tetraploid and triploid worms. In otherwise wild-type polyploids, chromosomes first sort into homolog groups, then multipartner interactions mature into exclusive pairwise associations. Pairwise synapsis associations still form in recombination-deficient tetraploids, confirming a propensity for synapsis to occur in a strictly pairwise manner. However, the transition from multipartner to pairwise association was perturbed in recombination-deficient triploids, implying a role for recombination in promoting this transition when three partners compete for synapsis. To evaluate the basis of synapsis partner preference, we generated polyploid worms heterozygous for normal sequence and rearranged chromosomes sharing the same pairing center (PC). Tetraploid worms had no detectable preference for identical partners, indicating that PC-adjacent homology drives partner choice in this context. In contrast, triploid worms exhibited a clear preference for identical partners, indicating that homology outside the PC region can influence partner choice. Together, our findings, suggest a two-phase model for C. elegans synapsis: an early phase, in which initial synapsis interactions are driven primarily by recombination-independent assessment of homology near PCs and by a propensity for pairwise SC assembly, and a later phase in which mature synaptic interactions are promoted by recombination. PMID:26500263

Laser Ignition of Nitramine Composite Propellants and Crack Propagation and Branching in Burning Solid Propellants

DTIC Science & Technology

1987-10-01

34 Proceedings of the 16th JANNAF Com- bustion Meeting, Sept. 1979, Vol. II, pp. 13-34. 44. Schroeder , M. A., " Critical Analysis of Nitramine Decomposition...34 Proceedings of the 19th JANNAF Combustion Meeting, Oct. 1982. 47. Schroeder , M. A., " Critical Analysis of Nitramine Decomposition Data: Ac- tivation...the surface of the propellant. This is consis- tent with the decomposition mechanism considered by Boggs[48] and Schroeder [43J. They concluded that the

Building dynamic population graph for accurate correspondence detection.

PubMed

Du, Shaoyi; Guo, Yanrong; Sanroma, Gerard; Ni, Dong; Wu, Guorong; Shen, Dinggang

2015-12-01

In medical imaging studies, there is an increasing trend for discovering the intrinsic anatomical difference across individual subjects in a dataset, such as hand images for skeletal bone age estimation. Pair-wise matching is often used to detect correspondences between each individual subject and a pre-selected model image with manually-placed landmarks. However, the large anatomical variability across individual subjects can easily compromise such pair-wise matching step. In this paper, we present a new framework to simultaneously detect correspondences among a population of individual subjects, by propagating all manually-placed landmarks from a small set of model images through a dynamically constructed image graph. Specifically, we first establish graph links between models and individual subjects according to pair-wise shape similarity (called as forward step). Next, we detect correspondences for the individual subjects with direct links to any of model images, which is achieved by a new multi-model correspondence detection approach based on our recently-published sparse point matching method. To correct those inaccurate correspondences, we further apply an error detection mechanism to automatically detect wrong correspondences and then update the image graph accordingly (called as backward step). After that, all subject images with detected correspondences are included into the set of model images, and the above two steps of graph expansion and error correction are repeated until accurate correspondences for all subject images are established. Evaluations on real hand X-ray images demonstrate that our proposed method using a dynamic graph construction approach can achieve much higher accuracy and robustness, when compared with the state-of-the-art pair-wise correspondence detection methods as well as a similar method but using static population graph. Copyright © 2015 Elsevier B.V. All rights reserved.

Structure based alignment and clustering of proteins (STRALCP)

DOEpatents

Zemla, Adam T.; Zhou, Carol E.; Smith, Jason R.; Lam, Marisa W.

2013-06-18

Disclosed are computational methods of clustering a set of protein structures based on local and pair-wise global similarity values. Pair-wise local and global similarity values are generated based on pair-wise structural alignments for each protein in the set of protein structures. Initially, the protein structures are clustered based on pair-wise local similarity values. The protein structures are then clustered based on pair-wise global similarity values. For each given cluster both a representative structure and spans of conserved residues are identified. The representative protein structure is used to assign newly-solved protein structures to a group. The spans are used to characterize conservation and assign a "structural footprint" to the cluster.

An effective hierarchical model for the biomolecular covalent bond: an approach integrating artificial chemistry and an actual terrestrial life system.

PubMed

Oohashi, Tsutomu; Ueno, Osamu; Maekawa, Tadao; Kawai, Norie; Nishina, Emi; Honda, Manabu

2009-01-01

Under the AChem paradigm and the programmed self-decomposition (PSD) model, we propose a hierarchical model for the biomolecular covalent bond (HBCB model). This model assumes that terrestrial organisms arrange their biomolecules in a hierarchical structure according to the energy strength of their covalent bonds. It also assumes that they have evolutionarily selected the PSD mechanism of turning biological polymers (BPs) into biological monomers (BMs) as an efficient biomolecular recycling strategy We have examined the validity and effectiveness of the HBCB model by coordinating two complementary approaches: biological experiments using existent terrestrial life, and simulation experiments using an AChem system. Biological experiments have shown that terrestrial life possesses a PSD mechanism as an endergonic, genetically regulated process and that hydrolysis, which decomposes a BP into BMs, is one of the main processes of such a mechanism. In simulation experiments, we compared different virtual self-decomposition processes. The virtual species in which the self-decomposition process mainly involved covalent bond cleavage from a BP to BMs showed evolutionary superiority over other species in which the self-decomposition process involved cleavage from BP to classes lower than BM. These converging findings strongly support the existence of PSD and the validity and effectiveness of the HBCB model.

Theoretical study on the mechanism of the reaction of FOX-7 with OH and NO2 radicals: bimolecular reactions with low barrier during the decomposition of FOX-7

NASA Astrophysics Data System (ADS)

Zhang, Ji-Dong; Zhang, Li-Li

2017-12-01

The decomposition of 1,1-diamino-2,2-dinitroethene (FOX-7) attracts great interests, while the studies on bimolecular reactions during the decomposition of FOX-7 are scarce. This study for the first time investigated the bimolecular reactions of OH and NO2 radicals, which are pyrolysis products of ammonium perchlorate (an efficient oxidant usually used in solid propellant), with FOX-7 by computational chemistry methods. The molecular geometries and energies were calculated using the (U)B3LYP/6-31++G(d,p) method. The rate constants of the reactions were calculated by canonical variational transition state theory. We found three mechanisms (H-abstraction, OH addition to C and N atom) for the reaction of OH + FOX-7 and two mechanisms (O abstraction and H abstraction) for the reaction of NO2 + FOX-7. OH radical can abstract H atom or add to C atom of FOX-7 with barriers near to zero, which means OH radical can effectively degrade FOX-7. The O abstraction channel of the reaction of NO2 + FOX-7 results in the formation of NO3 radical, which has never been detected experimentally during the decomposition of FOX-7.

Anaerobic decomposition of humic substances by Clostridium from the deep subsurface

PubMed Central

Ueno, Akio; Shimizu, Satoru; Tamamura, Shuji; Okuyama, Hidetoshi; Naganuma, Takeshi; Kaneko, Katsuhiko

2016-01-01

Decomposition of humic substances (HSs) is a slow and cryptic but non-negligible component of carbon cycling in sediments. Aerobic decomposition of HSs by microorganisms in the surface environment has been well documented; however, the mechanism of anaerobic microbial decomposition of HSs is not completely understood. Moreover, no microorganisms capable of anaerobic decomposition of HSs have been isolated. Here, we report the anaerobic decomposition of humic acids (HAs) by the anaerobic bacterium Clostridium sp. HSAI-1 isolated from the deep terrestrial subsurface. The use of 14C-labelled polycatechol as an HA analogue demonstrated that the bacterium decomposed this substance up to 7.4% over 14 days. The decomposition of commercial and natural HAs by the bacterium yielded lower molecular mass fractions, as determined using high-performance size-exclusion chromatography. Fourier transform infrared spectroscopy revealed the removal of carboxyl groups and polysaccharide-related substances, as well as the generation of aliphatic components, amide and aromatic groups. Therefore, our results suggest that Clostridium sp. HSAI-1 anaerobically decomposes and transforms HSs. This study improves our understanding of the anaerobic decomposition of HSs in the hidden carbon cycling in the Earth’s subsurface. PMID:26743007

Experimental and modeling study on decomposition kinetics of methane hydrates in different media.

PubMed

Liang, Minyan; Chen, Guangjin; Sun, Changyu; Yan, Lijun; Liu, Jiang; Ma, Qinglan

2005-10-13

The decomposition kinetic behaviors of methane hydrates formed in 5 cm3 porous wet activated carbon were studied experimentally in a closed system in the temperature range of 275.8-264.4 K. The decomposition rates of methane hydrates formed from 5 cm3 of pure free water and an aqueous solution of 650 g x m(-3) sodium dodecyl sulfate (SDS) were also measured for comparison. The decomposition rates of methane hydrates in seven different cases were compared. The results showed that the methane hydrates dissociate more rapidly in porous activated carbon than in free systems. A mathematical model was developed for describing the decomposition kinetic behavior of methane hydrates below ice point based on an ice-shielding mechanism in which a porous ice layer was assumed to be formed during the decomposition of hydrate, and the diffusion of methane molecules through it was assumed to be one of the control steps. The parameters of the model were determined by correlating the decomposition rate data, and the activation energies were further determined with respect to three different media. The model was found to well describe the decomposition kinetic behavior of methane hydrate in different media.

Modeling Oil Shale Pyrolysis: High-Temperature Unimolecular Decomposition Pathways for Thiophene.

PubMed

Vasiliou, AnGayle K; Hu, Hui; Cowell, Thomas W; Whitman, Jared C; Porterfield, Jessica; Parish, Carol A

2017-10-12

The thermal decomposition mechanism of thiophene has been investigated both experimentally and theoretically. Thermal decomposition experiments were done using a 1 mm × 3 cm pulsed silicon carbide microtubular reactor, C 4 H 4 S + Δ → Products. Unlike previous studies these experiments were able to identify the initial thiophene decomposition products. Thiophene was entrained in either Ar, Ne, or He carrier gas, passed through a heated (300-1700 K) SiC microtubular reactor (roughly ≤100 μs residence time), and exited into a vacuum chamber. The resultant molecular beam was probed by photoionization mass spectroscopy and IR spectroscopy. The pyrolysis mechanisms of thiophene were also investigated with the CBS-QB3 method using UB3LYP/6-311++G(2d,p) optimized geometries. In particular, these electronic structure methods were used to explore pathways for the formation of elemental sulfur as well as for the formation of H 2 S and 1,3-butadiyne. Thiophene was found to undergo unimolecular decomposition by five pathways: C 4 H 4 S → (1) S═C═CH 2 + HCCH, (2) CS + HCCCH 3 , (3) HCS + HCCCH 2 , (4) H 2 S + HCC-CCH, and (5) S + HCC-CH═CH 2 . The experimental and theoretical findings are in excellent agreement.

Temperature sensitivity and enzymatic mechanisms of soil organic matter decomposition along an altitudinal gradient on Mount Kilimanjaro

NASA Astrophysics Data System (ADS)

Blagodatskaya, Evgenia; Blagodatsky, Sergey; Khomyakov, Nikita; Myachina, Olga; Kuzyakov, Yakov

2016-02-01

Short-term acceleration of soil organic matter decomposition by increasing temperature conflicts with the thermal adaptation observed in long-term studies. Here we used the altitudinal gradient on Mt. Kilimanjaro to demonstrate the mechanisms of thermal adaptation of extra- and intracellular enzymes that hydrolyze cellulose, chitin and phytate and oxidize monomers (14C-glucose) in warm- and cold-climate soils. We revealed that no response of decomposition rate to temperature occurs because of a cancelling effect consisting in an increase in half-saturation constants (Km), which counteracts the increase in maximal reaction rates (Vmax with temperature). We used the parameters of enzyme kinetics to predict thresholds of substrate concentration (Scrit) below which decomposition rates will be insensitive to global warming. Increasing values of Scrit, and hence stronger canceling effects with increasing altitude on Mt. Kilimanjaro, explained the thermal adaptation of polymer decomposition. The reduction of the temperature sensitivity of Vmax along the altitudinal gradient contributed to thermal adaptation of both polymer and monomer degradation. Extrapolating the altitudinal gradient to the large-scale latitudinal gradient, these results show that the soils of cold climates with stronger and more frequent temperature variation are less sensitive to global warming than soils adapted to high temperatures.

Roots Stimulate Expression of Decomposition Transcripts in the Soil Microbiome

NASA Astrophysics Data System (ADS)

Nuccio, E. E.; Karaoz, U.; Zhou, J.; Brodie, E.; Firestone, M.; Pett-Ridge, J.

2016-12-01

The soil surrounding plant roots, the rhizosphere, has long been recognized as a zone of great functional importance in terrestrial ecosystems. Rhizosphere microorganisms can affect the breakdown of plant tissues and root litter, and can accelerate the decomposition of detrital plant biomass, which is a process commonly described as "priming." However, the molecular mechanisms underlying rhizosphere C cycling are poorly understood, and the carbohydrate and lignolytic gene transcripts mediating the decomposition of root litter in soil are largely unidentified. We hypothesized that root exudates stimulate the expression of enzymes that are involved in decomposition of macromolecular C compounds. To assess how the abundance and diversity of decomposition enzymes differs in the rhizosphere relative to the surrounding bulk soil, we sequenced the community gene expression (metatranscriptomes) and single cell genomes of rhizosphere and bulk soil associated with wild oat (Avena fatua) over time (3, 6, 12, and 22 days). To isolate roots of a defined age in a mature plant, we used microcosms with a transparent experimental sidecar to track roots as they grew. Our results showed that a large number of C decomposition enzymes were more highly expressed in the rhizosphere compared to bulk soil, and that overall, transcripts tended to be elevated in younger roots than older roots. Genes relevant to aromatic C breakdown (nitroreductase, 4-hydroxybenzoate degradation, pectin methylesterase) and organic N cycling (ammonification) were elevated in the rhizosphere. This work identifies the potential molecular mechanisms that underpin priming in rhizosphere soil.

A Deep Insight into the Details of the Interisomerization and Decomposition Mechanism of o-Quinolyl and o-Isoquinolyl Radicals. Quantum Chemical Calculations and Computer Modeling.

PubMed

Dubnikova, Faina; Tamburu, Carmen; Lifshitz, Assa

2016-09-29

The isomerization of o-quinolyl ↔ o-isoquinolyl radicals and their thermal decomposition were studied by quantum chemical methods, where potential energy surfaces of the reaction channels and their kinetics rate parameters were determined. A detailed kinetics scheme containing 40 elementary steps was constructed. Computer simulations were carried out to determine the isomerization mechanism and the distribution of reaction products in the decomposition. The calculated mole percent of the stable products was compared to the experimental values that were obtained in this laboratory in the past, using the single pulse shock tube. The agreement between the experimental and the calculated mole percents was very good. A map of the figures containing the mole percent's of eight stable products of the decomposition plotted vs T are presented. The fast isomerization of o-quinolyl → o-isoquinolyl radicals via the intermediate indene imine radical and the attainment of fast equilibrium between these two radicals is the reason for the identical product distribution regardless whether the reactant radical is o-quinolyl or o-isoquinolyl. Three of the main decomposition products of o-quinolyl radical, are those containing the benzene ring, namely, phenyl, benzonitrile, and phenylacetylene radicals. They undergo further decomposition mainly at high temperatures via two types of reactions: (1) Opening of the benzene ring in the radicals, followed by splitting into fragments. (2) Dissociative attachment of benzonitrile and phenyl acetylene by hydrogen atoms to form hydrogen cyanide and acetylene.

Metagenomic analysis of antibiotic resistance genes (ARGs) during refuse decomposition.

PubMed

Liu, Xi; Yang, Shu; Wang, Yangqing; Zhao, He-Ping; Song, Liyan

2018-04-12

Landfill is important reservoirs of residual antibiotics and antibiotic resistance genes (ARGs), but the mechanism of landfill application influence on antibiotic resistance remains unclear. Although refuse decomposition plays a crucial role in landfill stabilization, its impact on the antibiotic resistance has not been well characterized. To better understand the impact, we studied the dynamics of ARGs and the bacterial community composition during refuse decomposition in a bench-scale bioreactor after long term operation (265d) based on metagenomics analysis. The total abundances of ARGs increased from 431.0ppm in the initial aerobic phase (AP) to 643.9ppm in the later methanogenic phase (MP) during refuse decomposition, suggesting that application of landfill for municipal solid waste (MSW) treatment may elevate the level of ARGs. A shift from drug-specific (bacitracin, tetracycline and sulfonamide) resistance to multidrug resistance was observed during the refuse decomposition and was driven by a shift of potential bacteria hosts. The elevated abundance of Pseudomonas mainly contributed to the increasing abundance of multidrug ARGs (mexF and mexW). Accordingly, the percentage of ARGs encoding an efflux pump increased during refuse decomposition, suggesting that potential bacteria hosts developed this mechanism to adapt to the carbon and energy shortage when biodegradable substances were depleted. Overall, our findings indicate that the use of landfill for MSW treatment increased antibiotic resistance, and demonstrate the need for a comprehensive investigation of antibiotic resistance in landfill. Copyright © 2018. Published by Elsevier B.V.

Ab initio investigation of the thermal decomposition of n-butylcyclohexane.

PubMed

Ali, Mohamad Akbar; Dillstrom, V Tyler; Lai, Jason Y W; Violi, Angela

2014-02-13

Environmental and energy security concerns have motivated an increased focus on developing clean, efficient combustors, which increasingly relies on insight into the combustion chemistry of fuels. In particular, naphthenes (cycloalkanes and alkylcycloalkanes) are important chemical components of distillate fuels, such as diesel and jet fuels. As such, there is a growing interest in describing napthene reactivity with kinetic mechanisms. Use of these mechanisms in predictive combustion models aids in the development of combustors. This study focuses on the pyrolysis of n-butylcyclohexane (n-BCH), an important representative of naphthenes in jet fuels. Seven different unimolecular decomposition pathways of C-C bond fission were explored utilizing ab initio/DFT methods. Accurate reaction energies were computed using the high-level quantum composite G3B3 method. Variational transition state theory, Rice-Ramsperger-Kassel-Marcus/master equation simulations provided temperature- and pressure-dependent rate constants. Implementation of these pathways into an existing chemical kinetic mechanism improved the prediction of experimental OH radical and H2O speciation in shock tube oxidation. Simulations of this combustion showed a change in the expected decomposition chemistry of n-BCH, predicting increased production of cyclic alkyl radicals instead of straight-chain alkenes. The most prominent reaction pathway for the decomposition of n-BCH is n-BCH = C3H7 + C7H13. The results of this study provide insight into the combustion of n-BCH and will aid in the future development of naphthene kinetic mechanisms.

Pursuing reliable thermal analysis techniques for energetic materials: decomposition kinetics and thermal stability of dihydroxylammonium 5,5'-bistetrazole-1,1'-diolate (TKX-50).

PubMed

Muravyev, Nikita V; Monogarov, Konstantin A; Asachenko, Andrey F; Nechaev, Mikhail S; Ananyev, Ivan V; Fomenkov, Igor V; Kiselev, Vitaly G; Pivkina, Alla N

2016-12-21

Thermal decomposition of a novel promising high-performance explosive dihydroxylammonium 5,5'-bistetrazole-1,1'-diolate (TKX-50) was studied using a number of thermal analysis techniques (thermogravimetry, differential scanning calorimetry, and accelerating rate calorimetry, ARC). To obtain more comprehensive insight into the kinetics and mechanism of TKX-50 decomposition, a variety of complementary thermoanalytical experiments were performed under various conditions. Non-isothermal and isothermal kinetics were obtained at both atmospheric and low (up to 0.3 Torr) pressures. The gas products of thermolysis were detected in situ using IR spectroscopy, and the structure of solid-state decomposition products was determined by X-ray diffraction and scanning electron microscopy. Diammonium 5,5'-bistetrazole-1,1'-diolate (ABTOX) was directly identified to be the most important intermediate of the decomposition process. The important role of bistetrazole diol (BTO) in the mechanism of TKX-50 decomposition was also rationalized by thermolysis experiments with mixtures of TKX-50 and BTO. Several widely used thermoanalytical data processing techniques (Kissinger, isoconversional, formal kinetic approaches, etc.) were independently benchmarked against the ARC data, which are more germane to the real storage and application conditions of energetic materials. Our study revealed that none of the Arrhenius parameters reported before can properly describe the complex two-stage decomposition process of TKX-50. In contrast, we showed the superior performance of the isoconversional methods combined with isothermal measurements, which yielded the most reliable kinetic parameters of TKX-50 thermolysis. In contrast with the existing reports, the thermal stability of TKX-50 was determined in the ARC experiments to be lower than that of hexogen, but close to that of hexanitrohexaazaisowurtzitane (CL-20).

A review of plutonium oxalate decomposition reactions and effects of decomposition temperature on the surface area of the plutonium dioxide product

NASA Astrophysics Data System (ADS)

Orr, R. M.; Sims, H. E.; Taylor, R. J.

2015-10-01

Plutonium (IV) and (III) ions in nitric acid solution readily form insoluble precipitates with oxalic acid. The plutonium oxalates are then easily thermally decomposed to form plutonium dioxide powder. This simple process forms the basis of current industrial conversion or 'finishing' processes that are used in commercial scale reprocessing plants. It is also widely used in analytical or laboratory scale operations and for waste residues treatment. However, the mechanisms of the thermal decompositions in both air and inert atmospheres have been the subject of various studies over several decades. The nature of intermediate phases is of fundamental interest whilst understanding the evolution of gases at different temperatures is relevant to process control. The thermal decomposition is also used to control a number of powder properties of the PuO2 product that are important to either long term storage or mixed oxide fuel manufacturing. These properties are the surface area, residual carbon impurities and adsorbed volatile species whereas the morphology and particle size distribution are functions of the precipitation process. Available data and experience regarding the thermal and radiation-induced decompositions of plutonium oxalate to oxide are reviewed. The mechanisms of the thermal decompositions are considered with a particular focus on the likely redox chemistry involved. Also, whilst it is well known that the surface area is dependent on calcination temperature, there is a wide variation in the published data and so new correlations have been derived. Better understanding of plutonium (III) and (IV) oxalate decompositions will assist the development of more proliferation resistant actinide co-conversion processes that are needed for advanced reprocessing in future closed nuclear fuel cycles.

Upscaling of fungal-bacterial interactions: from the lab to the field.

PubMed

de Boer, Wietse

2017-06-01

Fungal-bacterial interactions (FBI) are an integral component of microbial community networks in terrestrial ecosystems. During the last decade, the attention for FBI has increased tremendously. For a wide variety of FBI, information has become available on the mechanisms and functional responses. Yet, most studies have focused on pairwise interactions under controlled conditions. The question to what extent such studies are relevant to assess the importance of FBI for functioning of natural microbial communities in real ecosystems remains largely unanswered. Here, the information obtained by studying a type of FBI, namely antagonistic interactions between bacteria and plant pathogenic fungi, is discussed for different levels of community complexity. Based on this, general recommendations are given to integrate pairwise and ecosystem FBI studies. This approach could lead to the development of novel strategies to steer terrestrial ecosystem functioning. Copyright © 2017 Elsevier Ltd. All rights reserved.

Solution to urn models of pairwise interaction with application to social, physical, and biological sciences

NASA Astrophysics Data System (ADS)

Pickering, William; Lim, Chjan

2017-07-01

We investigate a family of urn models that correspond to one-dimensional random walks with quadratic transition probabilities that have highly diverse applications. Well-known instances of these two-urn models are the Ehrenfest model of molecular diffusion, the voter model of social influence, and the Moran model of population genetics. We also provide a generating function method for diagonalizing the corresponding transition matrix that is valid if and only if the underlying mean density satisfies a linear differential equation and express the eigenvector components as terms of ordinary hypergeometric functions. The nature of the models lead to a natural extension to interaction between agents in a general network topology. We analyze the dynamics on uncorrelated heterogeneous degree sequence networks and relate the convergence times to the moments of the degree sequences for various pairwise interaction mechanisms.

Acid and alkali effects on the decomposition of HMX molecule: a computational study.

PubMed

Zhang, Chaoyang; Li, Yuzhen; Xiong, Ying; Wang, Xiaolin; Zhou, Mingfei

2011-11-03

The stored and wasted explosives are usually in an acid or alkali environment, leading to the importance of exploring the acid and alkali effects on the decomposition mechanism of explosives. The acid and alkali effects on the decomposition of HMX molecule in gaseous state and in aqueous solution at 298 K are studied using quantum chemistry and molecular force field calculations. The results show that both H(+) and OH(-) make the decomposition in gaseous state energetically favorable. However, the effect of H(+) is much different from that of OH(-) in aqueous solution: OH(-) can accelerate the decomposition but H(+) cannot. The difference is mainly caused by the large aqueous solvation energy difference between H(+) and OH(-). The results confirm that the dissociation of HMX is energetically favored only in the base solutions, in good agreement with previous HMX base hydrolysis experimental observations. The different acid and alkali effects on the HMX decomposition are dominated by the large aqueous solvation energy difference between H(+) and OH(-).

Photodegradation Pathways in Arid Ecosystems

NASA Astrophysics Data System (ADS)

King, J. Y.; Lin, Y.; Adair, E. C.; Brandt, L.; Carbone, M. S.

2013-12-01

Recent interest in improving our understanding of decomposition patterns in arid and semi-arid ecosystems and under potentially drier future conditions has led to a flurry of research related to abiotic degradation processes. Oxidation of organic matter by solar radiation (photodegradation) is one abiotic degradation process that contributes significantly to litter decomposition rates. Our meta-analysis results show that increasing solar radiation exposure corresponds to an average increase of 23% in litter mass loss rate with large variation among studies associated primarily with environmental and litter chemistry characteristics. Laboratory studies demonstrate that photodegradation results in CO2 emissions. Indirect estimates suggest that photodegradation could account for as much as 60% of ecosystem CO2 emissions from dry ecosystems, but these CO2 fluxes have not been measured in intact ecosystems. The current data suggest that photodegradation is important, not only for understanding decomposition patterns, but also for modeling organic matter turnover and ecosystem C cycling. However, the mechanisms by which photodegradation operates, along with their environmental and litter chemistry controls, are still poorly understood. Photodegradation can directly influence decomposition rates and ecosystem CO2 flux via photochemical mineralization. It can also indirectly influence biotic decomposition rates by facilitating microbial degradation through breakdown of more recalcitrant compounds into simpler substrates or by suppressing microbial activity directly. All of these pathways influence the decomposition process, but the relative importance of each is uncertain. Furthermore, a specific suite of controls regulates each of these pathways (e.g., environmental conditions such as temperature and relative humidity; physical environment such as canopy architecture and contact with soil; and litter chemistry characteristics such as lignin and cellulose content), and these controls have not yet been identified or quantified. To advance our understanding of photodegradation and its role in decomposition and in ecosystem C cycling, we must characterize its mechanisms and their associated controls and incorporate this understanding into biogeochemical models. Our objective is to summarize the current state of understanding of photodegradation and discuss some paths forward to address remaining critical gaps in knowledge about its mechanisms and influence on ecosystem C balance.

The relative importance of decomposition and transport mechanisms in accounting for C profiles

NASA Astrophysics Data System (ADS)

Guenet, B.; Eglin, T.; Vasilyeva, N.; Peylin, P.; Ciais, P.; Chenu, C.

2012-10-01

Soil is the major terrestrial reservoirs of carbon, and a substantial part of this carbon is stored in deep layers, typically deeper than 50 cm below the surface. Several studies underlined the quantitative importance of this deep Soil Organic Carbon (SOC) pool and models are needed to better understand this stock and its evolution under climate and land-uses changes. In this study, we test and compare 3 simple theoretical models of vertical transport for SOC against SOC profiles measurements from a long-term bare fallow experiment carried out by the Central-Chernozem State Natural Biosphere Reserve named after V.V. Alekhin, in the Kursk Region of Russia. The transport schemes tested are diffusion, advection or both diffusion and advection. They are coupled to two different formulations of soil carbon decomposition kinetics. The first formulation is a first order kinetics widely used in global SOC decomposition models; the second one links SOC decomposition rate to the amount of fresh organic matter, representing a "priming effect". Field data are from a set of three bare fallow plots where soil received no input during the past 20, 26 and 58 yr respectively. Parameters of the models were optimized using a Bayesian method. The best results are obtained when SOC decomposition is assumed to be controlled by fresh organic matter. In comparison to the first-order kinetic model, the "priming" model reduces the underestimation of SOC decomposition in the top layers and the over estimation in the deep layers. We also observe that the transport scheme that improved the fit with the data depends on the soil carbon mineralization formulation chosen. When soil carbon decomposition is modelled to depend on the fresh organic matter amount, the transport mechanisms which improves best the fit to the SOC profile data is the model representing both advection and diffusion. Interestingly, the older the bare fallow is, the lesser the need for diffusion is. This suggests that stabilized carbon may not be transported within the profile by the same mechanisms than more labile carbon.

Ab initio kinetics and thermal decomposition mechanism of mononitrobiuret and 1,5-dinitrobiuret

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sun, Hongyan, E-mail: hongyan.sun1@gmail.com, E-mail: ghanshyam.vaghjiani@us.af.mil; Vaghjiani, Ghanshyam L., E-mail: hongyan.sun1@gmail.com, E-mail: ghanshyam.vaghjiani@us.af.mil

2015-05-28

Mononitrobiuret (MNB) and 1,5-dinitrobiuret (DNB) are tetrazole-free, nitrogen-rich, energetic compounds. For the first time, a comprehensive ab initio kinetics study on the thermal decomposition mechanisms of MNB and DNB is reported here. In particular, the intramolecular interactions of amine H-atom with electronegative nitro O-atom and carbonyl O-atom have been analyzed for biuret, MNB, and DNB at the M06-2X/aug-cc-pVTZ level of theory. The results show that the MNB and DNB molecules are stabilized through six-member-ring moieties via intramolecular H-bonding with interatomic distances between 1.8 and 2.0 Å, due to electrostatic as well as polarization and dispersion interactions. Furthermore, it was foundmore » that the stable molecules in the solid state have the smallest dipole moment amongst all the conformers in the nitrobiuret series of compounds, thus revealing a simple way for evaluating reactivity of fuel conformers. The potential energy surface for thermal decomposition of MNB was characterized by spin restricted coupled cluster theory at the RCCSD(T)/cc-pV∞ Z//M06-2X/aug-cc-pVTZ level. It was found that the thermal decomposition of MNB is initiated by the elimination of HNCO and HNN(O)OH intermediates. Intramolecular transfer of a H-atom, respectively, from the terminal NH{sub 2} group to the adjacent carbonyl O-atom via a six-member-ring transition state eliminates HNCO with an energy barrier of 35 kcal/mol and from the central NH group to the adjacent nitro O-atom eliminates HNN(O)OH with an energy barrier of 34 kcal/mol. Elimination of HNN(O)OH is also the primary process involved in the thermal decomposition of DNB, which processes C{sub 2v} symmetry. The rate coefficients for the primary decomposition channels for MNB and DNB were quantified as functions of temperature and pressure. In addition, the thermal decomposition of HNN(O)OH was analyzed via Rice–Ramsperger–Kassel–Marcus/multi-well master equation simulations, the results of which reveal the formation of (NO{sub 2} + H{sub 2}O) to be the major decomposition path. Furthermore, we provide fundamental interpretations for the experimental results of Klapötke et al. [Combust. Flame 139, 358–366 (2004)] regarding the thermal stability of MNB and DNB, and their decomposition products. Notably, a fundamental understanding of fuel stability, decomposition mechanism, and key reactions leading to ignition is essential in the design and manipulation of molecular systems for the development of new energetic materials for advanced propulsion applications.« less

Deformation twinning induced decomposition of lamellar LPSO structure and its re-precipitation in an Mg-Zn-Y alloy

NASA Astrophysics Data System (ADS)

Shao, X. H.; Zheng, S. J.; Chen, D.; Jin, Q. Q.; Peng, Z. Z.; Ma, X. L.

2016-07-01

The high hardness or yield strength of an alloy is known to benefit from the presence of small-scale precipitation, whose hardening effect is extensively applied in various engineering materials. Stability of the precipitates is of critical importance in maintaining the high performance of a material under mechanical loading. The long period stacking ordered (LPSO) structures play an important role in tuning the mechanical properties of an Mg-alloy. Here, we report deformation twinning induces decomposition of lamellar LPSO structures and their re-precipitation in an Mg-Zn-Y alloy. Using atomic resolution scanning transmission electron microscopy (STEM), we directly illustrate that the misfit dislocations at the interface between the lamellar LPSO structure and the deformation twin is corresponding to the decomposition and re-precipitation of LPSO structure, owing to dislocation effects on redistribution of Zn/Y atoms. This finding demonstrates that deformation twinning could destabilize complex precipitates. An occurrence of decomposition and re-precipitation, leading to a variant spatial distribution of the precipitates under plastic loading, may significantly affect the precipitation strengthening.

Deformation twinning induced decomposition of lamellar LPSO structure and its re-precipitation in an Mg-Zn-Y alloy

PubMed Central

Shao, X. H.; Zheng, S. J.; Chen, D.; Jin, Q. Q.; Peng, Z. Z.; Ma, X. L.

2016-01-01

The high hardness or yield strength of an alloy is known to benefit from the presence of small-scale precipitation, whose hardening effect is extensively applied in various engineering materials. Stability of the precipitates is of critical importance in maintaining the high performance of a material under mechanical loading. The long period stacking ordered (LPSO) structures play an important role in tuning the mechanical properties of an Mg-alloy. Here, we report deformation twinning induces decomposition of lamellar LPSO structures and their re-precipitation in an Mg-Zn-Y alloy. Using atomic resolution scanning transmission electron microscopy (STEM), we directly illustrate that the misfit dislocations at the interface between the lamellar LPSO structure and the deformation twin is corresponding to the decomposition and re-precipitation of LPSO structure, owing to dislocation effects on redistribution of Zn/Y atoms. This finding demonstrates that deformation twinning could destabilize complex precipitates. An occurrence of decomposition and re-precipitation, leading to a variant spatial distribution of the precipitates under plastic loading, may significantly affect the precipitation strengthening. PMID:27435638

In Situ Probes of Capture and Decomposition of Chemical Warfare Agent Simulants by Zr-Based Metal Organic Frameworks

DOE Office of Scientific and Technical Information (OSTI.GOV)

Plonka, Anna M.; Wang, Qi; Gordon, Wesley O.

Recently, Zr-based metal organic frameworks (MOFs) were shown to be among the fastest catalysts of nerve-agent hydrolysis in solution. Here, we report a detailed study of the adsorption and decomposition of a nerve-agent simulant, dimethyl methylphosphonate (DMMP), on UiO-66, UiO-67, MOF-808, and NU-1000 using synchrotron-based X-ray powder diffraction, X-ray absorption, and infrared spectroscopy, which reveals key aspects of the reaction mechanism. The diffraction measurements indicate that all four MOFs adsorb DMMP (introduced at atmospheric pressures through a flow of helium or air) within the pore space. In addition, the combination of X-ray absorption and infrared spectra suggests direct coordination ofmore » DMMP to the Zr6 cores of all MOFs, which ultimately leads to decomposition to phosphonate products. Our experimental probes into the mechanism of adsorption and decomposition of chemical warfare agent simulants on Zr-based MOFs open new opportunities in rational design of new and superior decontamination materials.« less

In Situ Probes of Capture and Decomposition of Chemical Warfare Agent Simulants by Zr-Based Metal Organic Frameworks

DOE Office of Scientific and Technical Information (OSTI.GOV)

Plonka, Anna M.; Wang, Qi; Gordon, Wesley O.

Zr-based metal organic frameworks (MOFs) have been recently shown to be among the fastest catalysts of nerve-agent hydrolysis in solution. We report a detailed study of the adsorption and decomposition of a nerve-agent simulant, dimethyl methylphosphonate (DMMP), on UiO-66, UiO-67, MOF-808, and NU-1000 using synchrotron-based X-ray powder diffraction, X-ray absorption, and infrared spectroscopy, which reveals key aspects of the reaction mechanism. The diffraction measurements indicate that all four MOFs adsorb DMMP (introduced at atmospheric pressures through a flow of helium or air) within the pore space. In addition, the combination of X-ray absorption and infrared spectra suggests direct coordination ofmore » DMMP to the Zr6 cores of all MOFs, which ultimately leads to decomposition to phosphonate products. These experimental probes into the mechanism of adsorption and decomposition of chemical warfare agent simulants on Zr-based MOFs open new opportunities in rational design of new and superior decontamination materials.« less

In Situ Probes of Capture and Decomposition of Chemical Warfare Agent Simulants by Zr-Based Metal Organic Frameworks

DOE PAGES

Plonka, Anna M.; Wang, Qi; Gordon, Wesley O.; ...

2016-12-30

Recently, Zr-based metal organic frameworks (MOFs) were shown to be among the fastest catalysts of nerve-agent hydrolysis in solution. Here, we report a detailed study of the adsorption and decomposition of a nerve-agent simulant, dimethyl methylphosphonate (DMMP), on UiO-66, UiO-67, MOF-808, and NU-1000 using synchrotron-based X-ray powder diffraction, X-ray absorption, and infrared spectroscopy, which reveals key aspects of the reaction mechanism. The diffraction measurements indicate that all four MOFs adsorb DMMP (introduced at atmospheric pressures through a flow of helium or air) within the pore space. In addition, the combination of X-ray absorption and infrared spectra suggests direct coordination ofmore » DMMP to the Zr6 cores of all MOFs, which ultimately leads to decomposition to phosphonate products. Our experimental probes into the mechanism of adsorption and decomposition of chemical warfare agent simulants on Zr-based MOFs open new opportunities in rational design of new and superior decontamination materials.« less

Mechanism of the Thermal Decomposition of Ethanethiol and Dimethylsulfide

NASA Astrophysics Data System (ADS)

Melhado, William Francis; Whitman, Jared Connor; Kong, Jessica; Anderson, Daniel Easton; Vasiliou, AnGayle (AJ)

2016-06-01

Combustion of organosulfur contaminants in petroleum-based fuels and biofuels produces sulfur oxides (SO_x). These pollutants are highly regulated by the EPA because they have been linked to poor respiratory health and negative environmental impacts. Therefore much effort has been made to remove sulfur compounds in petroleum-based fuels and biofuels. Currently desulfurization methods used in the fuel industry are costly and inefficient. Research of the thermal decomposition mechanisms of organosulfur species can be implemented via engineering simulations to modify existing refining technologies to design more efficient sulfur removal processes. We have used a resistively-heated SiC tubular reactor to study the thermal decomposition of ethanethiol (CH_3CH_2SH) and dimethylsulfide (CH_3SCH_3). The decomposition products are identified by two independent techniques: 118.2 nm VUV photoionization mass spectroscopy and infrared spectroscopy. The thermal cracking products for CH_3CH_2SH are CH_2CH_2, SH, and H_2S and the thermal cracking products from CH_3SCH_3 are CH_3S, CH_2S, and CH_3.

The neural basis of novelty and appropriateness in processing of creative chunk decomposition.

PubMed

Huang, Furong; Fan, Jin; Luo, Jing

2015-06-01

Novelty and appropriateness have been recognized as the fundamental features of creative thinking. However, the brain mechanisms underlying these features remain largely unknown. In this study, we used event-related functional magnetic resonance imaging (fMRI) to dissociate these mechanisms in a revised creative chunk decomposition task in which participants were required to perform different types of chunk decomposition that systematically varied in novelty and appropriateness. We found that novelty processing involved functional areas for procedural memory (caudate), mental rewarding (substantia nigra, SN), and visual-spatial processing, whereas appropriateness processing was mediated by areas for declarative memory (hippocampus), emotional arousal (amygdala), and orthography recognition. These results indicate that non-declarative and declarative memory systems may jointly contribute to the two fundamental features of creative thinking. Copyright © 2015 Elsevier Inc. All rights reserved.

The mechanism of the photochemical oxidation of water to oxygen with silver chloride colloids

NASA Astrophysics Data System (ADS)

Chandrasekaran, K.; Thomas, J. K.

1983-05-01

Photoexcitation of silver chloride colloids in the presence of excess silver ions, leads to the decomposition of water. Hydroxyl radicals were found to be intermediates in the decomposition process. Irradiation leads to hydroxyl radicals, which recombine to give hydrogen peroxide, on the colloidal particle surface. Subsequent decomposition of H 2O 2 to give O 2 is catalyzed by silver ions. Addition of alcohols such as methanol and isopropanol reduce the oxygen yield, as they react with OH radicals and reduce the H 2O 2 yield.

Three phase crystallography and solute distribution analysis during residual austenite decomposition in tempered nanocrystalline bainitic steels

DOE Office of Scientific and Technical Information (OSTI.GOV)

Caballero, F.G.; Yen, Hung-Wei; Australian Centre for Microscopy and Microanalysis, The University of Sydney, NSW 2006

2014-02-15

Interphase carbide precipitation due to austenite decomposition was investigated by high resolution transmission electron microscopy and atom probe tomography in tempered nanostructured bainitic steels. Results showed that cementite (θ) forms by a paraequilibrium transformation mechanism at the bainitic ferrite–austenite interface with a simultaneous three phase crystallographic orientation relationship. - Highlights: • Interphase carbide precipitation due to austenite decomposition • Tempered nanostructured bainitic steels • High resolution transmission electron microscopy and atom probe tomography • Paraequilibrium θ with three phase crystallographic orientation relationship.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gao, Ning; Shen, Tielong; Kurtz, Richard

The properties of nano-scale interstitial dislocation loops under the coupling effect of stress and temperature are studied using atomistic simulation methods and experiments. The decomposition of a loop by the emission of smaller loops is identified as one of the major mechanisms to release the localized stress induced by the coupling effect, which is validated by the TEM observations. The classical conservation law of Burgers vector cannot be applied during such decomposition process. The dislocation network is formed from the decomposed loops, which may initiate the irradiation creep much earlier than expected through the mechanism of climb-controlled glide of dislocations.

Identifying the Thermal Decomposition Mechanism of Guaiacol on Pt(111): An Integrated X-ray Photoelectron Spectroscopy and Density Functional Theory Study

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hensley, Alyssa J.; Wockel, Claudia; Gleichweit, Christoph

Using a concerted effort from both experiment and theory, we determine the thermal decomposition mechanism for guaiacol on Pt(111), a reaction of interest in the area of bio-oil upgrading. This work serves as a demonstration of the power of combining in situ temperature-programmed X-ray photoelectron spectroscopy cos (TPXPS) and density functional theory (DFT) to elucidate complex reaction mechanisms occurring on heterogeneous surfaces. At low temperature (230 K), guaiacol was found to chemisorb with the aromatic ring parallel to the Pt(111) surface with five distinct carbon species and three oxygen species. As the temperature was increased, TPXPS showed several significant changesmore » to the surface species. The increase in the species associated with the decomposition of the functional groups of guaiacol is followed by their subsequent disappearance and an increase in the nonaromatic carbon signal. On the basis of an energetic analysis of the various mechanisms using DFT, along with the comparison of the experimentally and theoretically derived core-level binding energies, we determined that guaiacol's decomposition mechanism occurs via the dehydrogenation of both the methyl and hydroxyl functional groups, followed by demethylation of the CH2 or CH group to form 1,2-benzoquinone. Further heating to above 375 K likely breaks the aromatic ring and results in the rapid formation and desorption of CO, accounting for the disappearance of the 0 is signal above 450 K These results show that a knowledgeable application of TPXPS and DFT can result in the quantitative identification of surface species during complex reactions, providing insight useful for the design of future heterogeneous surfaces.« less

Catalytic effects of inorganic acids on the decomposition of ammonium nitrate.

PubMed

Sun, Jinhua; Sun, Zhanhui; Wang, Qingsong; Ding, Hui; Wang, Tong; Jiang, Chuansheng

2005-12-09

In order to evaluate the catalytic effects of inorganic acids on the decomposition of ammonium nitrate (AN), the heat releases of decomposition or reaction of pure AN and its mixtures with inorganic acids were analyzed by a heat flux calorimeter C80. Through the experiments, the different reaction mechanisms of AN and its mixtures were analyzed. The chemical reaction kinetic parameters such as reaction order, activation energy and frequency factor were calculated with the C80 experimental results for different samples. Based on these parameters and the thermal runaway models (Semenov and Frank-Kamenestkii model), the self-accelerating decomposition temperatures (SADTs) of AN and its mixtures were calculated and compared. The results show that the mixtures of AN with acid are more unsteady than pure AN. The AN decomposition reaction is catalyzed by acid. The calculated SADTs of AN mixtures with acid are much lower than that of pure AN.

Thermal decomposition of gaseous ammonium nitrate at low pressure: kinetic modeling of product formation and heterogeneous decomposition of nitric acid.

PubMed

Park, J; Lin, M C

2009-12-03

The thermal decomposition of ammonium nitrate, NH(4)NO(3) (AN), in the gas phase has been studied at 423-56 K by pyrolysis/mass spectrometry under low-pressure conditions using a Saalfeld reactor coated with boric acid. The sublimation of NH(4)NO(3) at 423 K was proposed to produce equal amounts of NH(3) and HNO(3), followed by the decomposition reaction of HNO(3), HNO(3) + M --> OH + NO(2) + M (where M = third-body and reactor surface). The absolute yields of N(2), N(2)O, H(2)O, and NH(3), which can be unambiguously measured and quantitatively calibrated under a constant pressure at 5-6.2 torr He are kinetically modeled using the detailed [H,N,O]-mechanism established earlier for the simulation of NH(3)-NO(2) (Park, J.; Lin, M. C. Technologies and Combustion for a Clean Environment. Proc. 4th Int. Conf. 1997, 34-1, 1-5) and ADN decomposition reactions (Park, J.; Chakraborty, D.; Lin, M. C. Proc. Combust. Inst. 1998, 27, 2351-2357). Since the homogeneous decomposition reaction of HNO(3) itself was found to be too slow to account for the consumption of reactants and the formation of products, we also introduced the heterogeneous decomposition of HNO(3) in our kinetic modeling. The heterogeneous decomposition rate of HNO(3), HNO(3) + (B(2)O(3)/SiO(2)) --> OH + NO(2) + (B(2)O(3)/SiO(2)), was determined by varying its rate to match the modeled result to the measured concentrations of NH(3) and H(2)O; the rate could be represented by k(2b) = 7.91 x 10(7) exp(-12 600/T) s(-1), which appears to be consistent with those reported by Johnston and co-workers (Johnston, H. S.; Foering, L.; Tao, Y.-S.; Messerly, G. H. J. Am. Chem. Soc. 1951, 73, 2319-2321) for HNO(3) decomposition on glass reactors at higher temperatures. Notably, the concentration profiles of all species measured could be satisfactorily predicted by the existing [H,N,O]-mechanism with the heterogeneous initiation process.

Thermal Decomposition of Gaseous Ammonium Nitrate at Low Pressure: Kinetic Modeling of Product Formation and Heterogeneous Decomposition of Nitric Acid

NASA Astrophysics Data System (ADS)

Park, J.; Lin, M. C.

2009-10-01

The thermal decomposition of ammonium nitrate, NH4NO3 (AN), in the gas phase has been studied at 423-56 K by pyrolysis/mass spectrometry under low-pressure conditions using a Saalfeld reactor coated with boric acid. The sublimation of NH4NO3 at 423 K was proposed to produce equal amounts of NH3 and HNO3, followed by the decomposition reaction of HNO3, HNO3 + M → OH + NO2 + M (where M = third-body and reactor surface). The absolute yields of N2, N2O, H2O, and NH3, which can be unambiguously measured and quantitatively calibrated under a constant pressure at 5-6.2 torr He are kinetically modeled using the detailed [H,N,O]-mechanism established earlier for the simulation of NH3-NO2 (Park, J.; Lin, M. C. Technologies and Combustion for a Clean Environment. Proc. 4th Int. Conf. 1997, 34-1, 1-5) and ADN decomposition reactions (Park, J.; Chakraborty, D.; Lin, M. C. Proc. Combust. Inst. 1998, 27, 2351-2357). Since the homogeneous decomposition reaction of HNO3 itself was found to be too slow to account for the consumption of reactants and the formation of products, we also introduced the heterogeneous decomposition of HNO3 in our kinetic modeling. The heterogeneous decomposition rate of HNO3, HNO3 + (B2O3/SiO2) → OH + NO2 + (B2O3/SiO2), was determined by varying its rate to match the modeled result to the measured concentrations of NH3 and H2O; the rate could be represented by k2b = 7.91 × 107 exp(-12 600/T) s-1, which appears to be consistent with those reported by Johnston and co-workers (Johnston, H. S.; Foering, L.; Tao, Y.-S.; Messerly, G. H. J. Am. Chem. Soc. 1951, 73, 2319-2321) for HNO3 decomposition on glass reactors at higher temperatures. Notably, the concentration profiles of all species measured could be satisfactorily predicted by the existing [H,N,O]-mechanism with the heterogeneous initiation process.

MEG masked priming evidence for form-based decomposition of irregular verbs

PubMed Central

Fruchter, Joseph; Stockall, Linnaea; Marantz, Alec

2013-01-01

To what extent does morphological structure play a role in early processing of visually presented English past tense verbs? Previous masked priming studies have demonstrated effects of obligatory form-based decomposition for genuinely affixed words (teacher-TEACH) and pseudo-affixed words (corner-CORN), but not for orthographic controls (brothel-BROTH). Additionally, MEG single word reading studies have demonstrated that the transition probability from stem to affix (in genuinely affixed words) modulates an early evoked response known as the M170; parallel findings have been shown for the transition probability from stem to pseudo-affix (in pseudo-affixed words). Here, utilizing the M170 as a neural index of visual form-based morphological decomposition, we ask whether the M170 demonstrates masked morphological priming effects for irregular past tense verbs (following a previous study which obtained behavioral masked priming effects for irregulars). Dual mechanism theories of the English past tense predict a rule-based decomposition for regulars but not for irregulars, while certain single mechanism theories predict rule-based decomposition even for irregulars. MEG data was recorded for 16 subjects performing a visual masked priming lexical decision task. Using a functional region of interest (fROI) defined on the basis of repetition priming and regular morphological priming effects within the left fusiform and inferior temporal regions, we found that activity in this fROI was modulated by the masked priming manipulation for irregular verbs, during the time window of the M170. We also found effects of the scores generated by the learning model of Albright and Hayes (2003) on the degree of priming for irregular verbs. The results favor a single mechanism account of the English past tense, in which even irregulars are decomposed into stems and affixes prior to lexical access, as opposed to a dual mechanism model, in which irregulars are recognized as whole forms. PMID:24319420

Differences in the sensitivity of fungi and bacteria to season and invertebrates affect leaf litter decomposition in a Mediterranean stream.

PubMed

Mora-Gómez, Juanita; Elosegi, Arturo; Duarte, Sofia; Cássio, Fernanda; Pascoal, Cláudia; Romaní, Anna M

2016-08-01

Microorganisms are key drivers of leaf litter decomposition; however, the mechanisms underlying the dynamics of different microbial groups are poorly understood. We investigated the effects of seasonal variation and invertebrates on fungal and bacterial dynamics, and on leaf litter decomposition. We followed the decomposition of Populus nigra litter in a Mediterranean stream through an annual cycle, using fine and coarse mesh bags. Irrespective of the season, microbial decomposition followed two stages. Initially, bacterial contribution to total microbial biomass was higher compared to later stages, and it was related to disaccharide and lignin degradation; in a later stage, bacteria were less important and were associated with hemicellulose and cellulose degradation, while fungi were related to lignin decomposition. The relevance of microbial groups in decomposition differed among seasons: fungi were more important in spring, whereas in summer, water quality changes seemed to favour bacteria and slowed down lignin and hemicellulose degradation. Invertebrates influenced litter-associated microbial assemblages (especially bacteria), stimulated enzyme efficiencies and reduced fungal biomass. We conclude that bacterial and fungal assemblages play distinctive roles in microbial decomposition and differ in their sensitivity to environmental changes, ultimately affecting litter decomposition, which might be particularly relevant in highly seasonal ecosystems, such as intermittent streams. © FEMS 2016. All rights reserved. For permissions, please e-mail: journals.permissions@oup.com.

Measurement of the energy dependence of X-ray-induced decomposition of potassium chlorate.

PubMed

Pravica, Michael; Bai, Ligang; Sneed, Daniel; Park, Changyong

2013-03-21

We report the first measurements of the X-ray induced decomposition of KClO3 as a function of energy in two experiments. KClO3 was pressurized to 3.5 GPa and irradiated with monochromatic synchrotron X-rays ranging in energy from 15 to 35 keV in 5 keV increments. A systematic increase in the decomposition rate as the energy was decreased was observed, which agrees with the 1/E(3) trend for the photoelectric process, except at the lowest energy studied. A second experiment was performed to access lower energies (10 and 12 keV) using a beryllium gasket; suggesting an apparent resonance near 15 keV or 0.83 Ǻ maximizing the chemical decomposition rate. A third experiment was performed using KIO3 to ascertain the anionic dependence of the decomposition rate, which was observed to be far slower than in KClO3, suggesting that the O-O distance is the critical factor in chemical reactions. These results will be important for more efficiently initiating chemical decomposition in materials using selected X-ray wavelengths that maximize decomposition to aid useful hard X-ray-induced chemistry and contribute understanding of the mechanism of X-ray-induced decomposition of the chlorates.

Lignin decomposition is sustained under fluctuating redox conditions in humid tropical forest soils

Treesearch

Steven J. Hall; Whendee L. Silver; Vitaliy I. Timokhin; Kenneth E. Hammel

2015-01-01

Lignin mineralization represents a critical flux in the terrestrial carbon (C) cycle, yet little is known about mechanisms and environmental factors controlling lignin breakdown in mineral soils. Hypoxia is thought to suppress lignin decomposition, yet potential effects of oxygen (O2) variability in surface soils have not been explored. Here, we...

Pairwise-Comparison Software

NASA Technical Reports Server (NTRS)

Ricks, Wendell R.

1995-01-01

Pairwise comparison (PWC) is computer program that collects data for psychometric scaling techniques now used in cognitive research. It applies technique of pairwise comparisons, which is one of many techniques commonly used to acquire the data necessary for analyses. PWC administers task, collects data from test subject, and formats data for analysis. Written in Turbo Pascal v6.0.

Score distributions of gapped multiple sequence alignments down to the low-probability tail

NASA Astrophysics Data System (ADS)

Fieth, Pascal; Hartmann, Alexander K.

2016-08-01

Assessing the significance of alignment scores of optimally aligned DNA or amino acid sequences can be achieved via the knowledge of the score distribution of random sequences. But this requires obtaining the distribution in the biologically relevant high-scoring region, where the probabilities are exponentially small. For gapless local alignments of infinitely long sequences this distribution is known analytically to follow a Gumbel distribution. Distributions for gapped local alignments and global alignments of finite lengths can only be obtained numerically. To obtain result for the small-probability region, specific statistical mechanics-based rare-event algorithms can be applied. In previous studies, this was achieved for pairwise alignments. They showed that, contrary to results from previous simple sampling studies, strong deviations from the Gumbel distribution occur in case of finite sequence lengths. Here we extend the studies to multiple sequence alignments with gaps, which are much more relevant for practical applications in molecular biology. We study the distributions of scores over a large range of the support, reaching probabilities as small as 10-160, for global and local (sum-of-pair scores) multiple alignments. We find that even after suitable rescaling, eliminating the sequence-length dependence, the distributions for multiple alignment differ from the pairwise alignment case. Furthermore, we also show that the previously discussed Gaussian correction to the Gumbel distribution needs to be refined, also for the case of pairwise alignments.

Thermal decomposition of FC(O)OCH3 and FC(O)OCH2CH3.

PubMed

Berasategui, M; Argüello, G A; Burgos Paci, M A

2018-05-09

The thermal decomposition of methyl and ethyl formates has been extensively studied due to their importance in the oxidation of several fuels, pesticidal properties and their presence in interstellar space. We hitherto present the study of the thermal decomposition of methyl and ethyl fluoroformates, which could help in the elucidation of the reaction mechanisms. The reaction mechanisms were studied using FTIR spectroscopy in the temperature range of 453-733 K in the presence of different pressures of N2 as bath gas. For FC(O)OCH3 two different channels were observed; the unimolecular decomposition which is favored at higher temperatures and has a rate constant kFC(O)OCH3 = (5.3 ± 0.5) × 1015 exp[-(246 ± 10 kJ mol-1/RT)] (in units of s-1) and a bimolecular channel with a rate constant kFC(O)OCH3 = (1.6 ± 0.5) × 1011 exp[-(148 ± 10 kJ mol-1/RT)] (in units of s-1 (mol L)-1). However for ethyl formate, only direct elimination of CO2, HF and ethylene operates. The rate constants of the homogeneous first-order process fit the Arrhenius equation kFC(O)OCH2CH3 = (2.06 ± 0.09) × 1013 exp[-(169 ± 6 kJ mol-1/RT)] (in units of s-1). The difference between the mechanisms of the two fluoroformates relies on the stabilization of a six-centered transition state that only exists for ethyl formate. First principles calculations for the different channels were carried out to understand the dynamics of the decomposition.

Initial mechanisms for the decomposition of electronically excited energetic materials: 1,5′-BT, 5,5′-BT, and AzTT

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yuan, Bing; Yu, Zijun; Bernstein, Elliot R., E-mail: erb@lamar.Colostate.edu

2015-03-28

Decomposition of nitrogen-rich energetic materials 1,5′-BT, 5,5′-BT, and AzTT (1,5′-Bistetrazole, 5,5′-Bistetrazole, and 5-(5-azido-(1 or 4)H-1,2,4-triazol-3-yl)tetrazole, respectively), following electronic state excitation, is investigated both experimentally and theoretically. The N{sub 2} molecule is observed as an initial decomposition product from the three materials, subsequent to UV excitation, with a cold rotational temperature (<30 K). Initial decomposition mechanisms for these three electronically excited materials are explored at the complete active space self-consistent field (CASSCF) level. Potential energy surface calculations at the CASSCF(12,8)/6-31G(d) level illustrate that conical intersections play an essential role in the decomposition mechanism. Electronically excited S{sub 1} molecules can non-adiabatically relaxmore » to their ground electronic states through (S{sub 1}/S{sub 0}){sub CI} conical intersections. 1,5′-BT and 5,5′-BT materials have several (S{sub 1}/S{sub 0}){sub CI} conical intersections between S{sub 1} and S{sub 0} states, related to different tetrazole ring opening positions, all of which lead to N{sub 2} product formation. The N{sub 2} product for AzTT is formed primarily by N–N bond rupture of the –N{sub 3} group. The observed rotational energy distributions for the N{sub 2} products are consistent with the final structures of the respective transition states for each molecule on its S{sub 0} potential energy surface. The theoretically derived vibrational temperature of the N{sub 2} product is high, which is similar to that found for energetic salts and molecules studied previously.« less

Assessment of a new method for the analysis of decomposition gases of polymers by a combining thermogravimetric solid-phase extraction and thermal desorption gas chromatography mass spectrometry.

PubMed

Duemichen, E; Braun, U; Senz, R; Fabian, G; Sturm, H

2014-08-08

For analysis of the gaseous thermal decomposition products of polymers, the common techniques are thermogravimetry, combined with Fourier transformed infrared spectroscopy (TGA-FTIR) and mass spectrometry (TGA-MS). These methods offer a simple approach to the decomposition mechanism, especially for small decomposition molecules. Complex spectra of gaseous mixtures are very often hard to identify because of overlapping signals. In this paper a new method is described to adsorb the decomposition products during controlled conditions in TGA on solid-phase extraction (SPE) material: twisters. Subsequently the twisters were analysed with thermal desorption gas chromatography mass spectrometry (TDS-GC-MS), which allows the decomposition products to be separated and identified using an MS library. The thermoplastics polyamide 66 (PA 66) and polybutylene terephthalate (PBT) were used as example polymers. The influence of the sample mass and of the purge gas flow during the decomposition process was investigated in TGA. The advantages and limitations of the method were presented in comparison to the common analysis techniques, TGA-FTIR and TGA-MS. Copyright © 2014 Elsevier B.V. All rights reserved.

Understanding paper degradation: identification of products of cellulosic paper decomposition at the wet-dry "tideline" interface using GC-MS.

PubMed

Sladkevich, Sergey; Dupont, Anne-Laurence; Sablier, Michel; Seghouane, Dalila; Cole, Richard B

2016-11-01

Cellulose paper degradation products forming in the "tideline" area at the wet-dry interface of pure cellulose paper were analyzed using gas chromatography-electron ionization-mass spectrometry (GC-EI-MS) and high-resolution electrospray ionization-mass spectrometry (ESI-MS, LTQ Orbitrap) techniques. Different extraction protocols were employed in order to solubilize the products of oxidative cellulose decomposition, i.e., a direct solvent extraction or a more laborious chromophore release and identification (CRI) technique aiming to reveal products responsible for paper discoloration in the tideline area. Several groups of low molecular weight compounds were identified, suggesting a complex pathway of cellulose decomposition in the tidelines formed at the cellulose-water-oxygen interface. Our findings, namely the appearance of a wide range of linear saturated carboxylic acids (from formic to nonanoic), support the oxidative autocatalytic mechanism of decomposition. In addition, the identification of several furanic compounds (which can be, in part, responsible for paper discoloration) plus anhydro carbohydrate derivatives sheds more light on the pathways of cellulose decomposition. Most notably, the mechanisms of tideline formation in the presence of molecular oxygen appear surprisingly similar to pathways of pyrolytic cellulose degradation. More complex chromophore compounds were not detected in this study, thereby revealing a difference between this short-term tideline experiment and longer-term cellulose aging.

Synthesis, characterization, thermal and explosive properties of potassium salts of trinitrophloroglucinol.

PubMed

Wang, Liqiong; Chen, Hongyan; Zhang, Tonglai; Zhang, Jianguo; Yang, Li

2007-08-17

Three different substituted potassium salts of trinitrophloroglucinol (H(3)TNPG) were prepared and characterized. The salts are all hydrates, and thermogravimetric analysis (TG) and elemental analysis confirmed that these salts contain crystal H2O and that the amount crystal H2O in potassium salts of H3TNPG is 1.0 hydrate for mono-substituted potassium salts of H3TNPG [K(H2TNPG)] and di-substituted potassium salt of H3TNPG [K2(HTNPG)], and 2.0 hydrate for tri-substituted potassium salt of H3TNPG [K3(TNPG)]. Their thermal decomposition mechanisms and kinetic parameters from 50 to 500 degrees C were studied under a linear heating rate by differential scanning calorimetry (DSC). Their thermal decomposition mechanisms undergo dehydration stage and intensive exothermic decomposition stage. FT-IR and TG studies verify that their final residua of decomposition are potassium cyanide or potassium carbonate. According to the onset temperature of the first exothermic decomposition process of dehydrated salts, the order of the thermal stability from low to high is from K(H2TNPG) and K2(HTNPG) to K3(TNPG), which is conform to the results of apparent activation energy calculated by Kissinger's and Ozawa-Doyle's method. Sensitivity test results showed that potassium salts of H3TNPG demonstrated higher sensitivity properties and had greater explosive probabilities.

Analysis on Vertical Scattering Signatures in Forestry with PolInSAR

NASA Astrophysics Data System (ADS)

Guo, Shenglong; Li, Yang; Zhang, Jingjing; Hong, Wen

2014-11-01

We apply accurate topographic phase to the Freeman-Durden decomposition for polarimetric SAR interferometry (PolInSAR) data. The cross correlation matrix obtained from PolInSAR observations can be decomposed into three scattering mechanisms matrices accounting for the odd-bounce, double-bounce and volume scattering. We estimate the phase based on the Random volume over Ground (RVoG) model, and as the initial input parameter of the numerical method which is used to solve the parameters of decomposition. In addition, the modified volume scattering model introduced by Y. Yamaguchi is applied to the PolInSAR target decomposition in forest areas rather than the pure random volume scattering as proposed by Freeman-Durden to make best fit to the actual measured data. This method can accurately retrieve the magnitude associated with each mechanism and their vertical location along the vertical dimension. We test the algorithms with L- and P- band simulated data.

HCOOH decomposition on Pt(111): A DFT study

DOE PAGES

Scaranto, Jessica; Mavrikakis, Manos

2015-10-13

Formic acid (HCOOH) decomposition on transition metal surfaces is important for hydrogen production and for its electro-oxidation in direct HCOOH fuel cells. HCOOH can decompose through dehydrogenation leading to formation of CO 2 and H 2 or dehydration leading to CO and H 2O; because CO can poison metal surfaces, dehydrogenation is typically the desirable decomposition path. Here we report a mechanistic analysis of HCOOH decomposition on Pt(111), obtained from a plane wave density functional theory (DFT-PW91) study. We analyzed the dehydrogenation mechanism by considering the two possible pathways involving the formate (HCOO) or the carboxyl (COOH) intermediate. We alsomore » considered several possible dehydration paths leading to CO formation. We studied HCOO and COOH decomposition both on the clean surface and in the presence of other relevant co-adsorbates. The results suggest that COOH formation is energetically more difficult than HCOO formation. In contrast, COOH dehydrogenation is easier than HCOO decomposition. Here, we found that CO 2 is the main product through both pathways and that CO is produced mainly through the dehydroxylation of the COOH intermediate.« less

HCOOH decomposition on Pt(111): A DFT study

DOE Office of Scientific and Technical Information (OSTI.GOV)

Scaranto, Jessica; Mavrikakis, Manos

Formic acid (HCOOH) decomposition on transition metal surfaces is important for hydrogen production and for its electro-oxidation in direct HCOOH fuel cells. HCOOH can decompose through dehydrogenation leading to formation of CO 2 and H 2 or dehydration leading to CO and H 2O; because CO can poison metal surfaces, dehydrogenation is typically the desirable decomposition path. Here we report a mechanistic analysis of HCOOH decomposition on Pt(111), obtained from a plane wave density functional theory (DFT-PW91) study. We analyzed the dehydrogenation mechanism by considering the two possible pathways involving the formate (HCOO) or the carboxyl (COOH) intermediate. We alsomore » considered several possible dehydration paths leading to CO formation. We studied HCOO and COOH decomposition both on the clean surface and in the presence of other relevant co-adsorbates. The results suggest that COOH formation is energetically more difficult than HCOO formation. In contrast, COOH dehydrogenation is easier than HCOO decomposition. Here, we found that CO 2 is the main product through both pathways and that CO is produced mainly through the dehydroxylation of the COOH intermediate.« less

Magnetite Formation from Thermal Decomposition of Siderite: Implications for Inorganic Magnetite Formation in Martian Meteorite ALH84001

NASA Technical Reports Server (NTRS)

Morris, RIchard V.

2002-01-01

A biogenic mechanism for formation of a subpopulation magnetite in Martian meteorite ALH84001 has been suggested [McKay et al., 1996; Thomas-Keprta, et al., 2000]. We are developing experimental evidence for an alternating working hypothesis, that the subpopulation was produced inorganically by the thermal decomposition of siderite [Golden et al., 2000].

Studies on thermal decomposition behaviors of polypropylene using molecular dynamics simulation

NASA Astrophysics Data System (ADS)

Huang, Jinbao; He, Chao; Tong, Hong; Pan, Guiying

2017-11-01

Polypropylene (PP) is one of the main components of waste plastics. In order to understand the mechanism of PP thermal decomposition, the pyrolysis behaviour of PP has been simulated from 300 to 1000 K in periodic boundary conditions by molecular dynamic method, based on AMBER force field. The simulation results show that the pyrolysis process of PP can mostly be divided into three stages: low temperature pyrolysis stage, intermediate temperature stage and high temperature pyrolysis stage. PP pyrolysis is typical of random main-chain scission, and the possible formation mechanism of major pyrolysis products was analyzed.

Decomposition and extraction: a new framework for visual classification.

PubMed

Fang, Yuqiang; Chen, Qiang; Sun, Lin; Dai, Bin; Yan, Shuicheng

2014-08-01

In this paper, we present a novel framework for visual classification based on hierarchical image decomposition and hybrid midlevel feature extraction. Unlike most midlevel feature learning methods, which focus on the process of coding or pooling, we emphasize that the mechanism of image composition also strongly influences the feature extraction. To effectively explore the image content for the feature extraction, we model a multiplicity feature representation mechanism through meaningful hierarchical image decomposition followed by a fusion step. In particularly, we first propose a new hierarchical image decomposition approach in which each image is decomposed into a series of hierarchical semantical components, i.e, the structure and texture images. Then, different feature extraction schemes can be adopted to match the decomposed structure and texture processes in a dissociative manner. Here, two schemes are explored to produce property related feature representations. One is based on a single-stage network over hand-crafted features and the other is based on a multistage network, which can learn features from raw pixels automatically. Finally, those multiple midlevel features are incorporated by solving a multiple kernel learning task. Extensive experiments are conducted on several challenging data sets for visual classification, and experimental results demonstrate the effectiveness of the proposed method.

Decreases in Soil Moisture and Organic Matter Quality Suppress Microbial Decomposition Following a Boreal Forest Fire

DOE Office of Scientific and Technical Information (OSTI.GOV)

Holden, Sandra R.; Berhe, Asmeret A.; Treseder, Kathleen K.

Climate warming is projected to increase the frequency and severity of wildfires in boreal forests, and increased wildfire activity may alter the large soil carbon (C) stocks in boreal forests. Changes in boreal soil C stocks that result from increased wildfire activity will be regulated in part by the response of microbial decomposition to fire, but post-fire changes in microbial decomposition are poorly understood. Here, we investigate the response of microbial decomposition to a boreal forest fire in interior Alaska and test the mechanisms that control post-fire changes in microbial decomposition. We used a reciprocal transplant between a recently burnedmore » boreal forest stand and a late successional boreal forest stand to test how post-fire changes in abiotic conditions, soil organic matter (SOM) composition, and soil microbial communities influence microbial decomposition. We found that SOM decomposing at the burned site lost 30.9% less mass over two years than SOM decomposing at the unburned site, indicating that post-fire changes in abiotic conditions suppress microbial decomposition. Our results suggest that moisture availability is one abiotic factor that constrains microbial decomposition in recently burned forests. In addition, we observed that burned SOM decomposed more slowly than unburned SOM, but the exact nature of SOM changes in the recently burned stand are unclear. Finally, we found no evidence that post-fire changes in soil microbial community composition significantly affect decomposition. Taken together, our study has demonstrated that boreal forest fires can suppress microbial decomposition due to post-fire changes in abiotic factors and the composition of SOM. Models that predict the consequences of increased wildfires for C storage in boreal forests may increase their predictive power by incorporating the observed negative response of microbial decomposition to boreal wildfires.« less

Hydrated electron based decomposition of perfluorooctane sulfonate (PFOS) in the VUV/sulfite system.

PubMed

Gu, Yurong; Liu, Tongzhou; Wang, Hongjie; Han, Huili; Dong, Wenyi

2017-12-31

As one of the most reactive species, hydrated electron (e aq - ) is promising for reductive decomposition of recalcitrant organic pollutants, such as perfluorooctane sulfonate (PFOS). In this study, PFOS decomposition using a vacuum ultraviolet (VUV)/sulfite system was systematically investigated in comparison with sole VUV and ultraviolet (UV)/sulfite systems. A fast and nearly complete (97.3%) PFOS decomposition was observed within 4h from its initial concentration of 37.2μM in the VUV/sulfite system. The observed rate constant (k obs ) for PFOS decomposition in the studied system was 0.87±0.0060h -1 , which was nearly 7.5 and 2 folds faster than that in sole VUV and UV/sulfite systems, respectively. Compared to previously studied UV/sulfite system, VUV/sulfite system enhanced PFOS decomposition in both weak acidic and alkaline pH conditions. In weak acidic condition (pH6.0), PFOS predominantly decomposed via direct VUV photolysis, whereas in alkaline condition (pH>9.0), PFOS decomposition was mainly induced by e aq - generated from both sulfite and VUV photolytic reactions. At a fixed initial solution pH (pH10.0), PFOS decomposition kinetics showed a positive linear dependence with sulfite dosage. The co-presence of humic acid (HA) and NO 3 - obviously suppressed PFOS decomposition, whereas HCO 3 - showed marginal inhibition. A few amount of short chain perfluorocarboxylic acids (PFCAs) were detected in PFOS decomposition process, and a high defluorination efficiency (75.4%) was achieved. These results suggested most fluorine atoms in PFOS molecule ultimately mineralized into fluoride ions, and the mechanisms for PFOS decomposition in the VUV/sulfite system were proposed. Copyright © 2017 Elsevier B.V. All rights reserved.

Potential macro-detritivore range expansion into the subarctic stimulates litter decomposition: a new positive feedback mechanism to climate change?

PubMed

van Geffen, Koert G; Berg, Matty P; Aerts, Rien

2011-12-01

As a result of low decomposition rates, high-latitude ecosystems store large amounts of carbon. Litter decomposition in these ecosystems is constrained by harsh abiotic conditions, but also by the absence of macro-detritivores. We have studied the potential effects of their climate change-driven northward range expansion on the decomposition of two contrasting subarctic litter types. Litter of Alnus incana and Betula pubescens was incubated in microcosms together with monocultures and all possible combinations of three functionally different macro-detritivores (the earthworm Lumbricus rubellus, isopod Oniscus asellus, and millipede Julus scandinavius). Our results show that these macro-detritivores stimulated decomposition, especially of the high-quality A. incana litter and that the macro-detritivores tested differed in their decomposition-stimulating effects, with earthworms having the largest influence. Decomposition processes increased with increasing number of macro-detritivore species, and positive net diveristy effects occurred in several macro-detritivore treatments. However, after correction for macro-detritivore biomass, all interspecific differences in macro-detritivore effects, as well as the positive effects of species number on subarctic litter decomposition disappeared. The net diversity effects also appeared to be driven by variation in biomass, with a possible exception of net diversity effects in mass loss. Based on these results, we conclude that the expected climate change-induced range expansion of macro-detritivores into subarctic regions is likely to result in accelerated decomposition rates. Our results also indicate that the magnitude of macro-detritivore effects on subarctic decomposition will mainly depend on macro-detritivore biomass, rather than on macro-detritivore species number or identity.

Understanding Litter Input Controls on Soil Organic Matter Turnover and Formation are Essential for Improving Carbon-Climate Feedback Predictions for Arctic, Tundra Ecosystems

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wallenstein, Matthew

The Arctic region stored vast amounts of carbon (C) in soils over thousands of years because decomposition has been limited by cold, wet conditions. Arctic soils now contain roughly as much C that is contained in all other soils across the globe combined. However, climate warming could unlock this oil C as decomposition accelerates and permafrost thaws. In addition to temperature-driven acceleration of decomposition, several additional processes could either counteract or augment warming-induced SOM losses. For example, increased plant growth under a warmer climate will increase organic matter inputs to soils, which could fuel further soil decomposition by microbes, butmore » will also increase the production of new SOM. Whether Arctic ecosystems store or release carbon in the future depends in part on the balance between these two counteracting processes. By differentiating SOM decomposition and formation and understanding the drivers of these processes, we will better understand how these systems function. We did not find evidence of priming under current conditions, defined as an increase in the decomposition of native SOM stocks. This suggests that decomposition is unlikely to be further accelerated through this mechanism. We did find that decomposition of native SOM did occur when nitrogen was added to these soils, suggesting that nitrogen limits decomposition in these systems. Our results highlight the resilience and extraordinary C storage capacity of these soils, and suggest shrub expansion may partially mitigate C losses from decomposition of old SOM as Arctic soils warm.« less

Infrared spectroscopy of radiation-chemical transformation of n-hexane on a beryllium surface

NASA Astrophysics Data System (ADS)

Gadzhieva, N. N.

2017-07-01

The radiation-chemical decomposition of n-hexane in a Be- n-hexane system under the effect of γ-irradiation at room temperature is studied by infrared reflection-absorption spectroscopy. In the absorbed dose range 5 kGy ≤ Vγ ≤ 50 kGy, intermediate surface products of radiation-heterogeneous decomposition of n-hexane (beryllium alkyls, π-olefin complexes, and beryllium hydrides) are detected. It is shown that complete radiolysis occurs at Vγ = 30 kGy; below this dose, decomposition of n-hexane occurs only partially, while higher doses lead to steady-state saturation. The radiation-chemical yield of the final decomposition product—molecular hydrogen—is determined to be G ads(H2) = 24.8 molecules/100 eV. A possible mechanism of this process is discussed.

Moisture drives surface decomposition in thawing tundra

NASA Astrophysics Data System (ADS)

Hicks Pries, Caitlin E.; Schuur, E. A. G.; Vogel, Jason G.; Natali, Susan M.

2013-07-01

Permafrost thaw can affect decomposition rates by changing environmental conditions and litter quality. As permafrost thaws, soils warm and thermokarst (ground subsidence) features form, causing some areas to become wetter while other areas become drier. We used a common substrate to measure how permafrost thaw affects decomposition rates in the surface soil in a natural permafrost thaw gradient and a warming experiment in Healy, Alaska. Permafrost thaw also changes plant community composition. We decomposed 12 plant litters in a common garden to test how changing plant litter inputs would affect decomposition. We combined species' tissue-specific decomposition rates with species and tissue-level estimates of aboveground net primary productivity to calculate community-weighted decomposition constants at both the thaw gradient and warming experiment. Moisture, specifically growing season precipitation and water table depth, was the most significant driver of decomposition. At the gradient, an increase in growing season precipitation from 200 to 300 mm increased mass loss of the common substrate by 100%. At the warming experiment, a decrease in the depth to the water table from 30 to 15 cm increased mass loss by 100%. At the gradient, community-weighted decomposition was 21% faster in extensive than in minimal thaw, but was similar when moss production was included. Overall, the effect of climate change and permafrost thaw on surface soil decomposition are driven more by precipitation and soil environment than by changes to plant communities. Increasing soil moisture is thereby another mechanism by which permafrost thaw can become a positive feedback to climate change.

Differential Item Functioning Detection across Two Methods of Defining Group Comparisons: Pairwise and Composite Group Comparisons

ERIC Educational Resources Information Center

Sari, Halil Ibrahim; Huggins, Anne Corinne

2015-01-01

This study compares two methods of defining groups for the detection of differential item functioning (DIF): (a) pairwise comparisons and (b) composite group comparisons. We aim to emphasize and empirically support the notion that the choice of pairwise versus composite group definitions in DIF is a reflection of how one defines fairness in DIF…

Metabolic network prediction through pairwise rational kernels.

PubMed

Roche-Lima, Abiel; Domaratzki, Michael; Fristensky, Brian

2014-09-26

Metabolic networks are represented by the set of metabolic pathways. Metabolic pathways are a series of biochemical reactions, in which the product (output) from one reaction serves as the substrate (input) to another reaction. Many pathways remain incompletely characterized. One of the major challenges of computational biology is to obtain better models of metabolic pathways. Existing models are dependent on the annotation of the genes. This propagates error accumulation when the pathways are predicted by incorrectly annotated genes. Pairwise classification methods are supervised learning methods used to classify new pair of entities. Some of these classification methods, e.g., Pairwise Support Vector Machines (SVMs), use pairwise kernels. Pairwise kernels describe similarity measures between two pairs of entities. Using pairwise kernels to handle sequence data requires long processing times and large storage. Rational kernels are kernels based on weighted finite-state transducers that represent similarity measures between sequences or automata. They have been effectively used in problems that handle large amount of sequence information such as protein essentiality, natural language processing and machine translations. We create a new family of pairwise kernels using weighted finite-state transducers (called Pairwise Rational Kernel (PRK)) to predict metabolic pathways from a variety of biological data. PRKs take advantage of the simpler representations and faster algorithms of transducers. Because raw sequence data can be used, the predictor model avoids the errors introduced by incorrect gene annotations. We then developed several experiments with PRKs and Pairwise SVM to validate our methods using the metabolic network of Saccharomyces cerevisiae. As a result, when PRKs are used, our method executes faster in comparison with other pairwise kernels. Also, when we use PRKs combined with other simple kernels that include evolutionary information, the accuracy values have been improved, while maintaining lower construction and execution times. The power of using kernels is that almost any sort of data can be represented using kernels. Therefore, completely disparate types of data can be combined to add power to kernel-based machine learning methods. When we compared our proposal using PRKs with other similar kernel, the execution times were decreased, with no compromise of accuracy. We also proved that by combining PRKs with other kernels that include evolutionary information, the accuracy can also also be improved. As our proposal can use any type of sequence data, genes do not need to be properly annotated, avoiding accumulation errors because of incorrect previous annotations.

Emissions of volatile organic compounds during the decomposition of plant litter

NASA Astrophysics Data System (ADS)

Gray, Christopher M.; Monson, Russell K.; Fierer, Noah

2010-09-01

Volatile organic compounds (VOCs) are emitted during plant litter decomposition, and such VOCs can have wide-ranging impacts on atmospheric chemistry, terrestrial biogeochemistry, and soil ecology. However, we currently have a limited understanding of the relative importance of biotic versus abiotic sources of these VOCs and whether distinct types of litter emit different types and quantities of VOCs during decomposition. We analyzed VOCs emitted by microbes or by abiotic mechanisms during the decomposition of litter from 12 plant species in a laboratory experiment using proton transfer reaction mass spectrometry (PTR-MS). Net emissions from litter with active microbial populations (non-sterile litters) were between 0 and 11 times higher than emissions from sterile controls over a 20-d incubation period, suggesting that abiotic sources of VOCs are generally less important than biotic sources. In all cases, the sterile and non-sterile litter treatments emitted different types of VOCs, with methanol being the dominant VOC emitted from litters during microbial decomposition, accounting for 78 to 99% of the net emissions. We also found that the types of VOCs released during biotic decomposition differed in a predictable manner among litter types with VOC profiles also changing as decomposition progressed over time. These results show the importance of incorporating both the biotic decomposition of litter and the species-dependent differences in terrestrial vegetation into global VOC emission models.

When things don't add up: quantifying impacts of multiple stressors from individual metabolism to ecosystem processing.

PubMed

Galic, Nika; Sullivan, Lauren L; Grimm, Volker; Forbes, Valery E

2018-04-01

Ecosystems are exposed to multiple stressors which can compromise functioning and service delivery. These stressors often co-occur and interact in different ways which are not yet fully understood. Here, we applied a population model representing a freshwater amphipod feeding on leaf litter in forested streams. We simulated impacts of hypothetical stressors, individually and in pairwise combinations that target the individuals' feeding, maintenance, growth and reproduction. Impacts were quantified by examining responses at three levels of biological organisation: individual-level body sizes and cumulative reproduction, population-level abundance and biomass and ecosystem-level leaf litter decomposition. Interactive effects of multiple stressors at the individual level were mostly antagonistic, that is, less negative than expected. Most population- and ecosystem-level responses to multiple stressors were stronger than expected from an additive model, that is, synergistic. Our results suggest that across levels of biological organisation responses to multiple stressors are rarely only additive. We suggest methods for efficiently quantifying impacts of multiple stressors at different levels of biological organisation. © 2018 John Wiley & Sons Ltd/CNRS.

Power and sample-size estimation for microbiome studies using pairwise distances and PERMANOVA.

PubMed

Kelly, Brendan J; Gross, Robert; Bittinger, Kyle; Sherrill-Mix, Scott; Lewis, James D; Collman, Ronald G; Bushman, Frederic D; Li, Hongzhe

2015-08-01

The variation in community composition between microbiome samples, termed beta diversity, can be measured by pairwise distance based on either presence-absence or quantitative species abundance data. PERMANOVA, a permutation-based extension of multivariate analysis of variance to a matrix of pairwise distances, partitions within-group and between-group distances to permit assessment of the effect of an exposure or intervention (grouping factor) upon the sampled microbiome. Within-group distance and exposure/intervention effect size must be accurately modeled to estimate statistical power for a microbiome study that will be analyzed with pairwise distances and PERMANOVA. We present a framework for PERMANOVA power estimation tailored to marker-gene microbiome studies that will be analyzed by pairwise distances, which includes: (i) a novel method for distance matrix simulation that permits modeling of within-group pairwise distances according to pre-specified population parameters; (ii) a method to incorporate effects of different sizes within the simulated distance matrix; (iii) a simulation-based method for estimating PERMANOVA power from simulated distance matrices; and (iv) an R statistical software package that implements the above. Matrices of pairwise distances can be efficiently simulated to satisfy the triangle inequality and incorporate group-level effects, which are quantified by the adjusted coefficient of determination, omega-squared (ω2). From simulated distance matrices, available PERMANOVA power or necessary sample size can be estimated for a planned microbiome study. © The Author 2015. Published by Oxford University Press. All rights reserved. For Permissions, please e-mail: journals.permissions@oup.com.

Ecological role of reindeer summer browsing in the mountain birch (Betula pubescens ssp. czerepanovii) forests: effects on plant defense, litter decomposition, and soil nutrient cycling.

PubMed

Stark, Sari; Julkunen-Tiitto, Riitta; Kumpula, Jouko

2007-03-01

Mammalian herbivores commonly alter the concentrations of secondary compounds in plants and, by this mechanism, have indirect effects on litter decomposition and soil carbon and nutrient cycling. In northernmost Fennoscandia, the subarctic mountain birch (Betula pubescens ssp. czerepanovii) forests are important pasture for the semidomestic reindeer (Rangifer tarandus). In the summer ranges, mountain birches are intensively browsed, whereas in the winter ranges, reindeer feed on ground lichens, and the mountain birches remain intact. We analyzed the effect of summer browsing on the concentrations of secondary substances, litter decomposition, and soil nutrient pools in areas that had been separated as summer or winter ranges for at least 20 years, and we predicted that summer browsing may reduce levels of secondary compounds in the mountain birch and, by this mechanism, have an indirect effect on the decomposition of mountain birch leaf litter and soil nutrient cycling. The effect of browsing on the concentration of secondary substances in the mountain birch leaves varied between different years and management districts, but in some cases, the concentration of condensed tannins was lower in the summer than in the winter ranges. In a reciprocal litter decomposition trial, both litter origin and emplacement significantly affected the litter decomposition rate. Decomposition rates were faster for the litter originating from and placed into the summer range. Soil inorganic nitrogen (N) concentrations were higher in the summer than in the winter ranges, which indicates that reindeer summer browsing may enhance the soil nutrient cycling. There was a tight inverse relationship between soil N and foliar tannin concentrations in the winter range but not in the summer range. This suggests that in these strongly nutrient-limited ecosystems, soil N availability regulates the patterns of resource allocation to condensed tannins in the absence but not in the presence of browsing.

Mechanical and Assembly Units of Viral Capsids Identified via Quasi-Rigid Domain Decomposition

PubMed Central

Polles, Guido; Indelicato, Giuliana; Potestio, Raffaello; Cermelli, Paolo; Twarock, Reidun; Micheletti, Cristian

2013-01-01

Key steps in a viral life-cycle, such as self-assembly of a protective protein container or in some cases also subsequent maturation events, are governed by the interplay of physico-chemical mechanisms involving various spatial and temporal scales. These salient aspects of a viral life cycle are hence well described and rationalised from a mesoscopic perspective. Accordingly, various experimental and computational efforts have been directed towards identifying the fundamental building blocks that are instrumental for the mechanical response, or constitute the assembly units, of a few specific viral shells. Motivated by these earlier studies we introduce and apply a general and efficient computational scheme for identifying the stable domains of a given viral capsid. The method is based on elastic network models and quasi-rigid domain decomposition. It is first applied to a heterogeneous set of well-characterized viruses (CCMV, MS2, STNV, STMV) for which the known mechanical or assembly domains are correctly identified. The validated method is next applied to other viral particles such as L-A, Pariacoto and polyoma viruses, whose fundamental functional domains are still unknown or debated and for which we formulate verifiable predictions. The numerical code implementing the domain decomposition strategy is made freely available. PMID:24244139

An investigation on the modelling of kinetics of thermal decomposition of hazardous mercury wastes.

PubMed

Busto, Yailen; M G Tack, Filip; Peralta, Luis M; Cabrera, Xiomara; Arteaga-Pérez, Luis E

2013-09-15

The kinetics of mercury removal from solid wastes generated by chlor-alkali plants were studied. The reaction order and model-free method with an isoconversional approach were used to estimate the kinetic parameters and reaction mechanism that apply to the thermal decomposition of hazardous mercury wastes. As a first approach to the understanding of thermal decomposition for this type of systems (poly-disperse and multi-component), a novel scheme of six reactions was proposed to represent the behaviour of mercury compounds in the solid matrix during the treatment. An integration-optimization algorithm was used in the screening of nine mechanistic models to develop kinetic expressions that best describe the process. The kinetic parameters were calculated by fitting each of these models to the experimental data. It was demonstrated that the D₁-diffusion mechanism appeared to govern the process at 250°C and high residence times, whereas at 450°C a combination of the diffusion mechanism (D₁) and the third order reaction mechanism (F3) fitted the kinetics of the conversions. The developed models can be applied in engineering calculations to dimension the installations and determine the optimal conditions to treat a mercury containing sludge. Copyright © 2013 Elsevier B.V. All rights reserved.

A Higher-Order Generalized Singular Value Decomposition for Comparison of Global mRNA Expression from Multiple Organisms

PubMed Central

Ponnapalli, Sri Priya; Saunders, Michael A.; Van Loan, Charles F.; Alter, Orly

2011-01-01

The number of high-dimensional datasets recording multiple aspects of a single phenomenon is increasing in many areas of science, accompanied by a need for mathematical frameworks that can compare multiple large-scale matrices with different row dimensions. The only such framework to date, the generalized singular value decomposition (GSVD), is limited to two matrices. We mathematically define a higher-order GSVD (HO GSVD) for N≥2 matrices , each with full column rank. Each matrix is exactly factored as Di = UiΣiVT, where V, identical in all factorizations, is obtained from the eigensystem SV = VΛ of the arithmetic mean S of all pairwise quotients of the matrices , i≠j. We prove that this decomposition extends to higher orders almost all of the mathematical properties of the GSVD. The matrix S is nondefective with V and Λ real. Its eigenvalues satisfy λk≥1. Equality holds if and only if the corresponding eigenvector vk is a right basis vector of equal significance in all matrices Di and Dj, that is σi,k/σj,k = 1 for all i and j, and the corresponding left basis vector ui,k is orthogonal to all other vectors in Ui for all i. The eigenvalues λk = 1, therefore, define the “common HO GSVD subspace.” We illustrate the HO GSVD with a comparison of genome-scale cell-cycle mRNA expression from S. pombe, S. cerevisiae and human. Unlike existing algorithms, a mapping among the genes of these disparate organisms is not required. We find that the approximately common HO GSVD subspace represents the cell-cycle mRNA expression oscillations, which are similar among the datasets. Simultaneous reconstruction in the common subspace, therefore, removes the experimental artifacts, which are dissimilar, from the datasets. In the simultaneous sequence-independent classification of the genes of the three organisms in this common subspace, genes of highly conserved sequences but significantly different cell-cycle peak times are correctly classified. PMID:22216090

DFT study of hydrogen production from formic acid decomposition on Pd-Au alloy nanoclusters

NASA Astrophysics Data System (ADS)

Liu, D.; Gao, Z. Y.; Wang, X. C.; Zeng, J.; Li, Y. M.

2017-12-01

Recently, it has been reported that the hydrogen production rate of formic acid decomposition can be significantly increased using Pd-Au binary alloy nano-catalysts [Wang et al. J. Mater. Chem. A 1 (2013) 12721-12725]. To explain the reaction mechanism of this alloy catalysis method, formic acid decomposition reactions on pure Pd and Pd-Au alloy nanoclusters are studied via density functional theory simulations. The simulation results indicate that the addition of inert element Au would not influence formic acid decomposition on Pd surface sites of Pd-Au alloy nanoclusters. On the other hand, the existence of Au surface sites brings relative weak hydrogen atom adsorption. On Pd-Au alloy nanoclusters, the dissociated hydrogen atoms from formic acid are easier to combine as hydrogen molecules than that on pure Pd clusters. Via the synergetic effect between Pd and Au, both formic acid decomposition and hydrogen production are events with large probability, which eventually results in high hydrogen production rate.

Kinetics of Thermal Decomposition of Ammonium Perchlorate by TG/DSC-MS-FTIR

NASA Astrophysics Data System (ADS)

Zhu, Yan-Li; Huang, Hao; Ren, Hui; Jiao, Qing-Jie

2014-01-01

The method of thermogravimetry/differential scanning calorimetry-mass spectrometry-Fourier transform infrared (TG/DSC-MS-FTIR) simultaneous analysis has been used to study thermal decomposition of ammonium perchlorate (AP). The processing of nonisothermal data at various heating rates was performed using NETZSCH Thermokinetics. The MS-FTIR spectra showed that N2O and NO2 were the main gaseous products of the thermal decomposition of AP, and there was a competition between the formation reaction of N2O and that of NO2 during the process with an iso-concentration point of N2O and NO2. The dependence of the activation energy calculated by Friedman's iso-conversional method on the degree of conversion indicated that the AP decomposition process can be divided into three stages, which are autocatalytic, low-temperature diffusion and high-temperature, stable-phase reaction. The corresponding kinetic parameters were determined by multivariate nonlinear regression and the mechanism of the AP decomposition process was proposed.

Multidrug resistant pathogens respond differently to the presence of co-pathogen, commensal, probiotic and host cells.

PubMed

Chan, Agnes P; Choi, Yongwook; Brinkac, Lauren M; Krishnakumar, Radha; DePew, Jessica; Kim, Maria; Hinkle, Mary K; Lesho, Emil P; Fouts, Derrick E

2018-06-05

In light of the ongoing antimicrobial resistance crisis, there is a need to understand the role of co-pathogens, commensals, and the local microbiome in modulating virulence and antibiotic resistance. To identify possible interactions that influence the expression of virulence or survival mechanisms in both the multidrug-resistant organisms (MDROs) and human host cells, unique cohorts of clinical isolates were selected for whole genome sequencing with enhanced assembly and full annotation, pairwise co-culturing, and transcriptome profiling. The MDROs were co-cultured in pairwise combinations either with: (1) another MDRO, (2) skin commensals (Staphylococcus epidermidis and Corynebacterium jeikeium), (3) the common probiotic Lactobacillus reuteri, and (4) human fibroblasts. RNA-Seq analysis showed distinct regulation of virulence and antimicrobial resistance gene responses across different combinations of MDROs, commensals, and human cells. Co-culture assays demonstrated that microbial interactions can modulate gene responses of both the target and pathogen/commensal species, and that the responses are specific to the identity of the pathogen/commensal species. In summary, bacteria have mechanisms to distinguish between friends, foe and host cells. These results provide foundational data and insight into the possibility of manipulating the local microbiome when treating complicated polymicrobial wound, intra-abdominal, or respiratory infections.

Stabilization of the Thermal Decomposition of Poly(Propylene Carbonate) Through Copper Ion Incorporation and Use in Self-Patterning

NASA Astrophysics Data System (ADS)

Spencer, Todd J.; Chen, Yu-Chun; Saha, Rajarshi; Kohl, Paul A.

2011-06-01

Incorporation of copper ions into poly(propylene carbonate) (PPC) films cast from γ-butyrolactone (GBL), trichloroethylene (TCE) or methylene chloride (MeCl) solutions containing a photo-acid generator is shown to stabilize the PPC from thermal decomposition. Copper ions were introduced into the PPC mixtures by bringing the polymer mixture into contact with copper metal. The metal was oxidized and dissolved into the PPC mixture. The dissolved copper interferes with the decomposition mechanism of PPC, raising its decomposition temperature. Thermogravimetric analysis shows that copper ions make PPC more stable by up to 50°C. Spectroscopic analysis indicates that copper ions may stabilize terminal carboxylic acid groups, inhibiting PPC decomposition. The change in thermal stability based on PPC exposure to patterned copper substrates was used to provide a self-aligned patterning method for PPC on copper traces without the need for an additional photopatterning registration step. Thermal decomposition of PPC is then used to create air isolation regions around the copper traces. The spatial resolution of the self-patterning PPC process is limited by the lateral diffusion of the copper ions within the PPC. The concentration profiles of copper within the PPC, patterning resolution, and temperature effects on the PPC decomposition have been studied.

Reaction Mechanisms of Energetic Materials in the Condensed Phase: Long-term Aging, Munition Safety and Condensed-Phase Processes in Propellants and Explosives

DTIC Science & Technology

2009-03-31

Journal of the American Society for Mass Spectrometry, 2002. 13(2): p. 135- 143 . 7. Delcorte, A., P. Bertrand, and B.J. Garrison, Collision cascade and...TNCHP. 49, 50 The presence of the keto group in K6 appears to promote a more direct reaction to the gaseous decomposition products. Decomposition

The relative importance of decomposition and transport mechanisms in accounting for soil organic carbon profiles

NASA Astrophysics Data System (ADS)

Guenet, B.; Eglin, T.; Vasilyeva, N.; Peylin, P.; Ciais, P.; Chenu, C.

2013-04-01

Soil is the major terrestrial reservoir of carbon and a substantial part of this carbon is stored in deep layers, typically deeper than 50 cm below the surface. Several studies underlined the quantitative importance of this deep soil organic carbon (SOC) pool and models are needed to better understand this stock and its evolution under climate and land-uses changes. In this study, we tested and compared three simple theoretical models of vertical transport for SOC against SOC profiles measurements from a long-term bare fallow experiment carried out by the Central-Chernozem State Natural Biosphere Reserve in the Kursk Region of Russia. The transport schemes tested are diffusion, advection and both diffusion and advection. They are coupled to three different formulations of soil carbon decomposition kinetics. The first formulation is a first order kinetics widely used in global SOC decomposition models; the second one, so-called "priming" model, links SOC decomposition rate to the amount of fresh organic matter, representing the substrate interactions. The last one is also a first order kinetics, but SOC is split into two pools. Field data are from a set of three bare fallow plots where soil received no input during the past 20, 26 and 58 yr, respectively. Parameters of the models were optimised using a Bayesian method. The best results are obtained when SOC decomposition is assumed to be controlled by fresh organic matter (i.e., the priming model). In comparison to the first-order kinetic model, the priming model reduces the overestimation in the deep layers. We also observed that the transport scheme that improved the fit with the data depended on the soil carbon mineralisation formulation chosen. When soil carbon decomposition was modelled to depend on the fresh organic matter amount, the transport mechanism which improved best the fit to the SOC profile data was the model representing both advection and diffusion. Interestingly, the older the bare fallow is, the lesser the need for diffusion is, suggesting that stabilised carbon may not be transported within the profile by the same mechanisms than more labile carbon.

Pairwise frictional profile between particles determines discontinuous shear thickening transition in non-colloidal suspensions

PubMed Central

Comtet, Jean; Chatté, Guillaume; Niguès, Antoine; Bocquet, Lydéric; Siria, Alessandro; Colin, Annie

2017-01-01

The process by which sheared suspensions go through a dramatic change in viscosity is known as discontinuous shear thickening. Although well-characterized on the macroscale, the microscopic mechanisms at play in this transition are still poorly understood. Here, by developing new experimental procedures based on quartz-tuning fork atomic force microscopy, we measure the pairwise frictional profile between approaching pairs of polyvinyl chloride and cornstarch particles in solvent. We report a clear transition from a low-friction regime, where pairs of particles support a finite normal load, while interacting purely hydrodynamically, to a high-friction regime characterized by hard repulsive contact between the particles and sliding friction. Critically, we show that the normal stress needed to enter the frictional regime at nanoscale matches the critical stress at which shear thickening occurs for macroscopic suspensions. Our experiments bridge nano and macroscales and provide long needed demonstration of the role of frictional forces in discontinuous shear thickening. PMID:28561032

Pairwise frictional profile between particles determines discontinuous shear thickening transition in non-colloidal suspensions.

PubMed

Comtet, Jean; Chatté, Guillaume; Niguès, Antoine; Bocquet, Lydéric; Siria, Alessandro; Colin, Annie

2017-05-31

The process by which sheared suspensions go through a dramatic change in viscosity is known as discontinuous shear thickening. Although well-characterized on the macroscale, the microscopic mechanisms at play in this transition are still poorly understood. Here, by developing new experimental procedures based on quartz-tuning fork atomic force microscopy, we measure the pairwise frictional profile between approaching pairs of polyvinyl chloride and cornstarch particles in solvent. We report a clear transition from a low-friction regime, where pairs of particles support a finite normal load, while interacting purely hydrodynamically, to a high-friction regime characterized by hard repulsive contact between the particles and sliding friction. Critically, we show that the normal stress needed to enter the frictional regime at nanoscale matches the critical stress at which shear thickening occurs for macroscopic suspensions. Our experiments bridge nano and macroscales and provide long needed demonstration of the role of frictional forces in discontinuous shear thickening.

Statistical Mechanics of the US Supreme Court

NASA Astrophysics Data System (ADS)

Lee, Edward D.; Broedersz, Chase P.; Bialek, William

2015-07-01

We build simple models for the distribution of voting patterns in a group, using the Supreme Court of the United States as an example. The maximum entropy model consistent with the observed pairwise correlations among justices' votes, an Ising spin glass, agrees quantitatively with the data. While all correlations (perhaps surprisingly) are positive, the effective pairwise interactions in the spin glass model have both signs, recovering the intuition that ideologically opposite justices negatively influence each another. Despite the competing interactions, a strong tendency toward unanimity emerges from the model, organizing the voting patterns in a relatively simple "energy landscape." Besides unanimity, other energy minima in this landscape, or maxima in probability, correspond to prototypical voting states, such as the ideological split or a tightly correlated, conservative core. The model correctly predicts the correlation of justices with the majority and gives us a measure of their influence on the majority decision. These results suggest that simple models, grounded in statistical physics, can capture essential features of collective decision making quantitatively, even in a complex political context.

Statistical mechanics of letters in words

PubMed Central

Stephens, Greg J.; Bialek, William

2013-01-01

We consider words as a network of interacting letters, and approximate the probability distribution of states taken on by this network. Despite the intuition that the rules of English spelling are highly combinatorial and arbitrary, we find that maximum entropy models consistent with pairwise correlations among letters provide a surprisingly good approximation to the full statistics of words, capturing ~92% of the multi-information in four-letter words and even “discovering” words that were not represented in the data. These maximum entropy models incorporate letter interactions through a set of pairwise potentials and thus define an energy landscape on the space of possible words. Guided by the large letter redundancy we seek a lower-dimensional encoding of the letter distribution and show that distinctions between local minima in the landscape account for ~68% of the four-letter entropy. We suggest that these states provide an effective vocabulary which is matched to the frequency of word use and much smaller than the full lexicon. PMID:20866490

A second order thermodynamic perturbation theory for hydrogen bond cooperativity in water

NASA Astrophysics Data System (ADS)

Marshall, Bennett D.

2017-05-01

It has been extensively demonstrated through first principles quantum mechanics calculations that water exhibits strong hydrogen bond cooperativity. Equations of state developed from statistical mechanics typically assume pairwise additivity, meaning they cannot account for these 3-body and higher cooperative effects. In this paper, we extend a second order thermodynamic perturbation theory to correct for hydrogen bond cooperativity in 4 site water. We demonstrate that the theory predicts hydrogen bonding structure consistent spectroscopy, neutron diffraction, and molecular simulation data. Finally, we implement the approach into a general equation of state for water.

Polymethacrylic acid as a new precursor of CuO nanoparticles

NASA Astrophysics Data System (ADS)

Hosny, Nasser Mohammed; Zoromba, Mohamed Shafick

2012-11-01

Polymethacrylic acid and its copper complexes have been synthesized and characterized. These complexes have been used as precursors to produce CuO nanoparticles by thermal decomposition in air. The stages of decompositions and the calcination temperature of the precursors have been determined from thermal analyses (TGA). The obtained CuO nanoparticles have been characterized by X-ray diffraction (XRD), scanning tunneling microscopy (STM) and transmission electron microscopy (TEM). XRD showed a monoclinic structure with particle size 8-20 nm for the synthesized copper oxide nanoparticles. These nanoparticles are catalytically active in decomposing hydrogen peroxide and a mechanism of decomposition has been suggested.

gamma-Irradiation effects on the thermal decomposition behaviour and IR absorption spectra of piperacillin

NASA Astrophysics Data System (ADS)

Mahfouz, R. M.; Gaffar, M. A.; Abu El-Fadl, A.; Hamad, Ar. G. K.

2003-11-01

The thermal decomposition behaviour of unirradiated and pre-gamma-irradiated piperacillin (pipril) as a semi-synthetic penicillin antibiotic has been studied in the temperature range of (273-1072 K). The decomposition was found to proceed through three major steps both for unirradiated and gamma-irradiated samples. Neither appearance nor disappearance of new bands in the IR spectrum of piperacillin was recorded as a result of gamma-irradiation but only a decrease in the intensity of most bands was observed. A degradation mechanism was suggested to explain the bond rupture and the decrease in the intensities of IR bands of gamma-irradiated piperacillin.

Pair-Wise Trajectory Management-Oceanic (PTM-O) . [Concept of Operations—Version 3.9

NASA Technical Reports Server (NTRS)

Jones, Kenneth M.

2014-01-01

This document describes the Pair-wise Trajectory Management-Oceanic (PTM-O) Concept of Operations (ConOps). Pair-wise Trajectory Management (PTM) is a concept that includes airborne and ground-based capabilities designed to enable and to benefit from, airborne pair-wise distance-monitoring capability. PTM includes the capabilities needed for the controller to issue a PTM clearance that resolves a conflict for a specific pair of aircraft. PTM avionics include the capabilities needed for the flight crew to manage their trajectory relative to specific designated aircraft. Pair-wise Trajectory Management PTM-Oceanic (PTM-O) is a regional specific application of the PTM concept. PTM is sponsored by the National Aeronautics and Space Administration (NASA) Concept and Technology Development Project (part of NASA's Airspace Systems Program). The goal of PTM is to use enhanced and distributed communications and surveillance along with airborne tools to permit reduced separation standards for given aircraft pairs, thereby increasing the capacity and efficiency of aircraft operations at a given altitude or volume of airspace.

A pairwise maximum entropy model accurately describes resting-state human brain networks

PubMed Central

Watanabe, Takamitsu; Hirose, Satoshi; Wada, Hiroyuki; Imai, Yoshio; Machida, Toru; Shirouzu, Ichiro; Konishi, Seiki; Miyashita, Yasushi; Masuda, Naoki

2013-01-01

The resting-state human brain networks underlie fundamental cognitive functions and consist of complex interactions among brain regions. However, the level of complexity of the resting-state networks has not been quantified, which has prevented comprehensive descriptions of the brain activity as an integrative system. Here, we address this issue by demonstrating that a pairwise maximum entropy model, which takes into account region-specific activity rates and pairwise interactions, can be robustly and accurately fitted to resting-state human brain activities obtained by functional magnetic resonance imaging. Furthermore, to validate the approximation of the resting-state networks by the pairwise maximum entropy model, we show that the functional interactions estimated by the pairwise maximum entropy model reflect anatomical connexions more accurately than the conventional functional connectivity method. These findings indicate that a relatively simple statistical model not only captures the structure of the resting-state networks but also provides a possible method to derive physiological information about various large-scale brain networks. PMID:23340410

Decomposition-based transfer distance metric learning for image classification.

PubMed

Luo, Yong; Liu, Tongliang; Tao, Dacheng; Xu, Chao

2014-09-01

Distance metric learning (DML) is a critical factor for image analysis and pattern recognition. To learn a robust distance metric for a target task, we need abundant side information (i.e., the similarity/dissimilarity pairwise constraints over the labeled data), which is usually unavailable in practice due to the high labeling cost. This paper considers the transfer learning setting by exploiting the large quantity of side information from certain related, but different source tasks to help with target metric learning (with only a little side information). The state-of-the-art metric learning algorithms usually fail in this setting because the data distributions of the source task and target task are often quite different. We address this problem by assuming that the target distance metric lies in the space spanned by the eigenvectors of the source metrics (or other randomly generated bases). The target metric is represented as a combination of the base metrics, which are computed using the decomposed components of the source metrics (or simply a set of random bases); we call the proposed method, decomposition-based transfer DML (DTDML). In particular, DTDML learns a sparse combination of the base metrics to construct the target metric by forcing the target metric to be close to an integration of the source metrics. The main advantage of the proposed method compared with existing transfer metric learning approaches is that we directly learn the base metric coefficients instead of the target metric. To this end, far fewer variables need to be learned. We therefore obtain more reliable solutions given the limited side information and the optimization tends to be faster. Experiments on the popular handwritten image (digit, letter) classification and challenge natural image annotation tasks demonstrate the effectiveness of the proposed method.

A three-way parallel ICA approach to analyze links among genetics, brain structure and brain function.

PubMed

Vergara, Victor M; Ulloa, Alvaro; Calhoun, Vince D; Boutte, David; Chen, Jiayu; Liu, Jingyu

2014-09-01

Multi-modal data analysis techniques, such as the Parallel Independent Component Analysis (pICA), are essential in neuroscience, medical imaging and genetic studies. The pICA algorithm allows the simultaneous decomposition of up to two data modalities achieving better performance than separate ICA decompositions and enabling the discovery of links between modalities. However, advances in data acquisition techniques facilitate the collection of more than two data modalities from each subject. Examples of commonly measured modalities include genetic information, structural magnetic resonance imaging (MRI) and functional MRI. In order to take full advantage of the available data, this work extends the pICA approach to incorporate three modalities in one comprehensive analysis. Simulations demonstrate the three-way pICA performance in identifying pairwise links between modalities and estimating independent components which more closely resemble the true sources than components found by pICA or separate ICA analyses. In addition, the three-way pICA algorithm is applied to real experimental data obtained from a study that investigate genetic effects on alcohol dependence. Considered data modalities include functional MRI (contrast images during alcohol exposure paradigm), gray matter concentration images from structural MRI and genetic single nucleotide polymorphism (SNP). The three-way pICA approach identified links between a SNP component (pointing to brain function and mental disorder associated genes, including BDNF, GRIN2B and NRG1), a functional component related to increased activation in the precuneus area, and a gray matter component comprising part of the default mode network and the caudate. Although such findings need further verification, the simulation and in-vivo results validate the three-way pICA algorithm presented here as a useful tool in biomedical data fusion applications. Copyright © 2014 Elsevier Inc. All rights reserved.

On the mechanism of penetration of ovicidal fungi through egg-shells of parasitic nematodes. Decomposition of chitinous and ascaroside layers.

PubMed

Kunert, J

1992-01-01

The decomposition of egg-shells of Ascaris lumbricoides L. was studied microscopically using topochemical methods in a set of 32 strains of soil ovicidal fungi. It was found that even fungi displaying minimal chitinolytic activity in tests on purified chitin in vitro are able to dissolve chitin of egg-shells during the attack on live eggs. Fungi without any chitinolytic activity penetrate probably only the mechanically damaged eggs. None of the studied fungi was capable of degrading enzymatically the glycolipid (ascaroside) layer of the egg-shell which remained intact after digestion of all other components of the egg.

Clathrate hydrates in cometary nuclei and porosity

NASA Technical Reports Server (NTRS)

Smoluchowski, R.

1988-01-01

Possible mechanisms of formation and decomposition of CO2-clathrate hydrate in cometary nuclei are discussed. As far as it is known, this is the only clathrate hydrate which is unstable at low temperatures. Calculation shows that, in accord with other evidence, neither volume nor grain boundary diffusion in the clathrate lattice can be responsible for the rate of these reactions and that a surface mechanism with the attendant sensitivity to pressure must play a crucial role. Density changes accompanying CO2-clathrate decomposition and formation can lead to microporosity and enhanced brittleness or even to fracture of cometary nuclei at low temperatures. Other clathrate hydrates and mixed clathrates are also discussed.

Functionally dissimilar neighbors accelerate litter decomposition in two grass species.

PubMed

Barbe, Lou; Jung, Vincent; Prinzing, Andreas; Bittebiere, Anne-Kristel; Butenschoen, Olaf; Mony, Cendrine

2017-05-01

Plant litter decomposition is a key regulator of nutrient recycling. In a given environment, decomposition of litter from a focal species depends on its litter quality and on the efficiency of local decomposers. Both may be strongly modified by functional traits of neighboring species, but the consequences for decomposition of litter from the focal species remain unknown. We tested whether decomposition of a focal plant's litter is influenced by the functional-trait dissimilarity to the neighboring plants. We cultivated two grass species (Brachypodium pinnatum and Elytrigia repens) in experimental mesocosms with functionally similar and dissimilar neighborhoods, and reciprocally transplanted litter. For both species, litter quality increased in functionally dissimilar neighborhoods, partly as a result of changes in functional traits involved in plant-plant interactions. Furthermore, functional dissimilarity increased overall decomposer efficiency in one species, probably via complementarity effects. Our results suggest a novel mechanism of biodiversity effects on ecosystem functioning in grasslands: interspecific functional diversity within plant communities can enhance intraspecific contributions to litter decomposition. Thus, plant species might better perform in diverse communities by benefiting from higher remineralization rates of their own litter. © 2017 The Authors. New Phytologist © 2017 New Phytologist Trust.

Fungal community structure of fallen pine and oak wood at different stages of decomposition in the Qinling Mountains, China.

PubMed

Yuan, Jie; Zheng, Xiaofeng; Cheng, Fei; Zhu, Xian; Hou, Lin; Li, Jingxia; Zhang, Shuoxin

2017-10-24

Historically, intense forest hazards have resulted in an increase in the quantity of fallen wood in the Qinling Mountains. Fallen wood has a decisive influence on the nutrient cycling, carbon budget and ecosystem biodiversity of forests, and fungi are essential for the decomposition of fallen wood. Moreover, decaying dead wood alters fungal communities. The development of high-throughput sequencing methods has facilitated the ongoing investigation of relevant molecular forest ecosystems with a focus on fungal communities. In this study, fallen wood and its associated fungal communities were compared at different stages of decomposition to evaluate relative species abundance and species diversity. The physical and chemical factors that alter fungal communities were also compared by performing correspondence analysis according to host tree species across all stages of decomposition. Tree species were the major source of differences in fungal community diversity at all decomposition stages, and fungal communities achieved the highest levels of diversity at the intermediate and late decomposition stages. Interactions between various physical and chemical factors and fungal communities shared the same regulatory mechanisms, and there was no tree species-specific influence. Improving our knowledge of wood-inhabiting fungal communities is crucial for forest ecosystem conservation.

Bulk Diffusion via a ``kick-out'' method for Lithium in the decomposition reaction LiAlH4/Li3AlH6

NASA Astrophysics Data System (ADS)

Rolih, Biljana; Ozolins, Vidvuds; Ozolins Team

2013-03-01

In the pursuit to find a practical system for hydrogen storage, complex metal hydrides have long been considered as viable candidates due to their high hydrogen content. However, some of the challenges faced with these types of systems are poor thermodynamics or kinetics. The underlying mechanisms, and their limiting processes, for the decomposition of these materials need to be understood. From experimental work on the decomposition of hydrogen storage materials, it has been suggested that bulk diffusion of metal species is the bottleneck for hydrogen release. In this work is the dehydrogenation we investigated the system LiAlH4  LiAlH6 with favorable hydrogen release (5.3 wt %), at moderate temperatures. Using first-principles density functional theory we found the defects facilitating mass transport by calculating individual formation energies, highest concentrations, and activation barriers for defect mobility. The mass transport of Lithium is found to be mediated by a ``kick-out'' mechanism. The results are used to further our understanding of the fundamental mechanism of mass transport and evaluate the possibility of kinetics as the limiting process in this reaction.

Study of thermal decomposition mechanisms and low-level detection of explosives using pulsed photoacoustic technique

NASA Astrophysics Data System (ADS)

Yehya, F.; Chaudhary, A. K.; Srinivas, D.; Muralidharan, K.

2015-11-01

We report a novel time-resolved photoacoustic-based technique for studying the thermal decomposition mechanisms of some secondary explosives such as RDX (hexahydro-1,3,5-trinitro-1,3,5-triazine), picric acid, 4,6-dinitro-5-(4-nitro-1 H-imidazol-1-yl)-1 H-benzo[ d] [1-3] triazole, and 5-chloro-1-(4-nitrophenyl)-1 H-tetrazole. A comparison of the thermal decomposition mechanisms of these secondary explosives was made by detecting NO2 molecules released under controlled pyrolysis between 25 and 350 °C. The results show excellent agreement with the thermogravimetric and differential thermal analysis (TGA-DTA) results. A specially designed PA cell made of stainless steel was filled with explosive vapor and pumped using second harmonic, i.e., λ = 532 nm, pulses of duration 7 ns at a 10 Hz repetition rate, obtained using a Q-switched Nd:YAG laser. The use of a combination of PA and TGA-DTA techniques enables the study of NO2 generation, and this method can be used to scale the performance of these explosives as rocket fuels. The minimum detection limits of the four explosives were 38 ppmv to 69 ppbv, depending on their respective vapor pressures.

Why rate when you could compare? Using the "EloChoice" package to assess pairwise comparisons of perceived physical strength.

PubMed

Clark, Andrew P; Howard, Kate L; Woods, Andy T; Penton-Voak, Ian S; Neumann, Christof

2018-01-01

We introduce "EloChoice", a package for R which uses Elo rating to assess pairwise comparisons between stimuli in order to measure perceived stimulus characteristics. To demonstrate the package and compare results from forced choice pairwise comparisons to those from more standard single stimulus rating tasks using Likert (or Likert-type) items, we investigated perceptions of physical strength from images of male bodies. The stimulus set comprised images of 82 men standing on a raised platform with minimal clothing. Strength-related anthropometrics and grip strength measurements were available for each man in the set. UK laboratory participants (Study 1) and US online participants (Study 2) viewed all images in both a Likert rating task, to collect mean Likert scores, and a pairwise comparison task, to calculate Elo, mean Elo (mElo), and Bradley-Terry scores. Within both studies, Likert, Elo and Bradley-Terry scores were closely correlated to mElo scores (all rs > 0.95), and all measures were correlated with stimulus grip strength (all rs > 0.38) and body size (all rs > 0.59). However, mElo scores were less variable than Elo scores and were hundreds of times quicker to compute than Bradley-Terry scores. Responses in pairwise comparison trials were 2/3 quicker than in Likert tasks, indicating that participants found pairwise comparisons to be easier. In addition, mElo scores generated from a data set with half the participants randomly excluded produced very comparable results to those produced with Likert scores from the full participant set, indicating that researchers require fewer participants when using pairwise comparisons.

Power and sample-size estimation for microbiome studies using pairwise distances and PERMANOVA

PubMed Central

Kelly, Brendan J.; Gross, Robert; Bittinger, Kyle; Sherrill-Mix, Scott; Lewis, James D.; Collman, Ronald G.; Bushman, Frederic D.; Li, Hongzhe

2015-01-01

Motivation: The variation in community composition between microbiome samples, termed beta diversity, can be measured by pairwise distance based on either presence–absence or quantitative species abundance data. PERMANOVA, a permutation-based extension of multivariate analysis of variance to a matrix of pairwise distances, partitions within-group and between-group distances to permit assessment of the effect of an exposure or intervention (grouping factor) upon the sampled microbiome. Within-group distance and exposure/intervention effect size must be accurately modeled to estimate statistical power for a microbiome study that will be analyzed with pairwise distances and PERMANOVA. Results: We present a framework for PERMANOVA power estimation tailored to marker-gene microbiome studies that will be analyzed by pairwise distances, which includes: (i) a novel method for distance matrix simulation that permits modeling of within-group pairwise distances according to pre-specified population parameters; (ii) a method to incorporate effects of different sizes within the simulated distance matrix; (iii) a simulation-based method for estimating PERMANOVA power from simulated distance matrices; and (iv) an R statistical software package that implements the above. Matrices of pairwise distances can be efficiently simulated to satisfy the triangle inequality and incorporate group-level effects, which are quantified by the adjusted coefficient of determination, omega-squared (ω2). From simulated distance matrices, available PERMANOVA power or necessary sample size can be estimated for a planned microbiome study. Availability and implementation: http://github.com/brendankelly/micropower. Contact: brendank@mail.med.upenn.edu or hongzhe@upenn.edu PMID:25819674

On formation mechanism of Pd-Ir bimetallic nanoparticles through thermal decomposition of [Pd(NH3)4][IrCl6

NASA Astrophysics Data System (ADS)

Asanova, Tatyana I.; Asanov, Igor P.; Kim, Min-Gyu; Gerasimov, Evgeny Yu.; Zadesenets, Andrey V.; Plyusnin, Pavel E.; Korenev, Sergey V.

2013-10-01

The formation mechanism of Pd-Ir nanoparticles during thermal decomposition of double complex salt [Pd(NH3)4][IrCl6] has been studied by in situ X-ray absorption (XAFS) and photoelectron (XPS) spectroscopies. The changes in the structure of the Pd and Ir closest to the surroundings and chemical states of Pd, Ir, Cl, and N atoms were traced in the range from room temperature to 420 °C in inert atmosphere. It was established that the thermal decomposition process is carried out in 5 steps. The Pd-Ir nanoparticles are formed in pyramidal/rounded Pd-rich (10-200 nm) and dendrite Ir-rich (10-50 nm) solid solutions. A d charge depletion at Ir site and a gain at Pd, as well as the intra-atomic charge redistribution between the outer d and s and p electrons of both Ir and Pd in Pd-Ir nanoparticles, were found to occur.

Solid solutions of platinum(II) and palladium(II) oxalato-complex salt as precursors of nanoalloys

NASA Astrophysics Data System (ADS)

Zadesenets, A. V.; Asanova, T. I.; Vikulova, E. S.; Filatov, E. Yu.; Plyusnin, P. E.; Baidina, I. A.; Asanov, I. P.; Korenev, S. V.

2013-03-01

A solid solution of platinum (II) and palladium (II) oxalato-complex salt, (NH4)2[Pt0.5Pd0.5(C2O4)2]·2H2O, has been synthesized and studied as a precursor for preparing bimetallic PtPd nanoparticles through its thermal decomposition. The smallest homogenous bimetallic PtPd nanoparticles were found to form in hydrogen and helium atmospheres. The annealing temperature and time have low effect on the bimetallic particles size. Comparative analysis of structural and thermal properties of the solid solution and individual Pt, Pd oxalato-complex salts was performed to investigate a mechanism of thermal decomposition of (NH4)2[Pt0.5Pd0.5(C2O4)2]·2H2O. Based on in situ X-ray photoemission spectroscopy investigation it was proposed a mechanism of formation of bimetallic PtPd nanoparticles from the solid-solution oxalato-complex salt during thermal decomposition.

Decomposition mechanisms and kinetics of novel energetic molecules BNFF-1 and ANFF-1: quantum-chemical modeling.

PubMed

Tsyshevsky, Roman V; Kuklja, Maija M

2013-07-18

Decomposition mechanisms, activation barriers, Arrhenius parameters, and reaction kinetics of the novel explosive compounds, 3,4-bis(4-nitro-1,2,5-oxadiazol-3-yl)-1,2,5-oxadiazole (BNFF-1), and 3-(4-amino-1,2,5-oxadiazol-3-yl)-4-(4-nitro-1,2,5-oxadiazol-3-yl)-1,2,5-oxadiazole (ANFF-1) were explored by means of density functional theory with a range of functionals combined with variational transition state theory. BNFF-1 and ANFF-1 were recently suggested to be good candidates for insensitive high energy density materials. Our modeling reveals that the decomposition initiation in both BNFF-1 and ANFF-1 molecules is triggered by ring cleavage reactions while the further process is defined by a competition between two major pathways, the fast C-NO₂ homolysis and slow nitro-nitrite isomerization releasing NO. We discuss insights on design of new energetic materials with targeted properties gained from our modeling.

First-principles study on the initial decomposition process of CH3NH3PbI3

NASA Astrophysics Data System (ADS)

Xue, Yuanbin; Shan, Yueyue; Xu, Hu

2017-09-01

Hybrid perovskites are promising materials for high-performance photovoltaics. Unfortunately, hybrid perovskites readily decompose in particular under humid conditions, and the mechanisms of this phenomenon have not yet been fully understood. In this work, we systematically studied the possible mechanisms and the structural properties during the initial decomposition process of MAPbI3 (MA = CH3NH3+) using first-principles calculations. The theoretical results show that it is energetically favorable for PbI2 to nucleate and crystalize from the MAPbI3 matrix ahead of other decomposition products. Additionally, the structural instability is an intrinsic property of MAPbI3, regardless of whether the system is exposed to humidity. We find that H2O could facilitate the desorption of gaseous components, acting as a catalyst to transfer the H+ ion. These results provide insight into the cause of the instability of MAPbI3 and may improve our understanding of the properties of hybrid perovskites.

A Light-Induced Reaction with Oxygen Leads to Chromophore Decomposition and Irreversible Photobleaching in GFP-Type Proteins.

PubMed

Grigorenko, Bella L; Nemukhin, Alexander V; Polyakov, Igor V; Khrenova, Maria G; Krylov, Anna I

2015-04-30

Photobleaching and photostability of proteins of the green fluorescent protein (GFP) family are crucially important for practical applications of these widely used biomarkers. On the basis of simulations, we propose a mechanism for irreversible bleaching in GFP-type proteins under intense light illumination. The key feature of the mechanism is a photoinduced reaction of the chromophore with molecular oxygen (O2) inside the protein barrel leading to the chromophore's decomposition. Using quantum mechanics/molecular mechanics (QM/MM) modeling we show that a model system comprising the protein-bound Chro(-) and O2 can be excited to an electronic state of the intermolecular charge-transfer (CT) character (Chro(•)···O2(-•)). Once in the CT state, the system undergoes a series of chemical reactions with low activation barriers resulting in the cleavage of the bridging bond between the phenolic and imidazolinone rings and disintegration of the chromophore.

Leaf Litter Mixtures Alter Microbial Community Development: Mechanisms for Non-Additive Effects in Litter Decomposition

PubMed Central

Chapman, Samantha K.; Newman, Gregory S.; Hart, Stephen C.; Schweitzer, Jennifer A.; Koch, George W.

2013-01-01

To what extent microbial community composition can explain variability in ecosystem processes remains an open question in ecology. Microbial decomposer communities can change during litter decomposition due to biotic interactions and shifting substrate availability. Though relative abundance of decomposers may change due to mixing leaf litter, linking these shifts to the non-additive patterns often recorded in mixed species litter decomposition rates has been elusive, and links community composition to ecosystem function. We extracted phospholipid fatty acids (PLFAs) from single species and mixed species leaf litterbags after 10 and 27 months of decomposition in a mixed conifer forest. Total PLFA concentrations were 70% higher on litter mixtures than single litter types after 10 months, but were only 20% higher after 27 months. Similarly, fungal-to-bacterial ratios differed between mixed and single litter types after 10 months of decomposition, but equalized over time. Microbial community composition, as indicated by principal components analyses, differed due to both litter mixing and stage of litter decomposition. PLFA biomarkers a15∶0 and cy17∶0, which indicate gram-positive and gram-negative bacteria respectively, in particular drove these shifts. Total PLFA correlated significantly with single litter mass loss early in decomposition but not at later stages. We conclude that litter mixing alters microbial community development, which can contribute to synergisms in litter decomposition. These findings advance our understanding of how changing forest biodiversity can alter microbial communities and the ecosystem processes they mediate. PMID:23658639

Soil organic matter decomposition follows plant productivity response to sea-level rise

NASA Astrophysics Data System (ADS)

Mueller, Peter; Jensen, Kai; Megonigal, James Patrick

2015-04-01

The accumulation of soil organic matter (SOM) is an important mechanism for many tidal wetlands to keep pace with sea-level rise. SOM accumulation is governed by the rates of production and decomposition of organic matter. While plant productivity responses to sea-level rise are well understood, far less is known about the response of SOM decomposition to accelerated sea-level rise. Here we quantified the effects of sea-level rise on SOM decomposition by exposing planted and unplanted tidal marsh monoliths to experimentally manipulated flood duration. The study was performed in a field-based mesocosm facility at the Smithsonian Global Change Research Wetland, a micro tidal brackish marsh in Maryland, US. SOM decomposition was quantified as CO2 efflux, with plant- and SOM-derived CO2 separated using a stable carbon isotope approach. Despite the dogma that decomposition rates are inversely related to flooding, SOM mineralization was not sensitive to varying flood duration over a 35 cm range in surface elevation in unplanted mesocoms. In the presence of plants, decomposition rates were strongly and positively related to aboveground biomass (p≤0.01, R2≥0.59). We conclude that rates of soil carbon loss through decomposition are driven by plant responses to sea level in this intensively studied tidal marsh. If our result applies more generally to tidal wetlands, it has important implications for modeling carbon sequestration and marsh accretion in response to accelerated sea-level rise.

Spatial assignment of symmetry adapted perturbation theory interaction energy components: The atomic SAPT partition

NASA Astrophysics Data System (ADS)

Parrish, Robert M.; Sherrill, C. David

2014-07-01

We develop a physically-motivated assignment of symmetry adapted perturbation theory for intermolecular interactions (SAPT) into atom-pairwise contributions (the A-SAPT partition). The basic precept of A-SAPT is that the many-body interaction energy components are computed normally under the formalism of SAPT, following which a spatially-localized two-body quasiparticle interaction is extracted from the many-body interaction terms. For electrostatics and induction source terms, the relevant quasiparticles are atoms, which are obtained in this work through the iterative stockholder analysis (ISA) procedure. For the exchange, induction response, and dispersion terms, the relevant quasiparticles are local occupied orbitals, which are obtained in this work through the Pipek-Mezey procedure. The local orbital atomic charges obtained from ISA additionally allow the terms involving local orbitals to be assigned in an atom-pairwise manner. Further summation over the atoms of one or the other monomer allows for a chemically intuitive visualization of the contribution of each atom and interaction component to the overall noncovalent interaction strength. Herein, we present the intuitive development and mathematical form for A-SAPT applied in the SAPT0 approximation (the A-SAPT0 partition). We also provide an efficient series of algorithms for the computation of the A-SAPT0 partition with essentially the same computational cost as the corresponding SAPT0 decomposition. We probe the sensitivity of the A-SAPT0 partition to the ISA grid and convergence parameter, orbital localization metric, and induction coupling treatment, and recommend a set of practical choices which closes the definition of the A-SAPT0 partition. We demonstrate the utility and computational tractability of the A-SAPT0 partition in the context of side-on cation-π interactions and the intercalation of DNA by proflavine. A-SAPT0 clearly shows the key processes in these complicated noncovalent interactions, in systems with up to 220 atoms and 2845 basis functions.

Spatial assignment of symmetry adapted perturbation theory interaction energy components: The atomic SAPT partition

DOE Office of Scientific and Technical Information (OSTI.GOV)

Parrish, Robert M.; Sherrill, C. David, E-mail: sherrill@gatech.edu

2014-07-28

We develop a physically-motivated assignment of symmetry adapted perturbation theory for intermolecular interactions (SAPT) into atom-pairwise contributions (the A-SAPT partition). The basic precept of A-SAPT is that the many-body interaction energy components are computed normally under the formalism of SAPT, following which a spatially-localized two-body quasiparticle interaction is extracted from the many-body interaction terms. For electrostatics and induction source terms, the relevant quasiparticles are atoms, which are obtained in this work through the iterative stockholder analysis (ISA) procedure. For the exchange, induction response, and dispersion terms, the relevant quasiparticles are local occupied orbitals, which are obtained in this work throughmore » the Pipek-Mezey procedure. The local orbital atomic charges obtained from ISA additionally allow the terms involving local orbitals to be assigned in an atom-pairwise manner. Further summation over the atoms of one or the other monomer allows for a chemically intuitive visualization of the contribution of each atom and interaction component to the overall noncovalent interaction strength. Herein, we present the intuitive development and mathematical form for A-SAPT applied in the SAPT0 approximation (the A-SAPT0 partition). We also provide an efficient series of algorithms for the computation of the A-SAPT0 partition with essentially the same computational cost as the corresponding SAPT0 decomposition. We probe the sensitivity of the A-SAPT0 partition to the ISA grid and convergence parameter, orbital localization metric, and induction coupling treatment, and recommend a set of practical choices which closes the definition of the A-SAPT0 partition. We demonstrate the utility and computational tractability of the A-SAPT0 partition in the context of side-on cation-π interactions and the intercalation of DNA by proflavine. A-SAPT0 clearly shows the key processes in these complicated noncovalent interactions, in systems with up to 220 atoms and 2845 basis functions.« less

Characteristic of root decomposition in a tropical rainforest in Sarawak, Malaysi

NASA Astrophysics Data System (ADS)

Ohashi, Mizue; Makita, Naoki; Katayam, Ayumi; Kume, Tomonori; Matsumoto, Kazuho; Khoon Kho, L.

2016-04-01

Woody roots play a significant role in forest carbon cycling, as up to 60 percent of tree photosynthetic production can be allocated to belowground. Root decay is one of the main processes of soil C dynamics and potentially relates to soil C sequestration. However, much less attention has been paid for root litter decomposition compared to the studies of leaf litter because roots are hidden from view. Previous studies have revealed that physico-chemical quality of roots, climate, and soil organisms affect root decomposition significantly. However, patterns and mechanisms of root decomposition are still poorly understood because of the high variability of root properties, field environment and potential decomposers. For example, root size would be a factor controlling decomposition rates, but general understanding of the difference between coarse and fine root decompositions is still lacking. Also, it is known that root decomposition is performed by soil animals, fungi and bacteria, but their relative importance is poorly understood. In this study, therefore, we aimed to characterize the root decomposition in a tropical rainforest in Sarawak, Malaysia, and clarify the impact of soil living organisms and root sizes on root litter decomposition. We buried soil cores with fine and coarse root litter bags in soil in Lambir Hills National Park. Three different types of soil cores that are covered by 1.5 cm plastic mesh, root-impermeable sheet (50um) and fungi-impermeable sheet (1um) were prepared. The soil cores were buried in February 2013 and collected 4 times, 134 days, 226 days, 786 days and 1151 days after the installation. We found that nearly 80 percent of the coarse root litter was decomposed after two years, whereas only 60 percent of the fine root litter was decomposed. Our results also showed significantly different ratio of decomposition between different cores, suggesting the different contribution of soil living organisms to decomposition process.

Methanol Oxidation on Pt3Sn(111) for Direct Methanol Fuel Cells: Methanol Decomposition.

PubMed

Lu, Xiaoqing; Deng, Zhigang; Guo, Chen; Wang, Weili; Wei, Shuxian; Ng, Siu-Pang; Chen, Xiangfeng; Ding, Ning; Guo, Wenyue; Wu, Chi-Man Lawrence

2016-05-18

PtSn alloy, which is a potential material for use in direct methanol fuel cells, can efficiently promote methanol oxidation and alleviate the CO poisoning problem. Herein, methanol decomposition on Pt3Sn(111) was systematically investigated using periodic density functional theory and microkinetic modeling. The geometries and energies of all of the involved species were analyzed, and the decomposition network was mapped out to elaborate the reaction mechanisms. Our results indicated that methanol and formaldehyde were weakly adsorbed, and the other derivatives (CHxOHy, x = 1-3, y = 0-1) were strongly adsorbed and preferred decomposition rather than desorption on Pt3Sn(111). The competitive methanol decomposition started with the initial O-H bond scission followed by successive C-H bond scissions, (i.e., CH3OH → CH3O → CH2O → CHO → CO). The Brønsted-Evans-Polanyi relations and energy barrier decomposition analyses identified the C-H and O-H bond scissions as being more competitive than the C-O bond scission. Microkinetic modeling confirmed that the vast majority of the intermediates and products from methanol decomposition would escape from the Pt3Sn(111) surface at a relatively low temperature, and the coverage of the CO residue decreased with an increase in the temperature and decrease in partial methanol pressure.

Catalytic Decomposition of Hydroxylammonium Nitrate Ionic Liquid: Enhancement of NO Formation.

PubMed

Chambreau, Steven D; Popolan-Vaida, Denisia M; Vaghjiani, Ghanshyam L; Leone, Stephen R

2017-05-18

Hydroxylammonium nitrate (HAN) is a promising candidate to replace highly toxic hydrazine in monopropellant thruster space applications. The reactivity of HAN aerosols on heated copper and iridium targets was investigated using tunable vacuum ultraviolet photoionization time-of-flight aerosol mass spectrometry. The reaction products were identified by their mass-to-charge ratios and their ionization energies. Products include NH 3 , H 2 O, NO, hydroxylamine (HA), HNO 3 , and a small amount of NO 2 at high temperature. No N 2 O was detected under these experimental conditions, despite the fact that N 2 O is one of the expected products according to the generally accepted thermal decomposition mechanism of HAN. Upon introduction of iridium catalyst, a significant enhancement of the NO/HA ratio was observed. This observation indicates that the formation of NO via decomposition of HA is an important pathway in the catalytic decomposition of HAN.

Activation energy and energy density: a bioenergetic framework for assessing soil organic matter stability

NASA Astrophysics Data System (ADS)

Williams, E. K.; Plante, A. F.

2017-12-01

The stability and cycling of natural organic matter depends on the input of energy needed to decompose it and the net energy gained from its decomposition. In soils, this relationship is complicated by microbial enzymatic activity which decreases the activation energies associated with soil organic matter (SOM) decomposition and by chemical and physical protection mechanisms which decreases the concentrations of the available organic matter substrate and also require additional energies to overcome for decomposition. In this study, we utilize differential scanning calorimetry and evolved CO2 gas analysis to characterize differences in the energetics (activation energy and energy density) in soils that have undergone degradation in natural (bare fallow), field (changes in land-use), chemical (acid hydrolysis), and laboratory (high temperature incubation) experimental conditions. We will present this data in a novel conceptual framework relating these energy dynamics to organic matter inputs, decomposition, and molecular complexity.

Kinetics of non-isothermal decomposition of cinnamic acid

NASA Astrophysics Data System (ADS)

Zhao, Ming-rui; Qi, Zhen-li; Chen, Fei-xiong; Yue, Xia-xin

2014-07-01

The thermal stability and kinetics of decomposition of cinnamic acid were investigated by thermogravimetry and differential scanning calorimetry at four heating rates. The activation energies of this process were calculated from analysis of TG curves by methods of Flynn-Wall-Ozawa, Doyle, Distributed Activation Energy Model, Šatava-Šesták and Kissinger, respectively. There are only one stage of thermal decomposition process in TG and two endothermic peaks in DSC. For this decomposition process of cinnamic acid, E and log A[s-1] were determined to be 81.74 kJ mol-1 and 8.67, respectively. The mechanism was Mampel Power law (the reaction order, n = 1), with integral form G(α) = α (α = 0.1-0.9). Moreover, thermodynamic properties of Δ H ≠, Δ S ≠, Δ G ≠ were 77.96 kJ mol-1, -90.71 J mol-1 K-1, 119.41 kJ mol-1.

Automatic network coupling analysis for dynamical systems based on detailed kinetic models.

PubMed

Lebiedz, Dirk; Kammerer, Julia; Brandt-Pollmann, Ulrich

2005-10-01

We introduce a numerical complexity reduction method for the automatic identification and analysis of dynamic network decompositions in (bio)chemical kinetics based on error-controlled computation of a minimal model dimension represented by the number of (locally) active dynamical modes. Our algorithm exploits a generalized sensitivity analysis along state trajectories and subsequent singular value decomposition of sensitivity matrices for the identification of these dominant dynamical modes. It allows for a dynamic coupling analysis of (bio)chemical species in kinetic models that can be exploited for the piecewise computation of a minimal model on small time intervals and offers valuable functional insight into highly nonlinear reaction mechanisms and network dynamics. We present results for the identification of network decompositions in a simple oscillatory chemical reaction, time scale separation based model reduction in a Michaelis-Menten enzyme system and network decomposition of a detailed model for the oscillatory peroxidase-oxidase enzyme system.

Formation and decomposition of ethane, propane, and carbon dioxide hydrates in silica gel mesopores under high pressure.

PubMed

Aladko, E Ya; Dyadin, Yu A; Fenelonov, V B; Larionov, E G; Manakov, A Yu; Mel'gunov, M S; Zhurko, F V

2006-10-05

The experimental data on decomposition temperatures for the gas hydrates of ethane, propane, and carbon dioxide dispersed in silica gel mesopores are reported. The studies were performed at pressures up to 1 GPa. It is shown that the experimental dependence of hydrate decomposition temperature on the size of pores that limit the size of hydrate particles can be described on the basis of the Gibbs-Thomson equation only if one takes into account changes in the shape coefficient that is present in the equation; in turn, the value of this coefficient depends on a method of mesopore size determination. A mechanism of hydrate formation in mesoporous medium is proposed. Experimental data providing evidence of the possibility of the formation of hydrate compounds in hydrophobic matrixes under high pressure are reported. Decomposition temperature of those hydrate compounds is higher than that for the bulk hydrates of the corresponding gases.

Why rate when you could compare? Using the “EloChoice” package to assess pairwise comparisons of perceived physical strength

PubMed Central

Howard, Kate L.; Woods, Andy T.; Penton-Voak, Ian S.; Neumann, Christof

2018-01-01

We introduce “EloChoice”, a package for R which uses Elo rating to assess pairwise comparisons between stimuli in order to measure perceived stimulus characteristics. To demonstrate the package and compare results from forced choice pairwise comparisons to those from more standard single stimulus rating tasks using Likert (or Likert-type) items, we investigated perceptions of physical strength from images of male bodies. The stimulus set comprised images of 82 men standing on a raised platform with minimal clothing. Strength-related anthropometrics and grip strength measurements were available for each man in the set. UK laboratory participants (Study 1) and US online participants (Study 2) viewed all images in both a Likert rating task, to collect mean Likert scores, and a pairwise comparison task, to calculate Elo, mean Elo (mElo), and Bradley-Terry scores. Within both studies, Likert, Elo and Bradley-Terry scores were closely correlated to mElo scores (all rs > 0.95), and all measures were correlated with stimulus grip strength (all rs > 0.38) and body size (all rs > 0.59). However, mElo scores were less variable than Elo scores and were hundreds of times quicker to compute than Bradley-Terry scores. Responses in pairwise comparison trials were 2/3 quicker than in Likert tasks, indicating that participants found pairwise comparisons to be easier. In addition, mElo scores generated from a data set with half the participants randomly excluded produced very comparable results to those produced with Likert scores from the full participant set, indicating that researchers require fewer participants when using pairwise comparisons. PMID:29293615

Stream ecosystem integrity is impaired by logging and shifting agriculture in a global megadiversity center (Sarawak, Borneo).

PubMed

Jinggut, Tajang; Yule, Catherine M; Boyero, Luz

2012-10-15

In common with most of Borneo, the Bakun region of Sarawak is currently subject to heavy deforestation mainly due to logging and, to a lesser extent, traditional slash-and-burn farming practices. This has the potential to affect stream ecosystems, which are integrators of environmental change in the surrounding terrestrial landscape. This study evaluated the effects of both types of deforestation by using functional and structural indicators (leaf litter decomposition rates and associated detritivores or 'shredders', respectively) to compare a fundamental ecosystem process, leaf litter decomposition, within logged, farmed and pristine streams. Slash-and-burn agricultural practices increased the overall rate of decomposition despite a decrease in shredder species richness (but not shredder abundance) due to increased microbial decomposition. In contrast, decomposition by microbes and invertebrates was slowed down in the logged streams, where shredders were less abundant and less species rich. This study suggests that shredder communities are less affected by traditional agricultural farming practices, while modern mechanized deforestation has an adverse effect on both shredder communities and leaf breakdown. Copyright © 2012 Elsevier B.V. All rights reserved.

Study on Kinetic Mechanism of Bastnaesite Concentrates Decomposition Using Calcium Hydroxide

NASA Astrophysics Data System (ADS)

Cen, Peng; Wu, Wenyuan; Bian, Xue

2018-06-01

The thermal decomposition of bastnaesite concentrates using calcium hydroxide was studied. Calcium hydroxide can effectively inhibit the emission of fluorine during roasting by transforming it to calcium fluoride. The decomposition rate increased with increasing reaction temperature and amount of calcium hydroxide. The decomposition kinetics were investigated. The decomposition reaction was determined to be a heterogeneous gas-solid reaction, and it followed an unreacted shrinking core model. By means of the integrated rate equation method, the reaction was proven to be kinetically first order. Different reaction models were fit to the experimental data to determine the reaction control process. The chemical reaction at the phase interface controlled the reaction rate in the temperatures ranging from 673 K to 773 K (400 °C to 500 °C) with an apparent activation energy of 82.044 kJ·mol-1. From 773 K to 973 K (500 °C to 700 °C), diffusion through the solid product's layer became the determining step, with a lower activation energy of 15.841 kJ·mol-1.

Controllable pneumatic generator based on the catalytic decomposition of hydrogen peroxide

NASA Astrophysics Data System (ADS)

Kim, Kyung-Rok; Kim, Kyung-Soo; Kim, Soohyun

2014-07-01

This paper presents a novel compact and controllable pneumatic generator that uses hydrogen peroxide decomposition. A fuel micro-injector using a piston-pump mechanism is devised and tested to control the chemical decomposition rate. By controlling the injection rate, the feedback controller maintains the pressure of the gas reservoir at a desired pressure level. Thermodynamic analysis and experiments are performed to demonstrate the feasibility of the proposed pneumatic generator. Using a prototype of the pneumatic generator, it takes 6 s to reach 3.5 bars with a reservoir volume of 200 ml at the room temperature, which is sufficiently rapid and effective to maintain the repetitive lifting of a 1 kg mass.

Controllable pneumatic generator based on the catalytic decomposition of hydrogen peroxide.

PubMed

Kim, Kyung-Rok; Kim, Kyung-Soo; Kim, Soohyun

2014-07-01

This paper presents a novel compact and controllable pneumatic generator that uses hydrogen peroxide decomposition. A fuel micro-injector using a piston-pump mechanism is devised and tested to control the chemical decomposition rate. By controlling the injection rate, the feedback controller maintains the pressure of the gas reservoir at a desired pressure level. Thermodynamic analysis and experiments are performed to demonstrate the feasibility of the proposed pneumatic generator. Using a prototype of the pneumatic generator, it takes 6 s to reach 3.5 bars with a reservoir volume of 200 ml at the room temperature, which is sufficiently rapid and effective to maintain the repetitive lifting of a 1 kg mass.

Plasma-catalyst hybrid reactor with CeO2/γ-Al2O3 for benzene decomposition with synergetic effect and nano particle by-product reduction.

PubMed

Mao, Lingai; Chen, Zhizong; Wu, Xinyue; Tang, Xiujuan; Yao, Shuiliang; Zhang, Xuming; Jiang, Boqiong; Han, Jingyi; Wu, Zuliang; Lu, Hao; Nozaki, Tomohiro

2018-04-05

A dielectric barrier discharge (DBD) catalyst hybrid reactor with CeO 2 /γ-Al 2 O 3 catalyst balls was investigated for benzene decomposition at atmospheric pressure and 30 °C. At an energy density of 37-40 J/L, benzene decomposition was as high as 92.5% when using the hybrid reactor with 5.0wt%CeO 2 /γ-Al 2 O 3 ; while it was 10%-20% when using a normal DBD reactor without a catalyst. Benzene decomposition using the hybrid reactor was almost the same as that using an O 3 catalyst reactor with the same CeO 2 /γ-Al 2 O 3 catalyst, indicating that O 3 plays a key role in the benzene decomposition. Fourier transform infrared spectroscopy analysis showed that O 3 adsorption on CeO 2 /γ-Al 2 O 3 promotes the production of adsorbed O 2 - and O 2 2‒ , which contribute benzene decomposition over heterogeneous catalysts. Nano particles as by-products (phenol and 1,4-benzoquinone) from benzene decomposition can be significantly reduced using the CeO 2 /γ-Al 2 O 3 catalyst. H 2 O inhibits benzene decomposition; however, it improves CO 2 selectivity. The deactivated CeO 2 /γ-Al 2 O 3 catalyst can be regenerated by performing discharges at 100 °C and 192-204 J/L. The decomposition mechanism of benzene over CeO 2 /γ-Al 2 O 3 catalyst was proposed. Copyright © 2017 Elsevier B.V. All rights reserved.

A Comparative Study of Pairwise Learning Methods Based on Kernel Ridge Regression.

PubMed

Stock, Michiel; Pahikkala, Tapio; Airola, Antti; De Baets, Bernard; Waegeman, Willem

2018-06-12

Many machine learning problems can be formulated as predicting labels for a pair of objects. Problems of that kind are often referred to as pairwise learning, dyadic prediction, or network inference problems. During the past decade, kernel methods have played a dominant role in pairwise learning. They still obtain a state-of-the-art predictive performance, but a theoretical analysis of their behavior has been underexplored in the machine learning literature. In this work we review and unify kernel-based algorithms that are commonly used in different pairwise learning settings, ranging from matrix filtering to zero-shot learning. To this end, we focus on closed-form efficient instantiations of Kronecker kernel ridge regression. We show that independent task kernel ridge regression, two-step kernel ridge regression, and a linear matrix filter arise naturally as a special case of Kronecker kernel ridge regression, implying that all these methods implicitly minimize a squared loss. In addition, we analyze universality, consistency, and spectral filtering properties. Our theoretical results provide valuable insights into assessing the advantages and limitations of existing pairwise learning methods.

Fast and accurate estimation of the covariance between pairwise maximum likelihood distances.

PubMed

Gil, Manuel

2014-01-01

Pairwise evolutionary distances are a model-based summary statistic for a set of molecular sequences. They represent the leaf-to-leaf path lengths of the underlying phylogenetic tree. Estimates of pairwise distances with overlapping paths covary because of shared mutation events. It is desirable to take these covariance structure into account to increase precision in any process that compares or combines distances. This paper introduces a fast estimator for the covariance of two pairwise maximum likelihood distances, estimated under general Markov models. The estimator is based on a conjecture (going back to Nei & Jin, 1989) which links the covariance to path lengths. It is proven here under a simple symmetric substitution model. A simulation shows that the estimator outperforms previously published ones in terms of the mean squared error.

Fast and accurate estimation of the covariance between pairwise maximum likelihood distances

PubMed Central

2014-01-01

Pairwise evolutionary distances are a model-based summary statistic for a set of molecular sequences. They represent the leaf-to-leaf path lengths of the underlying phylogenetic tree. Estimates of pairwise distances with overlapping paths covary because of shared mutation events. It is desirable to take these covariance structure into account to increase precision in any process that compares or combines distances. This paper introduces a fast estimator for the covariance of two pairwise maximum likelihood distances, estimated under general Markov models. The estimator is based on a conjecture (going back to Nei & Jin, 1989) which links the covariance to path lengths. It is proven here under a simple symmetric substitution model. A simulation shows that the estimator outperforms previously published ones in terms of the mean squared error. PMID:25279263

Mass-Spectrometric Studies of Catalytic Chemical Vapor Deposition Processes of Organic Silicon Compounds Containing Nitrogen

NASA Astrophysics Data System (ADS)

Morimoto, Takashi; Ansari, S. G.; Yoneyama, Koji; Nakajima, Teppei; Masuda, Atsushi; Matsumura, Hideki; Nakamura, Megumi; Umemoto, Hironobu

2006-02-01

The mechanism of catalytic chemical vapor deposition (Cat-CVD) processes for hexamethyldisilazane (HMDS) and trisdimethylaminosilane (TDMAS), which are used as source gases to prepare SiNx or SiCxNy films, was studied using three different mass spectrometric techniques: ionization by Li+ ion attachment, vacuum-ultraviolet radiation and electron impact. The results for HMDS show that Si-N bonds dissociate selectively, although Si-C bonds are weaker, and (CH3)3SiNH should be one of the main precursors of deposited films. This decomposition mechanism did not change when NH3 was introduced, but the decomposition efficiency was slightly increased. Similar results were obtained for TDMAS.

Short-term Dynamics of Photopriming Increase Carbon Loss During Litter Decomposition

NASA Astrophysics Data System (ADS)

Lin, Y.; King, J. Y.; Karlen, S. D.; Ralph, J.

2017-12-01

Solar radiation plays a key role in carbon (C) cycling by increasing the decomposition rates of plant litter through photodegradation. This process is particularly important in drylands where solar radiation is high and microbial activity may be limited by water availability. One mechanism of photodegradation may be the facilitation of microbial decomposition of litter by altering litter chemistry and consequently degradability, termed photopriming. However, it remains unclear to what extent photopriming contributes to litter decomposition. We evaluated photopriming by ultraviolet (UV) radiation through two laboratory experiments. In one experiment, we found that four months of UV exposure increased mass loss by 3-4% compared to dark treatment in two of three litter species commonly found in California oak savanna; however, UV exposure did not alter litter degradability as measured by microbial respiration in an incubation study. UV exposure had limited effects on lignin and other cell wall structures, but one month of microbial decomposition in the dark significantly reduced lignin β-aryl ether inter-unit linkages and acetylated xylans, which interestingly was the same pattern seen in litter exposed to UV radiation under field conditions and may account for the significant effects of UV exposure on litter mass loss observed in situ. These results indicate that microbial decomposition, not abiotic photodegradation, was ultimately responsible for changes in litter chemistry observed in the field. In a separate experiment, litter of a common grass was incubated for 128 days under either alternating UV radiation and dark conditions at two-day intervals or continuous darkness. During the second half of the experiment, alternating UV exposure increased CO2 production by 35% compared to continuous darkness, suggesting that UV exposure induces subtle but important changes in litter chemistry that facilitate microbial decomposition on a temporal scale of days. Together the results point to microbial facilitation as the primary mechanism of photodegradation and suggest that photopriming is governed by short-term dynamics at the litter-microbe interface. The C cycling associated with these short-term dynamics may be especially sensitive to anticipated increases in drought conditions in drylands.

Energy & Energetics

DTIC Science & Technology

2012-06-22

mechanical and structural failure and decomposition in ultra-fast time regimes. Our research teams are exploring novel ways to convert mechanical ...energy to thermal energy by examining initiation mechanisms , multi-phase combustion, detonation and the mechanisms that lead to the release of energy...understanding of the mechanisms of structural stability by doping Fe in LiCoPO4 and effectiveness of HFiP in stopping further oxidation of electrolytes are

Research@ARL: Energy & Energetics

DTIC Science & Technology

2012-06-01

enabling us to probe chemical, mechanical and structural failure and decomposition in ultra-fast time regimes. Our research teams are exploring novel ways...to convert mechanical energy to thermal energy by examining initiation mechanisms , multi-phase combustion, detonation and the mechanisms that lead...storage life. The understanding of the mechanisms of structural stability by doping Fe in LiCoPO4 and effectiveness of HFiP in stopping further

Study on the decomposition of trace benzene over V2O5-WO3 ...

EPA Pesticide Factsheets

Commercial and laboratory-prepared V2O5–WO3/TiO2-based catalysts with different compositions were tested for catalytic decomposition of chlorobenzene （ClBz） in simulated flue gas. Resonance enhanced multiphoton ionization-time of flight mass spectrometry (REMPI-TOFMS) was employed to measure real-time, trace concentrations of ClBz contained in the flue gas before and after the catalyst. The effects of various parameters, including vanadium content of the catalyst, the catalyst support, as well as the reaction temperature on decomposition of ClBz were investigated. The results showed that the ClBz decomposition efficiency was significantly enhanced when nano-TiO2 instead of conventional TiO2 was used as the catalyst support. No promotion effects were found in the ClBz decomposition process when the catalysts were wet-impregnated with CuO and CeO2. Tests with different concentrations (1,000, 500, and 100 ppb) of ClBz showed that ClBz-decomposition efficiency decreased with increasing concentration, unless active sites were plentiful. A comparison between ClBz and benzene decomposition on the V2O5–WO3/TiO2-based catalyst and the relative kinetics analysis showed that two different active sites were likely involved in the decomposition mechanism and the V=O and V-O-Ti groups may only work for the degradation of the phenyl group and the benzene ring rather than the C-Cl bond. V2O5-WO3/TiO2 based catalysts, that have been used for destruction of a wide variet

Dry-season ultraviolet radiation primes litter for wet season decomposition in a Mediterranean grassland

NASA Astrophysics Data System (ADS)

Baker, N. R.; Allison, S. D.

2013-12-01

Traditional decomposition models developed in mesic ecosystems often consistently underestimate rates of decomposition in more arid ecosystems such as deserts and Mediterranean grasslands. Photodegradation of plant litter by ultraviolet radiation (UV) is hypothesized to be one of the mechanisms accounting for the greater-than-expected rates of decomposition observed in these ecosystems. Putatively, photodegradation preferentially degrades complex aromatic compounds in litter such as lignin, whose decomposition is considered a rate-limiting step in the microbial decomposition of plant litter. This study tested the effects of attenuated ultraviolet radiation on the decomposition of two litter types over the course of a year in a Southern California Mediterranean grassland. The two types of litter differed primarily in lignin content to test for a differential effect of UV on high-lignin versus low-lignin litter. Rates of litter mass loss, changes in litter chemistry, and changes in microbial activity and microbial biomass were observed, and assays of extracellular enzymes were conducted at 5 points through the year, beginning during the dry season and continuing until the end of the following dry season. Litter exposed to attenuated ultraviolet radiation during the dry season had lower rates of mass loss than litter exposed to ambient radiation (6.1% vs. 8.6%, respectively, p < 0.04). Extracellular enzyme activities were significantly affected by UV attenuation, as low lignin samples exposed to attenuated UV displayed elevated cellulase enzyme activity potential during the wet season, while high lignin samples displayed decreased oxidative enzyme activity potential during the wet season. For example, potential activity of the cellulase cellobiohydrolase in low-lignin, ambient UV samples was 5286 μmol/hr*g during the wet season, compared to 7969 μmol/hr*g in attenuated UV samples (p < 0.003). Conversely, potential activity of the oxidative enzyme peroxidase in high-lignin, ambient UV samples was 85.9 μmol/hr*g during the wet season, compared to 44.1 μmol/hr*g in attenuated UV samples (p < 0.028). This increased potential cellulase activity under attenuated UV may indicate that dry season photodegradation primes low-lignin litter for wet season decomposition, reducing the selective pressure for microbial decomposers to invest in costly extracellular enzyme production. Similarly, the reduced potential oxidative enzyme activity in high-lignin samples exposed to attenuated UV may indicate that photodegradation is necessary to facilitate the breakdown of more complex compounds such as lignin by microbial decomposers. We conclude that while abiotic factors such as photodegradation can have a significant effect on the mechanisms of plant matter decomposition in semiarid ecosystems, these effects are not only restricted to the dry season and may also facilitate wet season decomposition.

Pattern and process of biotic homogenization in the New Pangaea

PubMed Central

Baiser, Benjamin; Olden, Julian D.; Record, Sydne; Lockwood, Julie L.; McKinney, Michael L.

2012-01-01

Human activities have reorganized the earth's biota resulting in spatially disparate locales becoming more or less similar in species composition over time through the processes of biotic homogenization and biotic differentiation, respectively. Despite mounting evidence suggesting that this process may be widespread in both aquatic and terrestrial systems, past studies have predominantly focused on single taxonomic groups at a single spatial scale. Furthermore, change in pairwise similarity is itself dependent on two distinct processes, spatial turnover in species composition and changes in gradients of species richness. Most past research has failed to disentangle the effect of these two mechanisms on homogenization patterns. Here, we use recent statistical advances and collate a global database of homogenization studies (20 studies, 50 datasets) to provide the first global investigation of the homogenization process across major faunal and floral groups and elucidate the relative role of changes in species richness and turnover. We found evidence of homogenization (change in similarity ranging from −0.02 to 0.09) across nearly all taxonomic groups, spatial extent and grain sizes. Partitioning of change in pairwise similarity shows that overall change in community similarity is driven by changes in species richness. Our results show that biotic homogenization is truly a global phenomenon and put into question many of the ecological mechanisms invoked in previous studies to explain patterns of homogenization. PMID:23055062

Pattern and process of biotic homogenization in the New Pangaea.

PubMed

Baiser, Benjamin; Olden, Julian D; Record, Sydne; Lockwood, Julie L; McKinney, Michael L

2012-12-07

Human activities have reorganized the earth's biota resulting in spatially disparate locales becoming more or less similar in species composition over time through the processes of biotic homogenization and biotic differentiation, respectively. Despite mounting evidence suggesting that this process may be widespread in both aquatic and terrestrial systems, past studies have predominantly focused on single taxonomic groups at a single spatial scale. Furthermore, change in pairwise similarity is itself dependent on two distinct processes, spatial turnover in species composition and changes in gradients of species richness. Most past research has failed to disentangle the effect of these two mechanisms on homogenization patterns. Here, we use recent statistical advances and collate a global database of homogenization studies (20 studies, 50 datasets) to provide the first global investigation of the homogenization process across major faunal and floral groups and elucidate the relative role of changes in species richness and turnover. We found evidence of homogenization (change in similarity ranging from -0.02 to 0.09) across nearly all taxonomic groups, spatial extent and grain sizes. Partitioning of change in pairwise similarity shows that overall change in community similarity is driven by changes in species richness. Our results show that biotic homogenization is truly a global phenomenon and put into question many of the ecological mechanisms invoked in previous studies to explain patterns of homogenization.

Dynamic Responses and Initial Decomposition under Shock Loading: A DFTB Calculation Combined with MSST Method for β-HMX with Molecular Vacancy.

PubMed

He, Zheng-Hua; Chen, Jun; Ji, Guang-Fu; Liu, Li-Min; Zhu, Wen-Jun; Wu, Qiang

2015-08-20

Despite extensive efforts on studying the decomposition mechanism of HMX under extreme condition, an intrinsic understanding of mechanical and chemical response processes, inducing the initial chemical reaction, is not yet achieved. In this work, the microscopic dynamic response and initial decomposition of β-HMX with (1 0 0) surface and molecular vacancy under shock condition, were explored by means of the self-consistent-charge density-functional tight-binding method (SCC-DFTB) in conjunction with multiscale shock technique (MSST). The evolutions of various bond lengths and charge transfers were analyzed to explore and understand the initial reaction mechanism of HMX. Our results discovered that the C-N bond close to major axes had less compression sensitivity and higher stretch activity. The charge was transferred mainly from the N-NO2 group along the minor axes and H atom to C atom during the early compression process. The first reaction of HMX primarily initiated with the fission of the molecular ring at the site of the C-N bond close to major axes. Further breaking of the molecular ring enhanced intermolecular interactions and promoted the cleavage of C-H and N-NO2 bonds. More significantly, the dynamic response behavior clearly depended on the angle between chemical bond and shock direction.

Leaf habit does not determine the investment in both physical and chemical defences and pair-wise correlations between these defensive traits.

PubMed

Moreira, X; Pearse, I S

2017-05-01

Plant life-history strategies associated with resource acquisition and economics (e.g. leaf habit) are thought to be fundamental determinants of the traits and mechanisms that drive herbivore pressure, resource allocation to plant defensive traits, and the simultaneous expression (positive correlations) or trade-offs (negative correlations) between these defensive traits. In particular, it is expected that evergreen species - which usually grow slower and support constant herbivore pressure in comparison with deciduous species - will exhibit higher levels of both physical and chemical defences and a higher predisposition to the simultaneous expression of physical and chemical defensive traits. Here, by using a dataset which included 56 oak species (Quercus genus), we investigated whether leaf habit of plant species governs the investment in both physical and chemical defences and pair-wise correlations between these defensive traits. Our results showed that leaf habit does not determine the production of most leaf physical and chemical defences. Although evergreen oak species had higher levels of leaf toughness and specific leaf mass (physical defences) than deciduous oak species, both traits are essentially prerequisites for evergreenness. Similarly, our results also showed that leaf habit does not determine pair-wise correlations between defensive traits because most physical and chemical defensive traits were simultaneously expressed in both evergreen and deciduous oak species. Our findings indicate that leaf habit does not substantially contribute to oak species differences in plant defence investment. © 2017 German Botanical Society and The Royal Botanical Society of the Netherlands.

Multi-scale Methods in Quantum Field Theory

NASA Astrophysics Data System (ADS)

Polyzou, W. N.; Michlin, Tracie; Bulut, Fatih

2018-05-01

Daubechies wavelets are used to make an exact multi-scale decomposition of quantum fields. For reactions that involve a finite energy that take place in a finite volume, the number of relevant quantum mechanical degrees of freedom is finite. The wavelet decomposition has natural resolution and volume truncations that can be used to isolate the relevant degrees of freedom. The application of flow equation methods to construct effective theories that decouple coarse and fine scale degrees of freedom is examined.

The decomposition of peroxynitrite to nitroxyl anion (NO−) and singlet oxygen in aqueous solution

PubMed Central

Khan, Ahsan Ullah; Kovacic, Dianne; Kolbanovskiy, Alexander; Desai, Mehul; Frenkel, Krystyna; Geacintov, Nicholas E.

2000-01-01

The mechanism of decomposition of peroxynitrite (OONO−) in aqueous sodium phosphate buffer solution at neutral pH was investigated. The OONO− was synthesized by directly reacting nitric oxide with superoxide anion at pH 13. The hypothesis was explored that OONO−, after protonation at pH 7.0 to HOONO, decomposes into 1O2 and HNO according to a spin-conserved unimolecular mechanism. Small aliquots of the concentrated alkaline OONO− solution were added to a buffer solution (final pH 7.0–7.2), and the formation of 1O2 and NO− in high yields was observed. The 1O2 generated was trapped as the transannular peroxide (DPAO2) of 9,10-diphenylanthracene (DPA) dissolved in carbon tetrachloride. The nitroxyl anion (NO−) formed from HNO (pKa 4.5) was trapped as nitrosylhemoglobin (HbNO) in an aqueous methemoglobin (MetHb) solution. In the presence of 25 mM sodium bicarbonate, which is known to accelerate the rate of decomposition of OONO−, the amount of singlet oxygen trapped was reduced by a factor of ≈2 whereas the yield of trapping of NO− by methemoglobin remained unaffected. Because NO3− is known to be the ultimate decomposition product of OONO−, these results suggest that the nitrate anion is not formed by a direct isomerization of OONO−, but by an indirect route originating from NO−. PMID:10716721

Non-pairwise additivity of the leading-order dispersion energy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hollett, Joshua W., E-mail: j.hollett@uwinnipeg.ca

2015-02-28

The leading-order (i.e., dipole-dipole) dispersion energy is calculated for one-dimensional (1D) and two-dimensional (2D) infinite lattices, and an infinite 1D array of infinitely long lines, of doubly occupied locally harmonic wells. The dispersion energy is decomposed into pairwise and non-pairwise additive components. By varying the force constant and separation of the wells, the non-pairwise additive contribution to the dispersion energy is shown to depend on the overlap of density between neighboring wells. As well separation is increased, the non-pairwise additivity of the dispersion energy decays. The different rates of decay for 1D and 2D lattices of wells is explained inmore » terms of a Jacobian effect that influences the number of nearest neighbors. For an array of infinitely long lines of wells spaced 5 bohrs apart, and an inter-well spacing of 3 bohrs within a line, the non-pairwise additive component of the leading-order dispersion energy is −0.11 kJ mol{sup −1} well{sup −1}, which is 7% of the total. The polarizability of the wells and the density overlap between them are small in comparison to that of the atomic densities that arise from the molecular density partitioning used in post-density-functional theory (DFT) damped dispersion corrections, or DFT-D methods. Therefore, the nonadditivity of the leading-order dispersion observed here is a conservative estimate of that in molecular clusters.« less

Computational Elucidation of Selectivities and Mechanisms Performed by Organometallic and Bioinorganic Catalysts

NASA Astrophysics Data System (ADS)

Grandner, Jessica Marie

Computational methods were used to determine the mechanisms and selectivities of organometallic-catalyzed reactions. The first half of the dissertation focuses on the study of metathesis catalysts in collaboration with the Grubbs group at CalTech. Chapter 1 describes the studies of the decomposition modes of several ruthenium-based metathesis catalysts. These studies were performed to better understand the decomposition of such catalysts in order to prevent decomposition (Chapter 1.2) or utilize decomposed catalysts for alternative reactions (Chapter 1.1). Chapter 2.1 describes the computational investigation of the origins of stereoretentive metathesis with ruthenium-based metathesis catalysts. These findings were then used to computationally design E-selective metathesis catalysts (Chapter 2.2). While the first half of the dissertation was centered around ruthenium catalysts, the second half of the dissertation pertains to iron-catalyzed reaction, in particular, iron-catalyzed reactions by P450 enzymes. The elements of Chapter 3 concentrate on the stereo- and chemo-selectivity of P450-catalyzed C-H hydroxylations. By combining multiple computational methods, the inherent activity of the iron-oxo catalyst and the influence of the active site on such reactions were illuminated. These discoveries allow for the engineering of new substrates and mutant enzymes for tailored C-H hydroxylation. While the mechanism of C-H hydroxylations catalyzed by P450 enzymes has been well studied, there are several P450-catalyzed transformations for which the mechanism is unknown. The components of Chapter 4 describe the use of computations to determine the mechanisms of complex, multi-step reactions catalyzed by P450s. The determination of these mechanisms elucidates how these enzymes react with various functional groups and substrate architectures and allows for a better understanding of how drug-like compounds may be broken down by human P450s.

Theoretical study of the reaction mechanism of CH₃NO₂ with NO₂, NO and CO: the bimolecular reactions that cannot be ignored.

PubMed

Zhang, Ji-Dong; Kang, Li-Hua; Cheng, Xin-Lu

2015-01-01

The intriguing decompositions of nitro-containing explosives have been attracting interest. While theoretical investigations have long been concentrated mainly on unimolecular decompositions, bimolecular reactions have received little theoretical attention. In this paper, we investigate theoretically the bimolecular reactions between nitromethane (CH3NO2)-the simplest nitro-containing explosive-and its decomposition products, such as NO2, NO and CO, that are abundant during the decomposition process of CH3NO2. The structures and potential energy surface (PES) were explored at B3LYP/6-31G(d), B3P86/6-31G(d) and MP2/6-311 + G(d,p) levels, and energies were refined using CCSD(T)/cc-pVTZ methods. Quantum chemistry calculations revealed that the title reactions possess small barriers that can be comparable to, or smaller than, that of the initial decomposition reactions of CH3NO2. Considering that their reactants are abundant in the decomposition process of CH3NO2, we consider bimolecular reactions also to be of great importance, and worthy of further investigation. Moreover, our calculations show that NO2 can be oxidized by CH3NO2 to NO3 radical, which confirms the conclusion reached formerly by Irikura and Johnson [(2006) J Phys Chem A 110:13974-13978] that NO3 radical can be formed during the decomposition of nitramine explosives.

Impact of cycling at low temperatures on the safety behavior of 18650-type lithium ion cells: Combined study of mechanical and thermal abuse testing accompanied by post-mortem analysis

NASA Astrophysics Data System (ADS)

Friesen, Alex; Horsthemke, Fabian; Mönnighoff, Xaver; Brunklaus, Gunther; Krafft, Roman; Börner, Markus; Risthaus, Tim; Winter, Martin; Schappacher, Falko M.

2016-12-01

The impact of cycling at low temperatures on the thermal and mechanical abuse behavior of commercial 18650-type lithium ion cells was compared to fresh cells. Post-mortem analyses revealed a deposition of high surface area lithium (HSAL) metal on the graphite surface accompanied by severe electrolyte decomposition. Heat wait search (HWS) tests in an accelerating rate calorimeter (ARC) were performed to investigate the thermal abuse behavior of aged and fresh cells under quasi-adiabatic conditions, showing a strong shift of the onset temperature for exothermic reactions. HSAL deposition promotes the reduction of the carbonate based electrolyte due to the high reactivity of lithium metal with high surface area, leading to a thermally induced decomposition of the electrolyte to produce volatile gaseous products. Nail penetration tests showed a change in the thermal runaway (TR) behavior affected by the decomposition reaction. This study indicates a greater thermal hazard for LIB cells at higher SOC and experiencing aging at low temperature.

Evaluation of a Pair-Wise Conflict Detection and Resolution Algorithm in a Multiple Aircraft Scenario

NASA Technical Reports Server (NTRS)

Carreno, Victor A.

2002-01-01

The KB3D algorithm is a pairwise conflict detection and resolution (CD&R) algorithm. It detects and generates trajectory vectoring for an aircraft which has been predicted to be in an airspace minima violation within a given look-ahead time. It has been proven, using mechanized theorem proving techniques, that for a pair of aircraft, KB3D produces at least one vectoring solution and that all solutions produced are correct. Although solutions produced by the algorithm are mathematically correct, they might not be physically executable by an aircraft or might not solve multiple aircraft conflicts. This paper describes a simple solution selection method which assesses all solutions generated by KB3D and determines the solution to be executed. The solution selection method and KB3D are evaluated using a simulation in which N aircraft fly in a free-flight environment and each aircraft in the simulation uses KB3D to maintain separation. Specifically, the solution selection method filters KB3D solutions which are procedurally undesirable or physically not executable and uses a predetermined criteria for selection.

First-principles and thermodynamic analysis of trimethylgallium (TMG) decomposition during MOVPE growth of GaN

NASA Astrophysics Data System (ADS)

Sekiguchi, K.; Shirakawa, H.; Yamamoto, Y.; Araidai, M.; Kangawa, Y.; Kakimoto, K.; Shiraishi, K.

2017-06-01

We analyzed the decomposition mechanisms of trimethylgallium (TMG) used for the gallium source of GaN fabrication based on first-principles calculations and thermodynamic analysis. We considered two conditions. One condition is under the total pressure of 1 atm and the other one is under metal organic vapor phase epitaxy (MOVPE) growth of GaN. Our calculated results show that H2 is indispensable for TMG decomposition under both conditions. In GaN MOVPE, TMG with H2 spontaneously decomposes into Ga(CH3) and Ga(CH3) decomposes into Ga atom gas when temperature is higher than 440 K. From these calculations, we confirmed that TMG surely becomes Ga atom gas near the GaN substrate surfaces.

Decomposition of a symmetric second-order tensor

NASA Astrophysics Data System (ADS)

Heras, José A.

2018-05-01

In the three-dimensional space there are different definitions for the dot and cross products of a vector with a second-order tensor. In this paper we show how these products can uniquely be defined for the case of symmetric tensors. We then decompose a symmetric second-order tensor into its ‘dot’ part, which involves the dot product, and the ‘cross’ part, which involves the cross product. For some physical applications, this decomposition can be interpreted as one in which the dot part identifies with the ‘parallel’ part of the tensor and the cross part identifies with the ‘perpendicular’ part. This decomposition of a symmetric second-order tensor may be suitable for undergraduate courses of vector calculus, mechanics and electrodynamics.

Investigation of induced unimolecular decomposition for development of visible chemical lasers. Quarterly progress report, 1 August 1976--30 October 1976

DOE Office of Scientific and Technical Information (OSTI.GOV)

Piper, L G; Taylor, R L

This report summarizes progress during the second quarterly period of the subject contract. The methods available for the production of excited electronic states following azide decomposition are summarized. It is concluded that an experiment designed to study the kinetics of and branching ratios for electronically excited products from azide radicals reactions will be most productive in elucidating excitation mechanisms for potential chemical lasers. A flow reactor is described in which these studies may be undertaken. The major feature of this apparatus is a clean azide radical source based upon the thermal decomposition of solid, ionic azides. The contruction of themore » experimental apparatus has been started.« less

Lyman α photolysis of solid nitromethane (CH3NO2) and D3-nitromethane (CD3NO2)--untangling the reaction mechanisms involved in the decomposition of model energetic materials.

PubMed

Maksyutenko, Pavlo; Muzangwa, Lloyd G; Jones, Brant M; Kaiser, Ralf I

2015-03-21

Solid nitromethane (CH3NO2) along with its isotopically labelled counterpart D3-nitromethane (CD3NO2) ices were exposed to Lyman α photons to investigate the mechanism involved in the decomposition of energetic materials in the condensed phase. The chemical processes in the ices were monitored online and in situ via infrared spectroscopy complimented by temperature programmed desorption studies utilizing highly sensitive reflectron time-of-flight mass spectrometry coupled with pulsed photoionization (ReTOF-PI) at 10.49 eV. The infrared data revealed the formation of cis-methylnitrite (CH3ONO), formaldehyde (H2CO), water (H2O), carbon monoxide (CO), and carbon dioxide (CO2). Upon sublimation of the irradiated samples, three classes of higher molecular weight products, which are uniquely formed in the condensed phase, were identified via ReTOF-PI: (i) nitroso compounds [nitrosomethane (CH3NO), nitrosoethane (C2H5NO), nitrosopropane (C3H7NO)], (ii) nitrite compounds [methylnitrite (CH3ONO), ethylnitrite (C2H5ONO), propylnitrite (C3H7ONO)], and (iii) higher molecular weight molecules [CH3NONOCH3, CH3NONO2CH3, CH3OCH2NO2, ONCH2CH2NO2]. The mechanistical information obtained in the present study suggest that the decomposition of nitromethane in the condensed phase is more complex compared to the gas phase under collision-free conditions opening up not only hitherto unobserved decomposition pathways of nitromethane (hydrogen atom loss, oxygen atom loss, retro carbene insertion), but also the blocking of several initial decomposition steps due to the 'matrix cage effect'.

Characterization of corncob-derived biochar and pyrolysis kinetics in comparison with corn stalk and sawdust.

PubMed

Liu, Xuan; Zhang, Yang; Li, Zifu; Feng, Rui; Zhang, Yaozhong

2014-10-01

In this study, thermal and physicochemical characterization results of corncob (CC) and its derived biochars were analyzed and differentiated from sawdust (SD) and cornstalk (CS). The pyrolysis temperature shows the largest effect on the yield of biochar produced compare with residing time, heating rate, and feedstock particle size. The CC-derived biochars produced at temperatures ranging from 300 to 600°C were analyzed. The CC was thermochemically altered to a stable biochar when the pyrolysis temperature was set to over 500°C. To deduce the reaction mechanism of the CC during the major thermal decomposition stage, 16 mechanisms in solid-state reactions were applied. The reaction order and nucleation mechanisms described the thermal decomposition of the CC. By using the best-fitted mechanisms, the kinetic parameters were calculated. The weight active energy of the CC was 122.42kJ/mol, which was the lowest value compared to those of CS and SD. Copyright © 2014 Elsevier Ltd. All rights reserved.

The demodulated band transform

PubMed Central

Kovach, Christopher K.; Gander, Phillip E.

2016-01-01

Background Windowed Fourier decompositions (WFD) are widely used in measuring stationary and non-stationary spectral phenomena and in describing pairwise relationships among multiple signals. Although a variety of WFDs see frequent application in electrophysiological research, including the short-time Fourier transform, continuous wavelets, band-pass filtering and multitaper-based approaches, each carries certain drawbacks related to computational efficiency and spectral leakage. This work surveys the advantages of a WFD not previously applied in electrophysiological settings. New Methods A computationally efficient form of complex demodulation, the demodulated band transform (DBT), is described. Results DBT is shown to provide an efficient approach to spectral estimation with minimal susceptibility to spectral leakage. In addition, it lends itself well to adaptive filtering of non-stationary narrowband noise. Comparison with existing methods A detailed comparison with alternative WFDs is offered, with an emphasis on the relationship between DBT and Thomson's multitaper. DBT is shown to perform favorably in combining computational efficiency with minimal introduction of spectral leakage. Conclusion DBT is ideally suited to efficient estimation of both stationary and non-stationary spectral and cross-spectral statistics with minimal susceptibility to spectral leakage. These qualities are broadly desirable in many settings. PMID:26711370

Decomposition mechanism of an artemisinin-type compound via hemin-electrocatalysis.

PubMed

Chen, H Y; Chen, Y; Zhu, S M; Bian, N S; Shan, F; Li, Y

1999-01-01

The interaction between a typical derivative of artemisinin and hemin was investigated by electrochemical and spectroelectrochemical methods. This derivative can be reduced via hemin-catalysis at the glassy carbon electrode, the cathodic overpotential is decreased by ca. 650 mV. A HPLC method for separating the products of the catalytic reaction was established. They were identified either in H(2)O-CH(3)CN solution or in tetrahydrofuran, respectively. The structures of these products show that the hemin-catalyzed decomposition of an artemisinin-type compound on the glassy carbon or reticulated vitreous carbon electrode can be achieved by both electrochemical reduction and rearrangement. The conclusion that the reaction of artemisinin with hemin is a critical step in the antimalarial mechanism of artemisinin can be drawn.

Decomposition reactions of (hydroxyalkyl) nitrosoureas and related compounds: possible relationship to carcinogenicity.

PubMed

Singer, S S

1985-08-01

(Hydroxyalkyl)nitrosoureas and the related cyclic carbamates N-nitrosooxazolidones are potent carcinogens. The decompositions of four such compounds, 1-nitroso-1-(2-hydroxyethyl)urea (I), 3-nitrosooxazolid-2-one (II), 1-nitroso-1-(2-hydroxypropyl)urea (III), and 5-methyl-3-nitrosooxazolid-2-one (IV), in aqueous buffers at physiological pH were studied to determine if any obvious differences in decomposition pathways could account for the variety of tumors obtained from these four compounds. The products predicted by the literature mechanisms for nitrosourea and nitrosooxazolidone decompositions (which were derived from experiments at pH 10-12) were indeed the products formed, including glycols, active carbonyl compounds, epoxides, and, from the oxazolidones, cyclic carbonates. Furthermore, it was shown that in pH 6.4-7.4 buffer epoxides were stable reaction products. However, in the presence of hepatocytes, most of the epoxide was converted to glycol. The analytical methods developed were then applied to the analysis of the decomposition products of some related dialkylnitrosoureas, and similar results were obtained. The formation of chemically reactive secondary products and the possible relevance of these results to carcinogenesis studies are discussed.

Unusual behavior in the reactivity of 5-substituted-1H-tetrazoles in a resistively heated microreactor

PubMed Central

Gutmann, Bernhard; Glasnov, Toma N; Razzaq, Tahseen; Goessler, Walter; Roberge, Dominique M

2011-01-01

Summary The decomposition of 5-benzhydryl-1H-tetrazole in an N-methyl-2-pyrrolidone/acetic acid/water mixture was investigated under a variety of high-temperature reaction conditions. Employing a sealed Pyrex glass vial and batch microwave conditions at 240 °C, the tetrazole is comparatively stable and complete decomposition to diphenylmethane requires more than 8 h. Similar kinetic data were obtained in conductively heated flow devices with either stainless steel or Hastelloy coils in the same temperature region. In contrast, in a flow instrument that utilizes direct electric resistance heating of the reactor coil, tetrazole decomposition was dramatically accelerated with rate constants increased by two orders of magnitude. When 5-benzhydryl-1H-tetrazole was exposed to 220 °C in this type of flow reactor, decomposition to diphenylmethane was complete within 10 min. The mechanism and kinetic parameters of tetrazole decomposition under a variety of reaction conditions were investigated. A number of possible explanations for these highly unusual rate accelerations are presented. In addition, general aspects of reactor degradation, corrosion and contamination effects of importance to continuous flow chemistry are discussed. PMID:21647324

Vacancy-induced initial decomposition of condensed phase NTO via bimolecular hydrogen transfer mechanisms at high pressure: a DFT-D study.

PubMed

Liu, Zhichao; Wu, Qiong; Zhu, Weihua; Xiao, Heming

2015-04-28

Density functional theory with dispersion-correction (DFT-D) was employed to study the effects of vacancy and pressure on the structure and initial decomposition of crystalline 5-nitro-2,4-dihydro-3H-1,2,4-triazol-3-one (β-NTO), a high-energy insensitive explosive. A comparative analysis of the chemical behaviors of NTO in the ideal bulk crystal and vacancy-containing crystals under applied hydrostatic compression was considered. Our calculated formation energy, vacancy interaction energy, electron density difference, and frontier orbitals reveal that the stability of NTO can be effectively manipulated by changing the molecular environment. Bimolecular hydrogen transfer is suggested to be a potential initial chemical reaction in the vacancy-containing NTO solid at 50 GPa, which is prior to the C-NO2 bond dissociation as its initiation decomposition in the gas phase. The vacancy defects introduced into the ideal bulk NTO crystal can produce a localized site, where the initiation decomposition is preferentially accelerated and then promotes further decompositions. Our results may shed some light on the influence of the molecular environments on the initial pathways in molecular explosives.

Effects of magnesium-based hydrogen storage materials on the thermal decomposition, burning rate, and explosive heat of ammonium perchlorate-based composite solid propellant.

PubMed

Liu, Leili; Li, Jie; Zhang, Lingyao; Tian, Siyu

2018-01-15

MgH 2 , Mg 2 NiH 4 , and Mg 2 CuH 3 were prepared, and their structure and hydrogen storage properties were determined through X-ray photoelectron spectroscopy and thermal analyzer. The effects of MgH 2 , Mg 2 NiH 4 , and Mg 2 CuH 3 on the thermal decomposition, burning rate, and explosive heat of ammonium perchlorate-based composite solid propellant were subsequently studied. Results indicated that MgH 2 , Mg 2 NiH 4 , and Mg 2 CuH 3 can decrease the thermal decomposition peak temperature and increase the total released heat of decomposition. These compounds can improve the effect of thermal decomposition of the propellant. The burning rates of the propellant increased using Mg-based hydrogen storage materials as promoter. The burning rates of the propellant also increased using MgH 2 instead of Al in the propellant, but its explosive heat was not enlarged. Nonetheless, the combustion heat of MgH 2 was higher than that of Al. A possible mechanism was thus proposed. Copyright © 2017. Published by Elsevier B.V.

Microbial genomics, transcriptomics and proteomics: new discoveries in decomposition research using complementary methods.

PubMed

Baldrian, Petr; López-Mondéjar, Rubén

2014-02-01

Molecular methods for the analysis of biomolecules have undergone rapid technological development in the last decade. The advent of next-generation sequencing methods and improvements in instrumental resolution enabled the analysis of complex transcriptome, proteome and metabolome data, as well as a detailed annotation of microbial genomes. The mechanisms of decomposition by model fungi have been described in unprecedented detail by the combination of genome sequencing, transcriptomics and proteomics. The increasing number of available genomes for fungi and bacteria shows that the genetic potential for decomposition of organic matter is widespread among taxonomically diverse microbial taxa, while expression studies document the importance of the regulation of expression in decomposition efficiency. Importantly, high-throughput methods of nucleic acid analysis used for the analysis of metagenomes and metatranscriptomes indicate the high diversity of decomposer communities in natural habitats and their taxonomic composition. Today, the metaproteomics of natural habitats is of interest. In combination with advanced analytical techniques to explore the products of decomposition and the accumulation of information on the genomes of environmentally relevant microorganisms, advanced methods in microbial ecophysiology should increase our understanding of the complex processes of organic matter transformation.

Effect of interacting second- and third-order stimulus-dependent correlations on population-coding asymmetries.

PubMed

Montangie, Lisandro; Montani, Fernando

2016-10-01

Spike correlations among neurons are widely encountered in the brain. Although models accounting for pairwise interactions have proved able to capture some of the most important features of population activity at the level of the retina, the evidence shows that pairwise neuronal correlation analysis does not resolve cooperative population dynamics by itself. By means of a series expansion for short time scales of the mutual information conveyed by a population of neurons, the information transmission can be broken down into firing rate and correlational components. In a proposed extension of this framework, we investigate the information components considering both second- and higher-order correlations. We show that the existence of a mixed stimulus-dependent correlation term defines a new scenario for the interplay between pairwise and higher-than-pairwise interactions in noise and signal correlations that would lead either to redundancy or synergy in the information-theoretic sense.

Automatic Camera Calibration Using Multiple Sets of Pairwise Correspondences.

PubMed

Vasconcelos, Francisco; Barreto, Joao P; Boyer, Edmond

2018-04-01

We propose a new method to add an uncalibrated node into a network of calibrated cameras using only pairwise point correspondences. While previous methods perform this task using triple correspondences, these are often difficult to establish when there is limited overlap between different views. In such challenging cases we must rely on pairwise correspondences and our solution becomes more advantageous. Our method includes an 11-point minimal solution for the intrinsic and extrinsic calibration of a camera from pairwise correspondences with other two calibrated cameras, and a new inlier selection framework that extends the traditional RANSAC family of algorithms to sampling across multiple datasets. Our method is validated on different application scenarios where a lack of triple correspondences might occur: addition of a new node to a camera network; calibration and motion estimation of a moving camera inside a camera network; and addition of views with limited overlap to a Structure-from-Motion model.

Shaped Ceria Nanocrystals Catalyze Efficient and Selective Para-Hydrogen-Enhanced Polarization.

PubMed

Zhao, Evan W; Zheng, Haibin; Zhou, Ronghui; Hagelin-Weaver, Helena E; Bowers, Clifford R

2015-11-23

Intense para-hydrogen-enhanced NMR signals are observed in the hydrogenation of propene and propyne over ceria nanocubes, nano-octahedra, and nanorods. The well-defined ceria shapes, synthesized by a hydrothermal method, expose different crystalline facets with various oxygen vacancy densities, which are known to play a role in hydrogenation and oxidation catalysis. While the catalytic activity of the hydrogenation of propene over ceria is strongly facet-dependent, the pairwise selectivity is low (2.4% at 375 °C), which is consistent with stepwise H atom transfer, and it is the same for all three nanocrystal shapes. Selective semi-hydrogenation of propyne over ceria nanocubes yields hyperpolarized propene with a similar pairwise selectivity of (2.7% at 300 °C), indicating product formation predominantly by a non-pairwise addition. Ceria is also shown to be an efficient pairwise replacement catalyst for propene. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Pairwise Force Smoothed Particle Hydrodynamics model for multiphase flow: Surface tension and contact line dynamics

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tartakovsky, Alexandre M.; Panchenko, Alexander

2016-01-01

We present a novel formulation of the Pairwise Force Smoothed Particle Hydrodynamics Model (PF-SPH) and use it to simulate two- and three-phase flows in bounded domains. In the PF-SPH model, the Navier-Stokes equations are discretized with the Smoothed Particle Hydrodynamics (SPH) method and the Young-Laplace boundary condition at the fluid-fluid interface and the Young boundary condition at the fluid-fluid-solid interface are replaced with pairwise forces added into the Navier-Stokes equations. We derive a relationship between the parameters in the pairwise forces and the surface tension and static contact angle. Next, we demonstrate the accuracy of the model under static andmore » dynamic conditions. Finally, to demonstrate the capabilities and robustness of the model we use it to simulate flow of three fluids in a porous material.« less

Reactive molecular dynamics simulation of solid nitromethane impact on (010) surfaces induced and nonimpact thermal decomposition.

PubMed

Guo, Feng; Cheng, Xin-lu; Zhang, Hong

2012-04-12

Which is the first step in the decomposition process of nitromethane is a controversial issue, proton dissociation or C-N bond scission. We applied reactive force field (ReaxFF) molecular dynamics to probe the initial decomposition mechanisms of nitromethane. By comparing the impact on (010) surfaces and without impact (only heating) for nitromethane simulations, we found that proton dissociation is the first step of the pyrolysis of nitromethane, and the C-N bond decomposes in the same time scale as in impact simulations, but in the nonimpact simulation, C-N bond dissociation takes place at a later time. At the end of these simulations, a large number of clusters are formed. By analyzing the trajectories, we discussed the role of the hydrogen bond in the initial process of nitromethane decompositions, the intermediates observed in the early time of the simulations, and the formation of clusters that consisted of C-N-C-N chain/ring structures.

Active sites and mechanisms for H2O2 decomposition over Pd catalysts

PubMed Central

Plauck, Anthony; Stangland, Eric E.; Dumesic, James A.; Mavrikakis, Manos

2016-01-01

A combination of periodic, self-consistent density functional theory (DFT-GGA-PW91) calculations, reaction kinetics experiments on a SiO2-supported Pd catalyst, and mean-field microkinetic modeling are used to probe key aspects of H2O2 decomposition on Pd in the absence of cofeeding H2. We conclude that both Pd(111) and OH-partially covered Pd(100) surfaces represent the nature of the active site for H2O2 decomposition on the supported Pd catalyst reasonably well. Furthermore, all reaction flux in the closed catalytic cycle is predicted to flow through an O–O bond scission step in either H2O2 or OOH, followed by rapid H-transfer steps to produce the H2O and O2 products. The barrier for O–O bond scission is sensitive to Pd surface structure and is concluded to be the central parameter governing H2O2 decomposition activity. PMID:27006504

Kinetics of methane hydrate decomposition studied via in situ low temperature X-ray powder diffraction.

PubMed

Everett, S Michelle; Rawn, Claudia J; Keffer, David J; Mull, Derek L; Payzant, E Andrew; Phelps, Tommy J

2013-05-02

Gas hydrate is known to have a slowed decomposition rate at ambient pressure and temperatures below the melting point of ice. As hydrate exothermically decomposes, gas is released and water of the clathrate cages transforms into ice. Based on results from the decomposition of three nominally similar methane hydrate samples, the kinetics of two regions, 180-200 and 230-260 K, within the overall decomposition range 140-260 K, were studied by in situ low temperature X-ray powder diffraction. The kinetic rate constants, k(a), and the reaction mechanisms, n, for ice formation from methane hydrate were determined by the Avrami model within each region, and activation energies, E(a), were determined by the Arrhenius plot. E(a) determined from the data for 180-200 K was 42 kJ/mol and for 230-260 K was 22 kJ/mol. The higher E(a) in the colder temperature range was attributed to a difference in the microstructure of ice between the two regions.

Synergies from using higher order symplectic decompositions both for ordinary differential equations and quantum Monte Carlo methods

DOE Office of Scientific and Technical Information (OSTI.GOV)

Matuttis, Hans-Georg; Wang, Xiaoxing

Decomposition methods of the Suzuki-Trotter type of various orders have been derived in different fields. Applying them both to classical ordinary differential equations (ODEs) and quantum systems allows to judge their effectiveness and gives new insights for many body quantum mechanics where reference data are scarce. Further, based on data for 6 × 6 system we conclude that sampling with sign (minus-sign problem) is probably detrimental to the accuracy of fermionic simulations with determinant algorithms.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Brezov, D. S.; Mladenova, C. D.; Mladenov, I. M., E-mail: mladenov@bio21.bas.bg

In this paper we obtain the Lie derivatives of the scalar parameters in the generalized Euler decomposition with respect to arbitrary axes under left and right deck transformations. This problem can be directly related to the representation of the angular momentum in quantum mechanics. As a particular example, we calculate the angular momentum and the corresponding quantum hamiltonian in the standard Euler and Bryan representations. Similarly, in the hyperbolic case, the Laplace-Beltrami operator is retrieved for the Iwasawa decomposition. The case of two axes is considered as well.

Hydrazine vapor detonations

NASA Technical Reports Server (NTRS)

Pedley, M. D.; Bishop, C. V.; Benz, F. J.; Bennett, C. A.; Mcclenagan, R. D.

1988-01-01

The detonation velocity and cell widths for hydrazine decomposition were measured over a wide range of temperatures and pressures. The detonation velocity in pure hydrazine was within 5 percent of the calculated C-J velocity. The detonation cell width measurements were interpreted using the Zeldovich-Doering-von Neumann model with a detailed reaction mechanism for hydrazine decomposition. Excellent agreement with experimental data for pure hydrazine was obtained using the empirical relation that detonation cell width was equal to 29 times the kinetically calculated reaction zone length.

Thermochemical and kinetic analysis of the thermal decomposition of monomethylhydrazine: an elementary reaction mechanism.

PubMed

Sun, Hongyan; Law, Chung K

2007-05-17

The reaction kinetics for the thermal decomposition of monomethylhydrazine (MMH) was studied with quantum Rice-Ramsperger-Kassel (QRRK) theory and a master equation analysis for pressure falloff. Thermochemical properties were determined by ab initio and density functional calculations. The entropies, S degrees (298.15 K), and heat capacities, Cp degrees (T) (0 < or = T/K < or = 1500), from vibrational, translational, and external rotational contributions were calculated using statistical mechanics based on the vibrational frequencies and structures obtained from the density functional study. Potential barriers for internal rotations were calculated at the B3LYP/6-311G(d,p) level, and hindered rotational contributions to S degrees (298.15 K) and Cp degrees (T) were calculated by solving the Schrödinger equation with free rotor wave functions, and the partition coefficients were treated by direct integration over energy levels of the internal rotation potentials. Enthalpies of formation, DeltafH degrees (298.15 K), for the parent MMH (CH3NHNH2) and its corresponding radicals CH3N*NH2, CH3NHN*H, and C*H2NHNH2 were determined to be 21.6, 48.5, 51.1, and 62.8 kcal mol(-1) by use of isodesmic reaction analysis and various ab initio methods. The kinetic analysis of the thermal decomposition, abstraction, and substitution reactions of MMH was performed at the CBS-QB3 level, with those of N-N and C-N bond scissions determined by high level CCSD(T)/6-311++G(3df,2p)//MPWB1K/6-31+G(d,p) calculations. Rate constants of thermally activated MMH to dissociation products were calculated as functions of pressure and temperature. An elementary reaction mechanism based on the calculated rate constants, thermochemical properties, and literature data was developed to model the experimental data on the overall MMH thermal decomposition rate. The reactions of N-N and C-N bond scission were found to be the major reaction paths for the modeling of MMH homogeneous decomposition at atmospheric conditions.

Decomposition of toluene in a steady-state atmospheric-pressure glow discharge

NASA Astrophysics Data System (ADS)

Trushkin, A. N.; Grushin, M. E.; Kochetov, I. V.; Trushkin, N. I.; Akishev, Yu. S.

2013-02-01

Results are presented from experimental studies of decomposition of toluene (C6H5CH3) in a polluted air flow by means of a steady-state atmospheric pressure glow discharge at different water vapor contents in the working gas. The experimental results on the degree of C6H5CH3 removal are compared with the results of computer simulations conducted in the framework of the developed kinetic model of plasma chemical decomposition of toluene in the N2: O2: H2O gas mixture. A substantial influence of the gas flow humidity on toluene decomposition in the atmospheric pressure glow discharge is demonstrated. The main mechanisms of the influence of humidity on C6H5CH3 decomposition are determined. The existence of two stages in the process of toluene removal, which differ in their duration and the intensity of plasma chemical decomposition of C6H5CH3 is established. Based on the results of computer simulations, the composition of the products of plasma chemical reactions at the output of the reactor is analyzed as a function of the specific energy deposition and gas flow humidity. The existence of a catalytic cycle in which hydroxyl radical OH acts a catalyst and which substantially accelerates the recombination of oxygen atoms and suppression of ozone generation when the plasma-forming gas contains water vapor is established.

Decomposition Mechanism of C5F10O: An Environmentally Friendly Insulation Medium.

PubMed

Zhang, Xiaoxing; Li, Yi; Xiao, Song; Tang, Ju; Tian, Shuangshuang; Deng, Zaitao

2017-09-05

SF 6 , the most widely used electrical-equipment-insulation gas, has serious greenhouse effects. C 5 F 10 O has attracted much attention as an alternative gas in recent two years, but the environmental impact of its decomposition products is unclear. In this work, the decomposition characteristics of C 5 F 10 O were studied based on gas chromatography-mass spectrometry and density functional theory. We found that the amount of decomposition products of C 5 F 10 O, namely, CF 4 , C 2 F 6 , C 3 F 6 , C 3 F 8 , C 4 F 10 , and C 6 F 14 , increased with increased number of discharges. Under a high-energy electric field, the C-C bond of C 5 F 10 O between carbonyl carbon and α-carbon atoms was most likely to break and generate CF 3 CO•, C 3 F 7 • or C 3 F 7 CO•, CF 3 • free radicals. CF 3 •, and C 3 F 7 • free radicals produced by the breakage more easily recombined to form small molecular products. By analyzing the ionization parameters, toxicity, and environmental effects of C 5 F 10 O and its decomposition products, we found that C 5 F 10 O gas mixtures exhibit great decomposition and environmental characteristics with low toxicity, with great potential to replace SF 6 .

Effect of sulfation on the surface activity of CaO for N2O decomposition

NASA Astrophysics Data System (ADS)

Wu, Lingnan; Hu, Xiaoying; Qin, Wu; Dong, Changqing; Yang, Yongping

2015-12-01

Limestone addition to circulating fluidized bed boilers for sulfur removal affects nitrous oxide (N2O) emission at the same time, but mechanism of how sulfation process influences the surface activity of CaO for N2O decomposition remains unclear. In this paper, we investigated the effect of sulfation on the surface properties and catalytic activity of CaO for N2O decomposition using density functional theory calculations. Sulfation of CaO (1 0 0) surface by the adsorption of a single gaseous SO2 or SO3 molecule forms stable local CaSO3 or CaSO4 on the CaO (1 0 0) surface with strong hybridization between the S atom of SOx and the surface O anion. The formed local CaSO3 increases the barrier energy of N2O decomposition from 0.989 eV (on the CaO (1 0 0) surface) to 1.340 eV, and further sulfation into local CaSO4 remarkably increases the barrier energy to 2.967 eV. Sulfation from CaSO3 into CaSO4 is therefore the crucial step for deactivating the surface activity for N2O decomposition. Completely sulfated CaSO4 (0 0 1) and (0 1 0) surfaces further validate the negligible catalytic ability of CaSO4 for N2O decomposition.

Direct vs. Microclimate-Driven Effects of Tree Species Diversity on Litter Decomposition in Young Subtropical Forest Stands.

PubMed

Seidelmann, Katrin N; Scherer-Lorenzen, Michael; Niklaus, Pascal A

2016-01-01

Effects of tree species diversity on decomposition can operate via a multitude of mechanism, including alterations of microclimate by the forest canopy. Studying such effects in natural settings is complicated by the fact that topography also affects microclimate and thus decomposition, so that effects of diversity are more difficult to isolate. Here, we quantified decomposition rates of standard litter in young subtropical forest stands, separating effects of canopy tree species richness and topography, and quantifying their direct and micro-climate-mediated components. Our litterbag study was carried out at two experimental sites of a biodiversity-ecosystem functioning field experiment in south-east China (BEF-China). The field sites display strong topographical heterogeneity and were planted with tree communities ranging from monocultures to mixtures of 24 native subtropical tree species. Litter bags filled with senescent leaves of three native tree species were placed from Nov. 2011 to Oct. 2012 on 134 plots along the tree species diversity gradient. Topographic features were measured for all and microclimate in a subset of plots. Stand species richness, topography and microclimate explained important fractions of the variations in litter decomposition rates, with diversity and topographic effects in part mediated by microclimatic changes. Tree stands were 2-3 years old, but nevertheless tree species diversity explained more variation (54.3%) in decomposition than topography (7.7%). Tree species richness slowed litter decomposition, an effect that slightly depended on litter species identity. A large part of the variance in decomposition was explained by tree species composition, with the presence of three tree species playing a significant role. Microclimate explained 31.4% of the variance in decomposition, and was related to lower soil moisture. Within this microclimate effect, species diversity (without composition) explained 8.9% and topography 34.4% of variance. Topography mainly affected diurnal temperature amplitudes by varying incident solar radiation.

Direct vs. Microclimate-Driven Effects of Tree Species Diversity on Litter Decomposition in Young Subtropical Forest Stands

PubMed Central

Seidelmann, Katrin N.; Scherer-Lorenzen, Michael; Niklaus, Pascal A.

2016-01-01

Effects of tree species diversity on decomposition can operate via a multitude of mechanism, including alterations of microclimate by the forest canopy. Studying such effects in natural settings is complicated by the fact that topography also affects microclimate and thus decomposition, so that effects of diversity are more difficult to isolate. Here, we quantified decomposition rates of standard litter in young subtropical forest stands, separating effects of canopy tree species richness and topography, and quantifying their direct and micro-climate-mediated components. Our litterbag study was carried out at two experimental sites of a biodiversity-ecosystem functioning field experiment in south-east China (BEF-China). The field sites display strong topographical heterogeneity and were planted with tree communities ranging from monocultures to mixtures of 24 native subtropical tree species. Litter bags filled with senescent leaves of three native tree species were placed from Nov. 2011 to Oct. 2012 on 134 plots along the tree species diversity gradient. Topographic features were measured for all and microclimate in a subset of plots. Stand species richness, topography and microclimate explained important fractions of the variations in litter decomposition rates, with diversity and topographic effects in part mediated by microclimatic changes. Tree stands were 2–3 years old, but nevertheless tree species diversity explained more variation (54.3%) in decomposition than topography (7.7%). Tree species richness slowed litter decomposition, an effect that slightly depended on litter species identity. A large part of the variance in decomposition was explained by tree species composition, with the presence of three tree species playing a significant role. Microclimate explained 31.4% of the variance in decomposition, and was related to lower soil moisture. Within this microclimate effect, species diversity (without composition) explained 8.9% and topography 34.4% of variance. Topography mainly affected diurnal temperature amplitudes by varying incident solar radiation. PMID:27490180

A decomposition theory for phylogenetic networks and incompatible characters.

PubMed

Gusfield, Dan; Bansal, Vikas; Bafna, Vineet; Song, Yun S

2007-12-01

Phylogenetic networks are models of evolution that go beyond trees, incorporating non-tree-like biological events such as recombination (or more generally reticulation), which occur either in a single species (meiotic recombination) or between species (reticulation due to lateral gene transfer and hybrid speciation). The central algorithmic problems are to reconstruct a plausible history of mutations and non-tree-like events, or to determine the minimum number of such events needed to derive a given set of binary sequences, allowing one mutation per site. Meiotic recombination, reticulation and recurrent mutation can cause conflict or incompatibility between pairs of sites (or characters) of the input. Previously, we used "conflict graphs" and "incompatibility graphs" to compute lower bounds on the minimum number of recombination nodes needed, and to efficiently solve constrained cases of the minimization problem. Those results exposed the structural and algorithmic importance of the non-trivial connected components of those two graphs. In this paper, we more fully develop the structural importance of non-trivial connected components of the incompatibility and conflict graphs, proving a general decomposition theorem (Gusfield and Bansal, 2005) for phylogenetic networks. The decomposition theorem depends only on the incompatibilities in the input sequences, and hence applies to many types of phylogenetic networks, and to any biological phenomena that causes pairwise incompatibilities. More generally, the proof of the decomposition theorem exposes a maximal embedded tree structure that exists in the network when the sequences cannot be derived on a perfect phylogenetic tree. This extends the theory of perfect phylogeny in a natural and important way. The proof is constructive and leads to a polynomial-time algorithm to find the unique underlying maximal tree structure. We next examine and fully solve the major open question from Gusfield and Bansal (2005): Is it true that for every input there must be a fully decomposed phylogenetic network that minimizes the number of recombination nodes used, over all phylogenetic networks for the input. We previously conjectured that the answer is yes. In this paper, we show that the answer in is no, both for the case that only single-crossover recombination is allowed, and also for the case that unbounded multiple-crossover recombination is allowed. The latter case also resolves a conjecture recently stated in (Huson and Klopper, 2007) in the context of reticulation networks. Although the conjecture from Gusfield and Bansal (2005) is disproved in general, we show that the answer to the conjecture is yes in several natural special cases, and establish necessary combinatorial structure that counterexamples to the conjecture must possess. We also show that counterexamples to the conjecture are rare (for the case of single-crossover recombination) in simulated data.

Reaction mechanisms in cellulose pyrolysis: a literature review

DOE Office of Scientific and Technical Information (OSTI.GOV)

Molton, P.M.; Demmitt, T.F.

1977-08-01

A bibliographic review of 195 references is presented outlining the history of the research into the mechanisms of cellulose pyrolysis. Topics discussed are: initial product identification, mechanism of initial formation of levoglucosan, from cellulose and from related compounds, decomposition of cellulose to other compounds, formation of aromatics, pyrolysis of levoglucosan, crosslinking of cellulose, pyrolytic reactions of cellulose derivatives, and the effects of inorganic salts on the pyrolysis mechanism. (JSR)

Thermochemical properties of nanometer CL-20 and PETN fabricated using a mechanical milling method

NASA Astrophysics Data System (ADS)

Song, Xiaolan; Wang, Yi; An, Chongwei

2018-06-01

2,4,6,8,10,12-Hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane (CL-20) and pentaerythritol tetranitrate (PETN), with mean sizes of 73.8 nm and 267.7 nm, respectively, were fabricated on a high-energy ball-mill. Scanning electron microscope (SEM) analysis was used to image the micron-scale morphology of nano-explosives, and the particle size distribution was calculated using the statistics of individual particle sizes obtained from the SEM images. Analyses, such as X-ray diffractometer (XRD), infrared spectroscopy (IR), and X-ray photoelectron spectroscopy (XPS), were also used to confirm whether the crystal phase, molecular structure, and surface elements changed after a long-term milling process. The results were as expected. Thermal analysis was performed at different heating rates. Parameters, such as the activation energy (ES), activation enthalpy (ΔH≠), activation free energy (ΔG≠), activation entropy (ΔS≠), and critical temperature of thermal explosion (Tb), were calculated to determine the decomposition courses of the explosives. Moreover, the thermal decomposition mechanisms of nano CL-20 and nano PETN were investigated using thermal-infrared spectrometry online (DSC-IR) analysis, by which their gas products were also detected. The results indicated that nano CL-20 decomposed to CO2 and N2O and that nano PETN decayed to NO2, which implied a remarkable difference between the decomposition mechanisms of the two explosives. In addition, the mechanical sensitivities of CL-20 and PETN were tested, and the results revealed that nano-explosives were more insensitive than raw ones, and the possible mechanism for this was discussed. Thermal sensitivity was also investigated with a 5 s bursting point test, from which the 5 s bursting point (T5s) and the activation of the deflagration were obtained.

Online Pairwise Learning Algorithms.

PubMed

Ying, Yiming; Zhou, Ding-Xuan

2016-04-01

Pairwise learning usually refers to a learning task that involves a loss function depending on pairs of examples, among which the most notable ones are bipartite ranking, metric learning, and AUC maximization. In this letter we study an online algorithm for pairwise learning with a least-square loss function in an unconstrained setting of a reproducing kernel Hilbert space (RKHS) that we refer to as the Online Pairwise lEaRning Algorithm (OPERA). In contrast to existing works (Kar, Sriperumbudur, Jain, & Karnick, 2013 ; Wang, Khardon, Pechyony, & Jones, 2012 ), which require that the iterates are restricted to a bounded domain or the loss function is strongly convex, OPERA is associated with a non-strongly convex objective function and learns the target function in an unconstrained RKHS. Specifically, we establish a general theorem that guarantees the almost sure convergence for the last iterate of OPERA without any assumptions on the underlying distribution. Explicit convergence rates are derived under the condition of polynomially decaying step sizes. We also establish an interesting property for a family of widely used kernels in the setting of pairwise learning and illustrate the convergence results using such kernels. Our methodology mainly depends on the characterization of RKHSs using its associated integral operators and probability inequalities for random variables with values in a Hilbert space.

Cosmology with the pairwise kinematic SZ effect: Calibration and validation using hydrodynamical simulations

NASA Astrophysics Data System (ADS)

Soergel, Bjoern; Saro, Alexandro; Giannantonio, Tommaso; Efstathiou, George; Dolag, Klaus

2018-05-01

We study the potential of the kinematic SZ effect as a probe for cosmology, focusing on the pairwise method. The main challenge is disentangling the cosmologically interesting mean pairwise velocity from the cluster optical depth and the associated uncertainties on the baryonic physics in clusters. Furthermore, the pairwise kSZ signal might be affected by internal cluster motions or correlations between velocity and optical depth. We investigate these effects using the Magneticum cosmological hydrodynamical simulations, one of the largest simulations of this kind performed to date. We produce tSZ and kSZ maps with an area of ≃ 1600 deg2, and the corresponding cluster catalogues with M500c ≳ 3 × 1013 h-1M⊙ and z ≲ 2. From these data sets we calibrate a scaling relation between the average Compton-y parameter and optical depth. We show that this relation can be used to recover an accurate estimate of the mean pairwise velocity from the kSZ effect, and that this effect can be used as an important probe of cosmology. We discuss the impact of theoretical and observational systematic effects, and find that further work on feedback models is required to interpret future high-precision measurements of the kSZ effect.

The Chemical Decomposition of 5-aza-2′-deoxycytidine (Decitabine): Kinetic Analyses and Identification of Products by NMR, HPLC, and Mass Spectrometry

PubMed Central

Rogstad, Daniel K.; Herring, Jason L.; Theruvathu, Jacob A.; Burdzy, Artur; Perry, Christopher C.; Neidigh, Jonathan W.; Sowers, Lawrence C.

2014-01-01

The nucleoside analog 5-aza-2′-deoxycytidine (Decitabine, DAC) is one of several drugs in clinical use that inhibit DNA methyltransferases, leading to a decrease of 5-methylcytosine in newly replicated DNA and subsequent transcriptional activation of genes silenced by cytosine methylation. In addition to methyltransferase inhibition, DAC has demonstrated toxicity and potential mutagenicity, and can induce a DNA-repair response. The mechanisms accounting for these events are not well understood. DAC is chemically unstable in aqueous solutions, but there is little consensus between previous reports as to its half-life and corresponding products of decomposition at physiological temperature and pH, potentially confounding studies on its mechanism of action and long-term use in humans. Here we have employed a battery of analytical methods to estimate kinetic rates and to characterize DAC decomposition products under conditions of physiological temperature and pH. Our results indicate that DAC decomposes into a plethora of products, formed by hydrolytic opening and deformylation of the triazine ring, in addition to anomerization and possibly other changes in the sugar ring structure. We also discuss the advantages and problems associated with each analytical method used. The results reported here will facilitate ongoing studies and clinical trials aimed at understanding the mechanisms of action, toxicity, and possible mutagenicity of DAC and related analogs. PMID:19480391

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lopes, E.S.N.; Cremasco, A.; Afonso, C.R.M.

Aging heat treatment can be a good way to optimize mechanical properties, changing the microstructure, and hence, the mechanical behavior of Ti alloys. The effects of aging heat treatments on {beta}-type Ti-30Nb alloy were investigated to evaluate the kinetics of {alpha}'' {yields} {alpha} + {beta} transformation. The results obtained from differential scanning calorimetry and high-temperature X-ray diffraction experiments indicated the complete decomposition of orthorhombic {alpha}'' phase at close to 300 deg. C, followed by {alpha} phase precipitation at 470 deg. C. The aging heat treatments also enabled us to observe a transformation sequence {alpha}'' {yields} {beta} + {omega} {yields} {beta}more » + {omega} + {alpha}, indicating martensite decomposition and {omega} phase precipitation at 260 deg. C after 2 h, followed by {alpha} phase nucleation after heating at 400 deg. C for 1 h. The elastic modulus and Vickers hardness of Ti-30Nb alloy were found to be very sensitive to the microstructural changes caused by heat treatment. - Highlights: {yields} DSC and XRD shed light on the {alpha}'' decomposition and nucleation of {omega} and {alpha} phases. {yields} Aging allows for {alpha}''{yields}{beta} transformation and nucleation of {omega} dispersed in the {beta} matrix. {yields} During aging, {alpha}'' interplanar distances are reduced to enable {beta} phase nucleation. {yields} Mechanical behavior is dependent on the microstructure and the phases in the alloy. {yields} It is not possible to obtain high strength and low elastic modulus by applying aging.« less

Chemical decomposition of 5-aza-2'-deoxycytidine (Decitabine): kinetic analyses and identification of products by NMR, HPLC, and mass spectrometry.

PubMed

Rogstad, Daniel K; Herring, Jason L; Theruvathu, Jacob A; Burdzy, Artur; Perry, Christopher C; Neidigh, Jonathan W; Sowers, Lawrence C

2009-06-01

The nucleoside analogue 5-aza-2'-deoxycytidine (Decitabine, DAC) is one of several drugs in clinical use that inhibit DNA methyltransferases, leading to a decrease of 5-methylcytosine in newly replicated DNA and subsequent transcriptional activation of genes silenced by cytosine methylation. In addition to methyltransferase inhibition, DAC has demonstrated toxicity and potential mutagenicity, and can induce a DNA-repair response. The mechanisms accounting for these events are not well understood. DAC is chemically unstable in aqueous solutions, but there is little consensus between previous reports as to its half-life and corresponding products of decomposition at physiological temperature and pH, potentially confounding studies on its mechanism of action and long-term use in humans. Here, we have employed a battery of analytical methods to estimate kinetic rates and to characterize DAC decomposition products under conditions of physiological temperature and pH. Our results indicate that DAC decomposes into a plethora of products, formed by hydrolytic opening and deformylation of the triazine ring, in addition to anomerization and possibly other changes in the sugar ring structure. We also discuss the advantages and problems associated with each analytical method used. The results reported here will facilitate ongoing studies and clinical trials aimed at understanding the mechanisms of action, toxicity, and possible mutagenicity of DAC and related analogues.

Uncertainty propagation in orbital mechanics via tensor decomposition

NASA Astrophysics Data System (ADS)

Sun, Yifei; Kumar, Mrinal

2016-03-01

Uncertainty forecasting in orbital mechanics is an essential but difficult task, primarily because the underlying Fokker-Planck equation (FPE) is defined on a relatively high dimensional (6-D) state-space and is driven by the nonlinear perturbed Keplerian dynamics. In addition, an enormously large solution domain is required for numerical solution of this FPE (e.g. encompassing the entire orbit in the x-y-z subspace), of which the state probability density function (pdf) occupies a tiny fraction at any given time. This coupling of large size, high dimensionality and nonlinearity makes for a formidable computational task, and has caused the FPE for orbital uncertainty propagation to remain an unsolved problem. To the best of the authors' knowledge, this paper presents the first successful direct solution of the FPE for perturbed Keplerian mechanics. To tackle the dimensionality issue, the time-varying state pdf is approximated in the CANDECOMP/PARAFAC decomposition tensor form where all the six spatial dimensions as well as the time dimension are separated from one other. The pdf approximation for all times is obtained simultaneously via the alternating least squares algorithm. Chebyshev spectral differentiation is employed for discretization on account of its spectral ("super-fast") convergence rate. To facilitate the tensor decomposition and control the solution domain size, system dynamics is expressed using spherical coordinates in a noninertial reference frame. Numerical results obtained on a regular personal computer are compared with Monte Carlo simulations.

Combustion modeling and kinetic rate calculations for a stoichiometric cyclohexane flame. 1. Major reaction pathways.

PubMed

Zhang, Hongzhi R; Huynh, Lam K; Kungwan, Nawee; Yang, Zhiwei; Zhang, Shaowen

2007-05-17

The Utah Surrogate Mechanism was extended in order to model a stoichiometric premixed cyclohexane flame (P = 30 Torr). Generic rates were assigned to reaction classes of hydrogen abstraction, beta scission, and isomerization, and the resulting mechanism was found to be adequate in describing the combustion chemistry of cyclohexane. Satisfactory results were obtained in comparison with the experimental data of oxygen, major products and important intermediates, which include major soot precursors of C2-C5 unsaturated species. Measured concentrations of immediate products of fuel decomposition were also successfully reproduced. For example, the maximum concentrations of benzene and 1,3-butadiene, two major fuel decomposition products via competing pathways, were predicted within 10% of the measured values. Ring-opening reactions compete with those of cascading dehydrogenation for the decomposition of the conjugate cyclohexyl radical. The major ring-opening pathways produce 1-buten-4-yl radical, molecular ethylene, and 1,3-butadiene. The butadiene species is formed via beta scission after a 1-4 internal hydrogen migration of 1-hexen-6-yl radical. Cascading dehydrogenation also makes an important contribution to the fuel decomposition and provides the exclusive formation pathway of benzene. Benzene formation routes via combination of C2-C4 hydrocarbon fragments were found to be insignificant under current flame conditions, inferred by the later concentration peak of fulvene, in comparison with benzene, because the analogous species series for benzene formation via dehydrogenation was found to be precursors with regard to parent species of fulvene.

A detailed kinetic modeling study of toluene oxidation in a premixed laminar flame

PubMed Central

Tian, Zhenyu; Pitz, William J.; Fournet, René; Glaude, Pierre-Alexander; Battin-Leclerc, Frédérique

2013-01-01

An improved chemical kinetic model for the toluene oxidation based on experimental data obtained in a premixed laminar low-pressure flame with vacuum ultraviolet (VUV) photoionization and molecular beam mass spectrometry (MBMS) techniques has been proposed. The present mechanism consists of 273 species up to chrysene and 1740 reactions. The rate constants of reactions of toluene decomposition, reaction with oxygen, ipso-additions and metatheses with abstraction of phenylic H-atom are updated; new pathways of C4 + C2 species giving benzene and fulvene are added. Based on the experimental observations, combustion intermediates such as fulvenallene, naphtol, methylnaphthalene, acenaphthylene, 2-ethynylnaphthalene, phenanthrene, anthracene, 1-methylphenanthrene, pyrene and chrysene are involved in the present mechanism. The final toluene model leads to an overall satisfactory agreement between the experimentally observed and predicted mole fraction profiles for the major products and most combustion intermediates. The toluene depletion is governed by metathese giving benzyl radicals, ipso-addition forming benzene and metatheses leading to C6H4CH3 radicals. A sensitivity analysis indicates that the unimolecular decomposition via the cleavage of a methyl C-H bond has a strong inhibiting effect, while decomposition via C-C bond breaking, ipso-addition of H-atom to toluene, decomposition of benzyl radicals and reactions related to C6H4CH3 radicals have promoting effect for the consumption of toluene. Moreover, flow rate analysis is performed to illustrate the formation pathways of mono- and polycyclic aromatics. PMID:23762016

Effect of self-interaction on the evolution of cooperation in complex topologies

NASA Astrophysics Data System (ADS)

Wu, Yu'e.; Zhang, Zhipeng; Chang, Shuhua

2017-09-01

Self-interaction, as a significant mechanism explaining the evolution of cooperation, has attracted great attention both theoretically and experimentally. In this text, we consider a new self-interaction mechanism in the two typical pairwise models including the prisoner's dilemma and the snowdrift games, where the cooperative agents will gain extra bonus for their selfless behavior. We find that under the mechanism the collective cooperation is elevated to a very high level especially after adopting the finite population analogue of replicator dynamics for evolution. The robustness of the new mechanism is tested for different complex topologies for the prisoner's dilemma game. All the presented results demonstrate that the enhancement effects are independent of the structure of the applied spatial networks and the potential evolutionary games, and thus showing a high degree of universality. Our conclusions might shed light on the understanding of the evolution of cooperation in the real world.

Impact of OH Radical-Initiated H2CO3 Degradation in the Earth's Atmosphere via Proton-Coupled Electron Transfer Mechanism.

PubMed

Ghoshal, Sourav; Hazra, Montu K

2016-02-04

The decomposition of isolated carbonic acid (H2CO3) molecule into CO2 and H2O (H2CO3 → CO2 + H2O) is prevented by a large activation barrier (>35 kcal/mol). Nevertheless, it is surprising that the detection of the H2CO3 molecule has not been possible yet, and the hunt for the free H2CO3 molecule has become challenging not only in the Earth's atmosphere but also on Mars. In view of this fact, we report here the high levels of quantum chemistry calculations investigating both the energetics and kinetics of the OH radical-initiated H2CO3 degradation reaction to interpret the loss of the H2CO3 molecule in the Earth's atmosphere. It is seen from our study that proton-coupled electron transfer (PCET) and hydrogen atom transfer (HAT) are the two mechanisms by which the OH radical initiates the degradation of the H2CO3 molecule. Moreover, the PCET mechanism is potentially the important one, as the effective barrier, defined as the difference between the zero point vibrational energy (ZPE) corrected energy of the transition state and the total energy of the isolated starting reactants in terms of bimolecular encounters, for the PCET mechanism at the CCSD(T)/6-311++G(3df,3pd) level of theory is ∼3 to 4 kcal/mol lower than the effective barrier height associated with the HAT mechanism. The CCSD(T)/6-311++G(3df,3pd) level predicted effective barrier heights for the degradations of the two most stable conformers of H2CO3 molecule via the PCET mechanism are only ∼2.7 and 4.3 kcal/mol. A comparative reaction rate analysis at the CCSD(T)/6-311++G(3df,3pd) level of theory has also been carried out to explore the potential impact of the OH radical-initiated H2CO3 degradation relative to that from water (H2O), formic acid (FA), acetic acid (AA) and sulfuric acid (SA) assisted H2CO3 → CO2 + H2O decomposition reactions in both the Earth's troposphere and stratosphere. The comparison of the reaction rates reveals that, although the atmospheric concentration of the OH radical is substantially lower than the concentrations of the H2O, FA, AA in the Earth's atmosphere, nevertheless, the OH radical-initiated H2CO3 degradation reaction has significant impact, especially toward the loss of the H2CO3 molecule in the Earth's atmosphere. In clean environments, which exist in greater numbers in comparison to the polluted environments of the Earth's atmosphere, the impact of the OH radical-initiated H2CO3 degradation reaction is seen to be comparable to that from a competing pathway which utilizes hydrogen bonded molecules such as H2O, FA or AA to catalyze the H2CO3 decomposition. Similarly, in the polluted environments, and especially in the Earth's troposphere, although the reactions rates for the OH radical-initiated H2CO3 degradation and FA-assisted H2CO3 decomposition are comparable within a factor of ∼15, nevertheless, the AA-assisted H2CO3 decomposition reaction is appeared to be the dominant channel. This follows only because of slightly greater catalytic efficiency of the AA over FA upon the H2CO3 → CO2 + H2O decomposition reaction. In contrary, although the catalytic efficiencies of SA, FA, and AA upon the H2CO3 decomposition reaction are similar to each other and the concentrations of both the SA and OH radical in the Earth's atmosphere are more-or-less equal to each other, but nevertheless, the SA-assisted H2CO3 decomposition reaction cannot compete with the OH radical-initiated H2CO3 degradation reaction.

Active Mechanism of the Interphase Film-Forming Process for an Electrolyte Based on a Sulfolane Solvent and a Chelato-Borate Complexe.

PubMed

Li, Chunlei; Wang, Peng; Li, Shiyou; Zhao, Dongni; Zhao, Qiuping; Liu, Haining; Cui, Xiao-Ling

2018-06-14

Electrolytes based on sulfolane (SL) solvents and lithium bis(oxalato)borate (LiBOB) chelato-borate complexes have been reported many times for use in advanced lithium-ion batteries due to their many advantages. This study aims to clarify the active mechanism of the interphase film-forming process to optimize the properties of these batteries by experimental analysis and theoretical calculations. The results indicate that the self-repairing film-forming process during the first cycle is divided into three stages: the initial film formation with an electric field force of ~1.80 V, the further growth of the preformation solid electrolyte interface (SEI) film at ~1.73 V, and the final formation of a complete SEI film at a potential below 0.7 V. Additionally, we can deduce that the decomposition of LiBOB and SL occurs throughout nearly the entire process of the formation of the SEI film. The decomposition product of BOB- anions tends to form films with an irregular structure, while the decomposition product of SL is in favor of the formation of a uniform SEI film.

Phase behaviour in complementary DNA-coated gold nanoparticles and fd-viruses mixtures: a numerical study.

PubMed

Chiappini, Massimiliano; Eiser, Erika; Sciortino, Francesco

2017-01-01

A new gel-forming colloidal system based on a binary mixture of fd-viruses and gold nanoparticles functionalized with complementary DNA single strands has been recently introduced. Upon quenching below the DNA melt temperature, such a system results in a highly porous gel state, that may be developed in a new functional material of tunable porosity. In order to shed light on the gelation mechanism, we introduce a model closely mimicking the experimental one and we explore via Monte Carlo simulations its equilibrium phase diagram. Specifically, we model the system as a binary mixture of hard rods and hard spheres mutually interacting via a short-range square-well attractive potential. In the experimental conditions, we find evidence of a phase separation occurring either via nucleation-and-growth or via spinodal decomposition. The spinodal decomposition leads to the formation of small clusters of bonded rods and spheres whose further diffusion and aggregation leads to the formation of a percolating network in the system. Our results are consistent with the hypothesis that the mixture of DNA-coated fd-viruses and gold nanoparticles undergoes a non-equilibrium gelation via an arrested spinodal decomposition mechanism.

Theoretical study on stabilization mechanisms of nitrate esters using aromatic amines as stabilizers.

PubMed

Sun, Zhi-Dan; Fu, Xiao-Long; Yu, Hong-Jian; Fan, Xue-Zhong; Ju, Xue-Hai

2017-10-05

The propellants of nitrate esters can be stabilized by some aromatic amines practically. To probe the mechanism of this phenomenon, we performed DFT calculations on: (1) The decompositions of nitrate esters (with and without the catalysis of NO 2 ) and (2) the reaction between the stabilizers and the nitro dioxide (NO 2 is released during the storage of nitrate esters). The structures on the reaction paths (reactants, intermediates and products) were optimized at the (U)B3LYP/6-31G** level. It was shown that NO 2 lowers the activation energy barrier in the decomposition of nitrate ester by 11.82-17.86kJ/mol and efficiently catalyzes the rupture of ONO 2 bond. However, the aromatic amines, typical stabilizers for nitrate esters, can easily eliminate NO 2 with activation barriers as low as 27-113kJ/mol (with one exception of 128kJ/mol). These values are, for most cases, lower or much lower than the activation energy barriers for reactions between nitrate esters and NO 2 (127-137kJ/mol). Consequently, the stabilizers can block the NO 2 catalysis for the decompositions of nitrate esters. Copyright © 2017 Elsevier B.V. All rights reserved.

Forest height estimation from mountain forest areas using general model-based decomposition for polarimetric interferometric synthetic aperture radar images

NASA Astrophysics Data System (ADS)

Minh, Nghia Pham; Zou, Bin; Cai, Hongjun; Wang, Chengyi

2014-01-01

The estimation of forest parameters over mountain forest areas using polarimetric interferometric synthetic aperture radar (PolInSAR) images is one of the greatest interests in remote sensing applications. For mountain forest areas, scattering mechanisms are strongly affected by the ground topography variations. Most of the previous studies in modeling microwave backscattering signatures of forest area have been carried out over relatively flat areas. Therefore, a new algorithm for the forest height estimation from mountain forest areas using the general model-based decomposition (GMBD) for PolInSAR image is proposed. This algorithm enables the retrieval of not only the forest parameters, but also the magnitude associated with each mechanism. In addition, general double- and single-bounce scattering models are proposed to fit for the cross-polarization and off-diagonal term by separating their independent orientation angle, which remains unachieved in the previous model-based decompositions. The efficiency of the proposed approach is demonstrated with simulated data from PolSARProSim software and ALOS-PALSAR spaceborne PolInSAR datasets over the Kalimantan areas, Indonesia. Experimental results indicate that forest height could be effectively estimated by GMBD.

Maximally informative pairwise interactions in networks

PubMed Central

Fitzgerald, Jeffrey D.; Sharpee, Tatyana O.

2010-01-01

Several types of biological networks have recently been shown to be accurately described by a maximum entropy model with pairwise interactions, also known as the Ising model. Here we present an approach for finding the optimal mappings between input signals and network states that allow the network to convey the maximal information about input signals drawn from a given distribution. This mapping also produces a set of linear equations for calculating the optimal Ising-model coupling constants, as well as geometric properties that indicate the applicability of the pairwise Ising model. We show that the optimal pairwise interactions are on average zero for Gaussian and uniformly distributed inputs, whereas they are nonzero for inputs approximating those in natural environments. These nonzero network interactions are predicted to increase in strength as the noise in the response functions of each network node increases. This approach also suggests ways for how interactions with unmeasured parts of the network can be inferred from the parameters of response functions for the measured network nodes. PMID:19905153

Acetaldehyde dissociates the PTP1B–E-cadherin–β-catenin complex in Caco-2 cell monolayers by a phosphorylation-dependent mechanism

PubMed Central

Sheth, Parimal; Seth, Ankur; Atkinson, Katherine J.; Gheyi, Tarun; Kale, Gautam; Giorgianni, Francesco; Desiderio, Dominic M.; Li, Chunying; Naren, Anjaparavanda; Rao, Radhakrishna

2006-01-01

Interactions between E-cadherin, β-catenin and PTP1B (protein tyrosine phosphatase 1B) are crucial for the organization of AJs (adherens junctions) and epithelial cell–cell adhesion. In the present study, the effect of acetaldehyde on the AJs and on the interactions between E-cadherin, β-catenin and PTP1B was determined in Caco-2 cell monolayers. Treatment of cell monolayers with acetaldehyde induced redistribution of E-cadherin and β-catenin from the intercellular junctions by a tyrosine phosphorylation-dependent mechanism. The PTPase activity associated with E-cadherin and β-catenin was significantly reduced and the interaction of PTP1B with E-cadherin and β-catenin was attenuated by acetaldehyde. Acetaldehyde treatment resulted in phosphorylation of β-catenin on tyrosine residues, and abolished the interaction of β-catenin with E-cadherin by a tyrosine kinase-dependent mechanism. Protein binding studies showed that the treatment of cells with acetaldehyde reduced the binding of β-catenin to the C-terminal region of E-cadherin. Pairwise binding studies using purified proteins indicated that the direct interaction between E-cadherin and β-catenin was reduced by tyrosine phosphorylation of β-catenin, but was unaffected by tyrosine phosphorylation of E-cadherin-C. Treatment of cells with acetaldehyde also reduced the binding of E-cadherin to GST (glutathione S-transferase)–PTP1B. The pairwise binding study showed that GST–E-cadherin-C binds to recombinant PTP1B, but this binding was significantly reduced by tyrosine phosphorylation of E-cadherin. Acetaldehyde increased the phosphorylation of β-catenin on Tyr-331, Tyr-333, Tyr-654 and Tyr-670. These results show that acetaldehyde induces disruption of interactions between E-cadherin, β-catenin and PTP1B by a phosphorylation-dependent mechanism. PMID:17087658

Evidence That Masking of Synapsis Imperfections Counterbalances Quality Control to Promote Efficient Meiosis

PubMed Central

Mlynarczyk-Evans, Susanna; Roelens, Baptiste; Villeneuve, Anne M.

2013-01-01

Reduction in ploidy to generate haploid gametes during sexual reproduction is accomplished by the specialized cell division program of meiosis. Pairing between homologous chromosomes and assembly of the synaptonemal complex at their interface (synapsis) represent intermediate steps in the meiotic program that are essential to form crossover recombination-based linkages between homologs, which in turn enable segregation of the homologs to opposite poles at the meiosis I division. Here, we challenge the mechanisms of pairing and synapsis during C. elegans meiosis by disrupting the normal 1∶1 correspondence between homologs through karyotype manipulation. Using a combination of cytological tools, including S-phase labeling to specifically identify X chromosome territories in highly synchronous cohorts of nuclei and 3D rendering to visualize meiotic chromosome structures and organization, our analysis of trisomic (triplo-X) and polyploid meiosis provides insight into the principles governing pairing and synapsis and how the meiotic program is “wired” to maximize successful sexual reproduction. We show that chromosomes sort into homologous groups regardless of chromosome number, then preferentially achieve pairwise synapsis during a period of active chromosome mobilization. Further, comparisons of synapsis configurations in triplo-X germ cells that are proficient or defective for initiating recombination suggest a role for recombination in restricting chromosomal interactions to a pairwise state. Increased numbers of homologs prolong markers of the chromosome mobilization phase and/or boost germline apoptosis, consistent with triggering quality control mechanisms that promote resolution of synapsis problems and/or cull meiocytes containing synapsis defects. However, we also uncover evidence for the existence of mechanisms that “mask” defects, thus allowing resumption of prophase progression and survival of germ cells despite some asynapsis. We propose that coupling of saturable masking mechanisms with stringent quality controls maximizes meiotic success by making progression and survival dependent on achieving a level of synapsis sufficient for crossover formation without requiring perfect synapsis. PMID:24339786

Mass loss and chemical structures of wheat and maize straws in response to ultraviolet-B radiation and soil contact.

PubMed

Zhou, Guixiang; Zhang, Jiabao; Mao, Jingdong; Zhang, Congzhi; Chen, Lin; Xin, Xiuli; Zhao, Bingzi

2015-10-01

The role of photodegradation, an abiotic process, has been largely overlooked during straw decomposition in mesic ecosystems. We investigated the mass loss and chemical structures of straw decomposition in response to elevated UV-B radiation with or without soil contact over a 12-month litterbag experiment. Wheat and maize straw samples with and without soil contact were exposed to three radiation levels: a no-sunlight control, ambient solar UV-B, and artificially elevated UV-B radiation. A block control with soil contact was not included. Compared with the no-sunlight control, UV-B radiation increased the mass loss by 14-19% and the ambient radiation by 9-16% for wheat and maize straws without soil contact after 12 months. Elevated UV-B exposure decreased the decomposition rates of both wheat and maize straws when in contact with soil. Light exposure resulted in decreased O-alkyl carbons and increased alkyl carbons for both the wheat and maize straws compared with no-sunlight control. The difference in soil contact may influence the contribution of photodegradation to the overall straw decomposition process. These results indicate that we must take into account the effects of photodegradation when explaining the mechanisms of straw decomposition in mesic ecosystems.

Limited-memory adaptive snapshot selection for proper orthogonal decomposition

DOE Office of Scientific and Technical Information (OSTI.GOV)

Oxberry, Geoffrey M.; Kostova-Vassilevska, Tanya; Arrighi, Bill

2015-04-02

Reduced order models are useful for accelerating simulations in many-query contexts, such as optimization, uncertainty quantification, and sensitivity analysis. However, offline training of reduced order models can have prohibitively expensive memory and floating-point operation costs in high-performance computing applications, where memory per core is limited. To overcome this limitation for proper orthogonal decomposition, we propose a novel adaptive selection method for snapshots in time that limits offline training costs by selecting snapshots according an error control mechanism similar to that found in adaptive time-stepping ordinary differential equation solvers. The error estimator used in this work is related to theory boundingmore » the approximation error in time of proper orthogonal decomposition-based reduced order models, and memory usage is minimized by computing the singular value decomposition using a single-pass incremental algorithm. Results for a viscous Burgers’ test problem demonstrate convergence in the limit as the algorithm error tolerances go to zero; in this limit, the full order model is recovered to within discretization error. The resulting method can be used on supercomputers to generate proper orthogonal decomposition-based reduced order models, or as a subroutine within hyperreduction algorithms that require taking snapshots in time, or within greedy algorithms for sampling parameter space.« less

Thermal decomposition pathways of hydroxylamine: theoretical investigation on the initial steps.

PubMed

Wang, Qingsheng; Wei, Chunyang; Pérez, Lisa M; Rogers, William J; Hall, Michael B; Mannan, M Sam

2010-09-02

Hydroxylamine (NH(2)OH) is an unstable compound at room temperature, and it has been involved in two tragic industrial incidents. Although experimental studies have been carried out to study the thermal stability of hydroxylamine, the detailed decomposition mechanism is still in debate. In this work, several density functional and ab initio methods were used in conjunction with several basis sets to investigate the initial thermal decomposition steps of hydroxylamine, including both unimolecular and bimolecular reaction pathways. The theoretical investigation shows that simple bond dissociations and unimolecular reactions are unlikely to occur. The energetically favorable initial step of decomposition pathways was determined as a bimolecular isomerization of hydroxylamine into ammonia oxide with an activation barrier of approximately 25 kcal/mol at the MPW1K level of theory. Because hydroxylamine is available only in aqueous solutions, solvent effects on the initial decomposition pathways were also studied using water cluster methods and the polarizable continuum model (PCM). In water, the activation barrier of the bimolecular isomerization reaction decreases to approximately 16 kcal/mol. The results indicate that the bimolecular isomerization pathway of hydroxylamine is more favorable in aqueous solutions. However, the bimolecular nature of this reaction means that more dilute aqueous solution will be more stable.

Thermal decomposition of condensed-phase nitromethane from molecular dynamics from ReaxFF reactive dynamics.

PubMed

Han, Si-ping; van Duin, Adri C T; Goddard, William A; Strachan, Alejandro

2011-05-26

We studied the thermal decomposition and subsequent reaction of the energetic material nitromethane (CH(3)NO(2)) using molecular dynamics with ReaxFF, a first principles-based reactive force field. We characterize the chemistry of liquid and solid nitromethane at high temperatures (2000-3000 K) and density 1.97 g/cm(3) for times up to 200 ps. At T = 3000 K the first reaction in the decomposition of nitromethane is an intermolecular proton transfer leading to CH(3)NOOH and CH(2)NO(2). For lower temperatures (T = 2500 and 2000 K) the first reaction during decomposition is often an isomerization reaction involving the scission of the C-N bond the formation of a C-O bond to form methyl nitrate (CH(3)ONO). Also at very early times we observe intramolecular proton transfer events. The main product of these reactions is H(2)O which starts forming following those initiation steps. The appearance of H(2)O marks the beginning of the exothermic chemistry. Recent quantum-mechanics-based molecular dynamics simulations on the chemical reactions and time scales for decomposition of a crystalline sample heated to T = 3000 K for a few picoseconds are in excellent agreement with our results, providing an important, direct validation of ReaxFF.

Laser augmented decomposition. II. D/sub 3/BPF/sub 3/. [Deuterium effects

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chien, K.R.; Bauer, S.H.

1976-06-17

The study of the accelerated decomposition of H/sub 3/BPF/sub 3/ induced by laser radiation (930-950 cm/sup -1/ was extended to the fully deuterated species. While in all essential respects the kinetics of the ir photolysis for the two compounds are identical, the few differences which were uncovered proved crucial in pointing to interesting features of the mechanism. These verified predictions were based on a normal mode analysis for the distribution of potential energy among the internal coordinates. For the laser augmented decomposition, E/sub a//sup L/ = 3.5 +- 1 kcal/mol, compared with E/sub a//sup th/ = 29.3 kcal/mol for themore » thermal process. The quantum efficiency is low, approximately 4 x 10/sup 4/ photons/molecule decomposed. The rates of decomposition depend on the isotopic content and are sensitively dependent on the frequency of the irradiating line. For example, with P(24) large fractionation ratios were found for D/sub 3/BPF/sub 3/ vs. H/sub 3/BPF/sub 3/, and small differences for D/sub 3//sup 11/BPF/sub 3/ vs. D/sub 3//sup 10/BPF/sub 3/. The levels of decomposition induced by the sequential three-photon absorption have been semiquantitatively accounted for.« less

Effect of the carbon coating in Fe-C-TiO(2) photocatalyst on phenol decomposition under UV irradiation via photo-Fenton process.

PubMed

Tryba, Beata; Morawski, Antoni W; Inagaki, Michio; Toyoda, Masahiro

2006-08-01

Fe-C-TiO(2) photocatalysts which contained the residue carbon (0.2-3.3 mass%) were prepared from a mixture of TiO(2) and FeC(2)O(4) through the heating at 673-1173 K in Ar. These photocatalysts did not show a high adsorption of phenol, but they were active in photo-Fenton reactions during decomposition of phenol under UV irradiation with addition of H(2)O(2). It was proved that Fe(2+) governed the photoactivity of Fe-C-TiO(2) photocatalysts, it decreased with heat-treatment temperature above 773 K. For comparison, Fe-TiO(2) photocatalyst was prepared by heating TiO(2) and FeC(2)O(4) at 823 K in air for 3h. Phenol decomposition was going much slower on Fe-TiO(2) photocatalyst in comparison with Fe-C-TiO(2), of which mechanism was different, on the former phenol was decomposed by the radical reaction, on the latter through a complex reaction with iron and intermediates of phenol decomposition. Therefore carbon-coating TiO(2) was found to be advantageous for mounting iron and its application for the phenol decomposition via photo-Fenton process.

Mass loss and chemical structures of wheat and maize straws in response to ultraviolet-B radiation and soil contact

PubMed Central

Zhou, Guixiang; Zhang, Jiabao; Mao, Jingdong; Zhang, Congzhi; Chen, Lin; Xin, Xiuli; Zhao, Bingzi

2015-01-01

The role of photodegradation, an abiotic process, has been largely overlooked during straw decomposition in mesic ecosystems. We investigated the mass loss and chemical structures of straw decomposition in response to elevated UV-B radiation with or without soil contact over a 12-month litterbag experiment. Wheat and maize straw samples with and without soil contact were exposed to three radiation levels: a no-sunlight control, ambient solar UV-B, and artificially elevated UV-B radiation. A block control with soil contact was not included. Compared with the no-sunlight control, UV-B radiation increased the mass loss by 14–19% and the ambient radiation by 9–16% for wheat and maize straws without soil contact after 12 months. Elevated UV-B exposure decreased the decomposition rates of both wheat and maize straws when in contact with soil. Light exposure resulted in decreased O-alkyl carbons and increased alkyl carbons for both the wheat and maize straws compared with no-sunlight control. The difference in soil contact may influence the contribution of photodegradation to the overall straw decomposition process. These results indicate that we must take into account the effects of photodegradation when explaining the mechanisms of straw decomposition in mesic ecosystems. PMID:26423726

Thermal decomposition of europium sulfates Eu2(SO4)3·8H2O and EuSO4

NASA Astrophysics Data System (ADS)

Denisenko, Yu. G.; Khritokhin, N. A.; Andreev, O. V.; Basova, S. A.; Sal'nikova, E. I.; Polkovnikov, A. A.

2017-11-01

Reactions of europium sulfates Eu2(SO4)3·8H2O and EuSO4 complete decomposition were studied by Simultaneous Thermal Analysis. It was revealed that one-step dehydratation of Eu2(SO4)3·8H2O crystallohydrate is accompanied by the formation of amorphous anhydrous europium sulfate Eu2(SO4)3. Crystallization of amorphous europium (III) sulfate occurs at 381.1 °C (in argon) and 391.3 °C (in air). The average enthalpy values for dehydratation reaction of Eu2(SO4)3·8H2O (ΔH° = 141.1 kJ/mol), decomposition reactions of Eu2(SO4)3 (ΔH = 463.1 kJ/mol), Eu2O2SO4 (ΔH = 378.4 kJ/mol) and EuSO4 (ΔH = 124.1 kJ/mol) were determined. The step process mechanisms of thermal decomposition of europium (III) sulfate in air and europium (II) sulfate in inert atmosphere were established and justified. The kinetic parameters of complete thermal decomposition of europium (III) sulfate octahydrate were calculated by Kissinger model. The standard enthalpies of compound formation were calculated using thermal effects and formation enthalpy data for binary compounds.

Decomposition of toluene in a steady-state atmospheric-pressure glow discharge

DOE Office of Scientific and Technical Information (OSTI.GOV)

Trushkin, A. N.; Grushin, M. E.; Kochetov, I. V.

Results are presented from experimental studies of decomposition of toluene (C{sub 6}H{sub 5}CH{sub 3}) in a polluted air flow by means of a steady-state atmospheric pressure glow discharge at different water vapor contents in the working gas. The experimental results on the degree of C{sub 6}H{sub 5}CH{sub 3} removal are compared with the results of computer simulations conducted in the framework of the developed kinetic model of plasma chemical decomposition of toluene in the N{sub 2}: O{sub 2}: H{sub 2}O gas mixture. A substantial influence of the gas flow humidity on toluene decomposition in the atmospheric pressure glow discharge ismore » demonstrated. The main mechanisms of the influence of humidity on C{sub 6}H{sub 5}CH{sub 3} decomposition are determined. The existence of two stages in the process of toluene removal, which differ in their duration and the intensity of plasma chemical decomposition of C{sub 6}H{sub 5}CH{sub 3} is established. Based on the results of computer simulations, the composition of the products of plasma chemical reactions at the output of the reactor is analyzed as a function of the specific energy deposition and gas flow humidity. The existence of a catalytic cycle in which hydroxyl radical OH acts a catalyst and which substantially accelerates the recombination of oxygen atoms and suppression of ozone generation when the plasma-forming gas contains water vapor is established.« less

Stability analysis of gyroscopic systems with delay via decomposition

NASA Astrophysics Data System (ADS)

Aleksandrov, A. Yu.; Zhabko, A. P.; Chen, Y.

2018-05-01

A mechanical system describing by the second order linear differential equations with a positive parameter at the velocity forces and with time delay in the positional forces is studied. Using the decomposition method and Lyapunov-Krasovskii functionals, conditions are obtained under which from the asymptotic stability of two auxiliary first order subsystems it follows that, for sufficiently large values of the parameter, the original system is also asymptotically stable. Moreover, it is shown that the proposed approach can be applied to the stability investigation of linear gyroscopic systems with switched positional forces.

Comment on “A novel and facile decay path of Criegee intermediates by intramolecular insertion reactions via roaming transition states” [J. Chem. Phys. 142, 124312 (2015)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Harding, Lawrence B.; Klippenstein, Stephen J.

2015-10-28

We discuss the recent report of a roaming type mechanism for the decomposition of the Criegee intermediate. We show that the predicted barrier height for this new pathway is too low by ∼30 kcal/mol owing to an inconsistent use of spin-restricted and spin-unrestricted calculations. As a result, this new pathway is not expected to compete significantly with the well-known dioxirane pathways for the decomposition of the Criegee intermediate.

A transient semimetallic layer in detonating nitromethane

NASA Astrophysics Data System (ADS)

Reed, Evan J.; Riad Manaa, M.; Fried, Laurence E.; Glaesemann, Kurt R.; Joannopoulos, J. D.

2008-01-01

Despite decades of research, the microscopic details and extreme states of matter found within a detonating high explosive have yet to be elucidated. Here we present the first quantum molecular-dynamics simulation of a shocked explosive near detonation conditions. We discover that the wide-bandgap insulator nitromethane (CH3NO2) undergoes chemical decomposition and a transformation into a semimetallic state for a limited distance behind the detonation front. We find that this transformation is associated with the production of charged decomposition species and provides a mechanism to explain recent experimental observations.

Ab initio molecular dynamics simulations of the initial stages of solid-electrolyte interphase formation on lithium ion battery graphitic anodes.

PubMed

Leung, Kevin; Budzien, Joanne L

2010-07-07

The decomposition of ethylene carbonate (EC) during the initial growth of solid-electrolyte interphase (SEI) films at the solvent-graphitic anode interface is critical to lithium ion battery operations. Ab initio molecular dynamics simulations of explicit liquid EC/graphite interfaces are conducted to study these electrochemical reactions. We show that carbon edge terminations are crucial at this stage, and that achievable experimental conditions can lead to surprisingly fast EC breakdown mechanisms, yielding decomposition products seen in experiments but not previously predicted.

0 ν β β -decay nuclear matrix element for light and heavy neutrino mass mechanisms from deformed quasiparticle random-phase approximation calculations for 76Ge, 82Se, 130Te, 136Xe, and 150Nd with isospin restoration

NASA Astrophysics Data System (ADS)

Fang, Dong-Liang; Faessler, Amand; Šimkovic, Fedor

2018-04-01

In this paper, with restored isospin symmetry, we evaluated the neutrinoless double-β -decay nuclear matrix elements for 76Ge, 82Se, 130Te, 136Xe, and 150Nd for both the light and heavy neutrino mass mechanisms using the deformed quasiparticle random-phase approximation approach with realistic forces. We give detailed decompositions of the nuclear matrix elements over different intermediate states and nucleon pairs, and discuss how these decompositions are affected by the model space truncations. Compared to the spherical calculations, our results show reductions from 30 % to about 60 % of the nuclear matrix elements for the calculated isotopes mainly due to the presence of the BCS overlap factor between the initial and final ground states. The comparison between different nucleon-nucleon (NN) forces with corresponding short-range correlations shows that the choice of the NN force gives roughly 20 % deviations for the light exchange neutrino mechanism and much larger deviations for the heavy neutrino exchange mechanism.

Biomass pyrolysis: Thermal decomposition mechanisms of furfural and benzaldehyde

NASA Astrophysics Data System (ADS)

Vasiliou, AnGayle K.; Kim, Jong Hyun; Ormond, Thomas K.; Piech, Krzysztof M.; Urness, Kimberly N.; Scheer, Adam M.; Robichaud, David J.; Mukarakate, Calvin; Nimlos, Mark R.; Daily, John W.; Guan, Qi; Carstensen, Hans-Heinrich; Ellison, G. Barney

2013-09-01

The thermal decompositions of furfural and benzaldehyde have been studied in a heated microtubular flow reactor. The pyrolysis experiments were carried out by passing a dilute mixture of the aromatic aldehydes (roughly 0.1%-1%) entrained in a stream of buffer gas (either He or Ar) through a pulsed, heated SiC reactor that is 2-3 cm long and 1 mm in diameter. Typical pressures in the reactor are 75-150 Torr with the SiC tube wall temperature in the range of 1200-1800 K. Characteristic residence times in the reactor are 100-200 μsec after which the gas mixture emerges as a skimmed molecular beam at a pressure of approximately 10 μTorr. Products were detected using matrix infrared absorption spectroscopy, 118.2 nm (10.487 eV) photoionization mass spectroscopy and resonance enhanced multiphoton ionization. The initial steps in the thermal decomposition of furfural and benzaldehyde have been identified. Furfural undergoes unimolecular decomposition to furan + CO: C4H3O-CHO (+ M) → CO + C4H4O. Sequential decomposition of furan leads to the production of HC≡CH, CH2CO, CH3C≡CH, CO, HCCCH2, and H atoms. In contrast, benzaldehyde resists decomposition until higher temperatures when it fragments to phenyl radical plus H atoms and CO: C6H5CHO (+ M) → C6H5CO + H → C6H5 + CO + H. The H atoms trigger a chain reaction by attacking C6H5CHO: H + C6H5CHO → [C6H6CHO]* → C6H6 + CO + H. The net result is the decomposition of benzaldehyde to produce benzene and CO.

Surface-Mediated Solvent Decomposition in Li–Air Batteries: Impact of Peroxide and Superoxide Surface Terminations

DOE PAGES

Kumar, Nitin; Radin, Maxwell D.; Wood, Brandon C.; ...

2015-04-13

A viable Li/O 2 battery will require the development of stable electrolytes that do not continuously decompose during cell operation. In some recent experiments it is suggested that reactions occurring at the interface between the liquid electrolyte and the solid lithium peroxide (Li 2O 2) discharge phase are a major contributor to these instabilities. To clarify the mechanisms associated with these reactions, a variety of atomistic simulation techniques, classical Monte Carlo, van der Waals-augmented density functional theory, ab initio molecular dynamics, and various solvation models, are used to study the initial decomposition of the common electrolyte solvent, dimethoxyethane (DME), onmore » surfaces of Li 2O 2. Comparisons are made between the two predominant Li 2O 2 surface charge states by calculating decomposition pathways on peroxide-terminated (O 2 2–) and superoxide-terminated (O 2 1–) facets. For both terminations, DME decomposition proceeds exothermically via a two-step process comprised of hydrogen abstraction (H-abstraction) followed by nucleophilic attack. In the first step, abstracted H dissociates a surface O 2 dimer, and combines with a dissociated oxygen to form a hydroxide ion (OH –). In the remaining surface oxygen then attacks the DME, resulting in a DME fragment that is strongly bound to the Li 2O 2 surface. DME decomposition is predicted to be more exothermic on the peroxide facet; nevertheless, the rate of DME decomposition is faster on the superoxide termination. The impact of solvation (explicit vs implicit) and an applied electric field on the reaction energetics are investigated. Finally, our calculations suggest that surface-mediated electrolyte decomposition should out-pace liquid-phase processes such as solvent auto-oxidation by dissolved O 2.« less

Comparison of Techniques for Sampling Adult Necrophilous Insects From Pig Carcasses.

PubMed

Cruise, Angela; Hatano, Eduardo; Watson, David W; Schal, Coby

2018-02-06

Studies of the pre-colonization interval and mechanisms driving necrophilous insect ecological succession depend on effective sampling of adult insects and knowledge of their diel and successional activity patterns. The number of insects trapped, their diversity, and diel periodicity were compared with four sampling methods on neonate pigs. Sampling method, time of day and decomposition age of the pigs significantly affected the number of insects sampled from pigs. We also found significant interactions of sampling method and decomposition day, time of sampling and decomposition day. No single method was superior to the other methods during all three decomposition days. Sampling times after noon yielded the largest samples during the first 2 d of decomposition. On day 3 of decomposition however, all sampling times were equally effective. Therefore, to maximize insect collections from neonate pigs, the method used to sample must vary by decomposition day. The suction trap collected the most species-rich samples, but sticky trap samples were the most diverse, when both species richness and evenness were factored into a Shannon diversity index. Repeated sampling during the noon to 18:00 hours period was most effective to obtain the maximum diversity of trapped insects. The integration of multiple sampling techniques would most effectively sample the necrophilous insect community. However, because all four tested methods were deficient at sampling beetle species, future work should focus on optimizing the most promising methods, alone or in combinations, and incorporate hand-collections of beetles. © The Author(s) 2018. Published by Oxford University Press on behalf of Entomological Society of America. All rights reserved. For permissions, please e-mail: journals.permissions@oup.com.

The interactive effect of the degradation of cotton clothing and decomposition fluid production associated with decaying remains.

PubMed

Ueland, Maiken; Nizio, Katie D; Forbes, Shari L; Stuart, Barbara H

2015-10-01

Textiles are a commonly encountered source of evidence in forensic cases. In the past, most research has been focused on how textiles affect the decomposition process while little attention has been paid to how the decomposition products interact with the textiles. While some studies have shown that the presence of remains will have an effect on the degradation of clothing associated with a decaying body, very little work has been carried out on the specific mechanisms that prevent or delay textile degradation when in contact with decomposing remains. In order to investigate the effect of decomposition fluid on textile degradation, three clothed domestic pig (Sus scrofa domesticus) carcasses were placed on a soil surface, textile specimens were collected over a period of a year and were then analysed using ATR-FTIR spectroscopy and GC-MS. Multivariate statistical analysis was used to analyse the data. Cotton specimens not associated with remains degraded markedly, whereas the samples exposed to decomposition fluids remained relatively intact over the same time frame. An investigation of the decomposition by-products found that the protein-related bands remained stable and unchanged throughout the experiment. Lipid components, on the other hand, demonstrated a significant change; this was confirmed with the use of both ATR-FTIR spectroscopy and GC-MS. Through an advanced statistical approach, information about the decomposition by-products and their characteristics was obtained. There is potential that the lipid profile in a textile specimen could be a valuable tool used in the examination of clothing located at a crime scene. Copyright © 2015 Elsevier Ireland Ltd. All rights reserved.

Obtaining tight bounds on higher-order interferences with a 5-path interferometer

NASA Astrophysics Data System (ADS)

Kauten, Thomas; Keil, Robert; Kaufmann, Thomas; Pressl, Benedikt; Brukner, Časlav; Weihs, Gregor

2017-03-01

Within the established theoretical framework of quantum mechanics, interference always occurs between pairs of paths through an interferometer. Higher order interferences with multiple constituents are excluded by Born’s rule and can only exist in generalized probabilistic theories. Thus, high-precision experiments searching for such higher order interferences are a powerful method to distinguish between quantum mechanics and more general theories. Here, we perform such a test in an optical multi-path interferometer, which avoids crucial systematic errors, has access to the entire phase space and is more stable than previous experiments. Our results are in accordance with quantum mechanics and rule out the existence of higher order interference terms in optical interferometry to an extent that is more than four orders of magnitude smaller than the expected pairwise interference, refining previous bounds by two orders of magnitude.

Modal decomposition of turbulent supersonic cavity

NASA Astrophysics Data System (ADS)

Soni, R. K.; Arya, N.; De, A.

2018-06-01

Self-sustained oscillations in a Mach 3 supersonic cavity with a length-to-depth ratio of three are investigated using wall-modeled large eddy simulation methodology for ReD = 3.39× 105 . The unsteady data obtained through computation are utilized to investigate the spatial and temporal evolution of the flow field, especially the second invariant of the velocity tensor, while the phase-averaged data are analyzed over a feedback cycle to study the spatial structures. This analysis is accompanied by the proper orthogonal decomposition (POD) data, which reveals the presence of discrete vortices along the shear layer. The POD analysis is performed in both the spanwise and streamwise planes to extract the coherence in flow structures. Finally, dynamic mode decomposition is performed on the data sequence to obtain the dynamic information and deeper insight into the self-sustained mechanism.

Preparation of surface modified TiO2/rGO microspheres and application in the photocatalytic decomposition of oleic acid

NASA Astrophysics Data System (ADS)

Wu, Xin; Zeng, Min; Tong, Xiaoling; Li, Fuyun; Xu, Youyou

2018-05-01

The comprehensive utilization of waste cooking oil is an important research topic in food science. In this study, the surface modified mesoporous anatase TiO2/reduced graphene oxide (rGO) microspheres with a high specific surface area have been successfully synthesized, through hydrothermal routes and hydrazine reduced graphene oxide. The photocatalytic decomposition of waste rapeseed oil has also been studied using TiO2/rGO microspheres as photocatalyst. The result shows that the reduced graphene oxide in these nanocomposites can act as adsorbent and photocatalyst, and the temperature and the oxygen amount also are the most important factors affecting the oleic acid decomposition products. There interesting results not only helpful for the study of the mechanism of photocatalytic, but also useful for the rational use of waste cooking oil.

Preparation, non-isothermal decomposition kinetics, heat capacity and adiabatic time-to-explosion of NTOxDNAZ.

PubMed

Ma, Haixia; Yan, Biao; Li, Zhaona; Guan, Yulei; Song, Jirong; Xu, Kangzhen; Hu, Rongzu

2009-09-30

NTOxDNAZ was prepared by mixing 3,3-dinitroazetidine (DNAZ) and 3-nitro-1,2,4-triazol-5-one (NTO) in ethanol solution. The thermal behavior of the title compound was studied under a non-isothermal condition by DSC and TG/DTG methods. The kinetic parameters were obtained from analysis of the DSC and TG/DTG curves by Kissinger method, Ozawa method, the differential method and the integral method. The main exothermic decomposition reaction mechanism of NTOxDNAZ is classified as chemical reaction, and the kinetic parameters of the reaction are E(a)=149.68 kJ mol(-1) and A=10(15.81)s(-1). The specific heat capacity of the title compound was determined with continuous C(p) mode of microcalorimeter. The standard mole specific heat capacity of NTOxDNAZ was 352.56 J mol(-1)K(-1) in 298.15K. Using the relationship between C(p) and T and the thermal decomposition parameters, the time of the thermal decomposition from initialization to thermal explosion (adiabatic time-to-explosion) was obtained.

Initial decomposition of the condensed-phase β-HMX under shock waves: molecular dynamics simulations.

PubMed

Ge, Ni-Na; Wei, Yong-Kai; Ji, Guang-Fu; Chen, Xiang-Rong; Zhao, Feng; Wei, Dong-Qing

2012-11-26

We have performed quantum-based multiscale simulations to study the initial chemical processes of condensed-phase octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX) under shock wave loading. A self-consistent charge density-functional tight-binding (SCC-DFTB) method was employed. The results show that the initial decomposition of shocked HMX is triggered by the N-NO(2) bond breaking under the low velocity impact (8 km/s). As the shock velocity increases (11 km/s), the homolytic cleavage of the N-NO(2) bond is suppressed under high pressure, the C-H bond dissociation becomes the primary pathway for HMX decomposition in its early stages. It is accompanied by a five-membered ring formation and hydrogen transfer from the CH(2) group to the -NO(2) group. Our simulations suggest that the initial chemical processes of shocked HMX are dependent on the impact velocity, which gain new insights into the initial decomposition mechanism of HMX upon shock loading at the atomistic level, and have important implications for understanding and development of energetic materials.

Solid state green synthesis and catalytic activity of CuO nanorods in thermal decomposition of potassium periodate

NASA Astrophysics Data System (ADS)

Patel, Vinay Kumar; Bhattacharya, Shantanu

2017-09-01

The present study reports a facile solid state green synthesis process using the leaf extracts of Hibiscus rosa-sinensis to synthesize CuO nanorods with average diameters of 15-20 nm and lengths up to 100 nm. The as-synthesized CuO nanorods were characterized by x-ray diffraction, Fourier transform infrared spectroscopy, transmission electron microscopy and selected area electron diffraction. The formation mechanism of CuO nanorods has been explained by involving the individual role of amide I (amino groups) and carboxylate groups under excess hydroxyl ions released from NaOH. The catalytic activity of CuO nanorods in thermal decomposition of potassium periodate microparticles (µ-KIO4) microparticles was studied by thermo gravimetric analysis measurement. The original size (~100 µm) of commercially procured potassium periodate was reduced to microscale length scale to about one-tenth by PEG200 assisted emulsion process. The CuO nanorods prepared by solid state green route were found to catalyze the thermal decomposition of µ-KIO4 with a reduction of 18 °C in the final thermal decomposition temperature of potassium periodate.

Blazing Signature Filter: a library for fast pairwise similarity comparisons

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lee, Joon-Yong; Fujimoto, Grant M.; Wilson, Ryan

Identifying similarities between datasets is a fundamental task in data mining and has become an integral part of modern scientific investigation. Whether the task is to identify co-expressed genes in large-scale expression surveys or to predict combinations of gene knockouts which would elicit a similar phenotype, the underlying computational task is often a multi-dimensional similarity test. As datasets continue to grow, improvements to the efficiency, sensitivity or specificity of such computation will have broad impacts as it allows scientists to more completely explore the wealth of scientific data. A significant practical drawback of large-scale data mining is the vast majoritymore » of pairwise comparisons are unlikely to be relevant, meaning that they do not share a signature of interest. It is therefore essential to efficiently identify these unproductive comparisons as rapidly as possible and exclude them from more time-intensive similarity calculations. The Blazing Signature Filter (BSF) is a highly efficient pairwise similarity algorithm which enables extensive data mining within a reasonable amount of time. The algorithm transforms datasets into binary metrics, allowing it to utilize the computationally efficient bit operators and provide a coarse measure of similarity. As a result, the BSF can scale to high dimensionality and rapidly filter unproductive pairwise comparison. Two bioinformatics applications of the tool are presented to demonstrate the ability to scale to billions of pairwise comparisons and the usefulness of this approach.« less

The structure of pairwise correlation in mouse primary visual cortex reveals functional organization in the absence of an orientation map.

PubMed

Denman, Daniel J; Contreras, Diego

2014-10-01

Neural responses to sensory stimuli are not independent. Pairwise correlation can reduce coding efficiency, occur independent of stimulus representation, or serve as an additional channel of information, depending on the timescale of correlation and the method of decoding. Any role for correlation depends on its magnitude and structure. In sensory areas with maps, like the orientation map in primary visual cortex (V1), correlation is strongly related to the underlying functional architecture, but it is unclear whether this correlation structure is an essential feature of the system or arises from the arrangement of cells in the map. We assessed the relationship between functional architecture and pairwise correlation by measuring both synchrony and correlated spike count variability in mouse V1, which lacks an orientation map. We observed significant pairwise synchrony, which was organized by distance and relative orientation preference between cells. We also observed nonzero correlated variability in both the anesthetized (0.16) and awake states (0.18). Our results indicate that the structure of pairwise correlation is maintained in the absence of an underlying anatomical organization and may be an organizing principle of the mammalian visual system preserved by nonrandom connectivity within local networks. © The Author 2013. Published by Oxford University Press. All rights reserved. For Permissions, please e-mail: journals.permissions@oup.com.

Pairwise Maximum Entropy Models for Studying Large Biological Systems: When They Can Work and When They Can't

PubMed Central

Roudi, Yasser; Nirenberg, Sheila; Latham, Peter E.

2009-01-01

One of the most critical problems we face in the study of biological systems is building accurate statistical descriptions of them. This problem has been particularly challenging because biological systems typically contain large numbers of interacting elements, which precludes the use of standard brute force approaches. Recently, though, several groups have reported that there may be an alternate strategy. The reports show that reliable statistical models can be built without knowledge of all the interactions in a system; instead, pairwise interactions can suffice. These findings, however, are based on the analysis of small subsystems. Here, we ask whether the observations will generalize to systems of realistic size, that is, whether pairwise models will provide reliable descriptions of true biological systems. Our results show that, in most cases, they will not. The reason is that there is a crossover in the predictive power of pairwise models: If the size of the subsystem is below the crossover point, then the results have no predictive power for large systems. If the size is above the crossover point, then the results may have predictive power. This work thus provides a general framework for determining the extent to which pairwise models can be used to predict the behavior of large biological systems. Applied to neural data, the size of most systems studied so far is below the crossover point. PMID:19424487

A periodic energy decomposition analysis method for the investigation of chemical bonding in extended systems

DOE Office of Scientific and Technical Information (OSTI.GOV)

Raupach, Marc; Tonner, Ralf, E-mail: tonner@chemie.uni-marburg.de

The development and first applications of a new periodic energy decomposition analysis (pEDA) scheme for extended systems based on the Kohn-Sham approach to density functional theory are described. The pEDA decomposes the bonding energy between two fragments (e.g., the adsorption energy of a molecule on a surface) into several well-defined terms: preparation, electrostatic, Pauli repulsion, and orbital relaxation energies. This is complemented by consideration of dispersion interactions via a pairwise scheme. One major extension toward a previous implementation [Philipsen and Baerends, J. Phys. Chem. B 110, 12470 (2006)] lies in the separate discussion of electrostatic and Pauli and the additionmore » of a dispersion term. The pEDA presented here for an implementation based on atomic orbitals can handle restricted and unrestricted fragments for 0D to 3D systems considering periodic boundary conditions with and without the determination of fragment occupations. For the latter case, reciprocal space sampling is enabled. The new method gives comparable results to established schemes for molecular systems and shows good convergence with respect to the basis set (TZ2P), the integration accuracy, and k-space sampling. Four typical bonding scenarios for surface-adsorbate complexes were chosen to highlight the performance of the method representing insulating (CO on MgO(001)), metallic (H{sub 2} on M(001), M = Pd, Cu), and semiconducting (CO and C{sub 2}H{sub 2} on Si(001)) substrates. These examples cover diverse substrates as well as bonding scenarios ranging from weakly interacting to covalent (shared electron and donor acceptor) bonding. The results presented lend confidence that the pEDA will be a powerful tool for the analysis of surface-adsorbate bonding in the future, enabling the transfer of concepts like ionic and covalent bonding, donor-acceptor interaction, steric repulsion, and others to extended systems.« less

Mechanisms of propylene glycol and triacetin pyrolysis.

PubMed

Laino, Teodoro; Tuma, Christian; Moor, Philippe; Martin, Elyette; Stolz, Steffen; Curioni, Alessandro

2012-05-10

Propylene glycol and triacetin are chemical compounds, commonly used as food additives. Though the usage of the pure chemicals is not considered harmful when used as dietary supplements, little is known about the nature of their thermal degradation products and the impact they may have on human health. For these reasons, in this manuscript we investigate the thermal decomposition mechanisms of both neutral propylene glycol and triacetin in the gas phase by a novel simulation framework. This is based on a free energy sampling methodology followed by an accurate energy refinement. Structures, Gibbs free energy barriers, and rate constants at 800 K were computed for the different steps involved in the two pyrolytic processes. The thermal decomposition mechanisms found theoretically for propylene glycol and triacetin were validated by a qualitative experimental investigation using gas-phase chromatography-mass spectroscopy, with excellent agreement. The results provide a validation of the novel simulation framework and shed light on the potential hazard to the health that propylene glycol and triacetin may have when exposed to high temperatures.

A density functional approach to ferrogels

NASA Astrophysics Data System (ADS)

Cremer, P.; Heinen, M.; Menzel, A. M.; Löwen, H.

2017-07-01

Ferrogels consist of magnetic colloidal particles embedded in an elastic polymer matrix. As a consequence, their structural and rheological properties are governed by a competition between magnetic particle-particle interactions and mechanical matrix elasticity. Typically, the particles are permanently fixed within the matrix, which makes them distinguishable by their positions. Over time, particle neighbors do not change due to the fixation by the matrix. Here we present a classical density functional approach for such ferrogels. We map the elastic matrix-induced interactions between neighboring colloidal particles distinguishable by their positions onto effective pairwise interactions between indistinguishable particles similar to a ‘pairwise pseudopotential’. Using Monte-Carlo computer simulations, we demonstrate for one-dimensional dipole-spring models of ferrogels that this mapping is justified. We then use the pseudopotential as an input into classical density functional theory of inhomogeneous fluids and predict the bulk elastic modulus of the ferrogel under various conditions. In addition, we propose the use of an ‘external pseudopotential’ when one switches from the viewpoint of a one-dimensional dipole-spring object to a one-dimensional chain embedded in an infinitely extended bulk matrix. Our mapping approach paves the way to describe various inhomogeneous situations of ferrogels using classical density functional concepts of inhomogeneous fluids.

Statistical Mechanics of US Supreme Court

NASA Astrophysics Data System (ADS)

Lee, Edward; Broedersz, Chase; Bialek, William; Biophysics Theory Group Team

2014-03-01

We build simple models for the distribution of voting patterns in a group, using the Supreme Court of the United States as an example. The least structured, or maximum entropy, model that is consistent with the observed pairwise correlations among justices' votes is equivalent to an Ising spin glass. While all correlations (perhaps surprisingly) are positive, the effective pairwise interactions in the spin glass model have both signs, recovering some of our intuition that justices on opposite sides of the ideological spectrum should have a negative influence on one another. Despite the competing interactions, a strong tendency toward unanimity emerges from the model, and this agrees quantitatively with the data. The model shows that voting patterns are organized in a relatively simple ``energy landscape,'' correctly predicts the extent to which each justice is correlated with the majority, and gives us a measure of the influence that justices exert on one another. These results suggest that simple models, grounded in statistical physics, can capture essential features of collective decision making quantitatively, even in a complex political context. Funded by National Science Foundation Grants PHY-0957573 and CCF-0939370, WM Keck Foundation, Lewis-Sigler Fellowship, Burroughs Wellcome Fund, and Winston Foundation.

Soil C and N availability determine the priming effect: microbial N mining and stoichiometric decomposition theories.

PubMed

Chen, Ruirui; Senbayram, Mehmet; Blagodatsky, Sergey; Myachina, Olga; Dittert, Klaus; Lin, Xiangui; Blagodatskaya, Evgenia; Kuzyakov, Yakov

2014-07-01

The increasing input of anthropogenically derived nitrogen (N) to ecosystems raises a crucial question: how does available N modify the decomposer community and thus affects the mineralization of soil organic matter (SOM). Moreover, N input modifies the priming effect (PE), that is, the effect of fresh organics on the microbial decomposition of SOM. We studied the interactive effects of C and N on SOM mineralization (by natural (13) C labelling adding C4 -sucrose or C4 -maize straw to C3 -soil) in relation to microbial growth kinetics and to the activities of five hydrolytic enzymes. This encompasses the groups of parameters governing two mechanisms of priming effects - microbial N mining and stoichiometric decomposition theories. In sole C treatments, positive PE was accompanied by a decrease in specific microbial growth rates, confirming a greater contribution of K-strategists to the decomposition of native SOM. Sucrose addition with N significantly accelerated mineralization of native SOM, whereas mineral N added with plant residues accelerated decomposition of plant residues. This supports the microbial mining theory in terms of N limitation. Sucrose addition with N was accompanied by accelerated microbial growth, increased activities of β-glucosidase and cellobiohydrolase, and decreased activities of xylanase and leucine amino peptidase. This indicated an increased contribution of r-strategists to the PE and to decomposition of cellulose but the decreased hemicellulolytic and proteolytic activities. Thus, the acceleration of the C cycle was primed by exogenous organic C and was controlled by N. This confirms the stoichiometric decomposition theory. Both K- and r-strategists were beneficial for priming effects, with an increasing contribution of K-selected species under N limitation. Thus, the priming phenomenon described in 'microbial N mining' theory can be ascribed to K-strategists. In contrast, 'stoichiometric decomposition' theory, that is, accelerated OM mineralization due to balanced microbial growth, is explained by domination of r-strategists. © 2013 John Wiley & Sons Ltd.

Soil C and N availability determine the priming effect: microbial N mining and stoichiometric decomposition theories

NASA Astrophysics Data System (ADS)

Chen, Ruirui; Senbayram, Mehmet; Blagodatsky, Sergey; Dittert, Klaus; Lin, Xiangui; Blagodatskaya, Evgenia; Kuzyakov, Yakov

2014-05-01

The increasing input of anthropogenically derived nitrogen (N) to ecosystems raises a crucial question: how does available N modify the decomposer community and thus affects the mineralization of soil organic matter (SOM). Moreover, N input modifies the priming effect (PE), that is, the effect of fresh organics on the microbial decomposition of SOM. We studied the interactive effects of C and N on SOM mineralization (by natural 13C labelling adding C4-sucrose or C4-maize straw to C3-soil) in relation to microbial growth kinetics and to the activities of five hydrolytic enzymes. This encompasses the groups of parameters governing two mechanisms of priming effects - microbial N mining and stoichiometric decomposition theories. In sole C treatments, positive PE was accompanied by a decrease in specific microbial growth rates, confirming a greater contribution of K-strategists to the decomposition of native SOM. Sucrose addition with N significantly accelerated mineralization of native SOM, whereas mineral N added with plant residues accelerated decomposition of plant residues. This supports the microbial mining theory in terms of N limitation. Sucrose addition with N was accompanied by accelerated microbial growth, increased activities of β-glucosidase and cellobiohydrolase, and decreased activities of xylanase and leucine amino peptidase. This indicated an increased contribution of r-strategists to the PE and to decomposition of cellulose but the decreased hemicellulolytic and proteolytic activities. Thus, the acceleration of the C cycle was primed by exogenous organic C and was controlled by N. This confirms the stoichiometric decomposition theory. Both K- and r-strategists were beneficial for priming effects, with an increasing contribution of K-selected species under N limitation. Thus, the priming phenomenon described in 'microbial N mining' theory can be ascribed to K-strategists. In contrast, 'stoichiometric decomposition' theory, that is, accelerated OM mineralization due to balanced microbial growth, is explained by domination of r-strategists.

MM-ISMSA: An Ultrafast and Accurate Scoring Function for Protein-Protein Docking.

PubMed

Klett, Javier; Núñez-Salgado, Alfonso; Dos Santos, Helena G; Cortés-Cabrera, Álvaro; Perona, Almudena; Gil-Redondo, Rubén; Abia, David; Gago, Federico; Morreale, Antonio

2012-09-11

An ultrafast and accurate scoring function for protein-protein docking is presented. It includes (1) a molecular mechanics (MM) part based on a 12-6 Lennard-Jones potential; (2) an electrostatic component based on an implicit solvent model (ISM) with individual desolvation penalties for each partner in the protein-protein complex plus a hydrogen bonding term; and (3) a surface area (SA) contribution to account for the loss of water contacts upon protein-protein complex formation. The accuracy and performance of the scoring function, termed MM-ISMSA, have been assessed by (1) comparing the total binding energies, the electrostatic term, and its components (charge-charge and individual desolvation energies), as well as the per residue contributions, to results obtained with well-established methods such as APBSA or MM-PB(GB)SA for a set of 1242 decoy protein-protein complexes and (2) testing its ability to recognize the docking solution closest to the experimental structure as that providing the most favorable total binding energy. For this purpose, a test set consisting of 15 protein-protein complexes with known 3D structure mixed with 10 decoys for each complex was used. The correlation between the values afforded by MM-ISMSA and those from the other methods is quite remarkable (r(2) ∼ 0.9), and only 0.2-5.0 s (depending on the number of residues) are spent on a single calculation including an all vs all pairwise energy decomposition. On the other hand, MM-ISMSA correctly identifies the best docking solution as that closest to the experimental structure in 80% of the cases. Finally, MM-ISMSA can process molecular dynamics trajectories and reports the results as averaged values with their standard deviations. MM-ISMSA has been implemented as a plugin to the widely used molecular graphics program PyMOL, although it can also be executed in command-line mode. MM-ISMSA is distributed free of charge to nonprofit organizations.

Design, Implementation and Deployment of PAIRwise

ERIC Educational Resources Information Center

Knight, Allan; Almeroth, Kevin; Bimber, Bruce

2008-01-01

Increased access to the Internet has dramatically increased the sources from which students can deliberately or accidentally copy information. This article discusses our motivation to design, implement, and deploy an Internet based plagiarism detection system, called PAIRwise, to address this growing problem. We give details as to how we detect…

Alumina nanowire growth by water decomposition and the peritectic reaction of decagonal Al{sub 65}Cu{sub 15}Co{sub 20} quasicrystals

DOE Office of Scientific and Technical Information (OSTI.GOV)

Téllez-Vázquez, J.O., E-mail: oswald.tellez@gmail.com; Patiño-Carachure, C., E-mail: cpatino@pampano.unacar.mx; Rosas, G., E-mail: grtrejo@yahoo07.com.mx

2016-02-15

In this paper, the results of the Al{sub 2}O{sub 3} nanowires' growth through a chemical reaction between Al and water vapor at 1050 °C are presented. Our approach is based on two primary considerations. First, at room temperature, the Al{sub 65}Cu{sub 15}Co{sub 20} alloy is affected by the following mechanism: 2Al (s) + 3H{sub 2}O (g) → Al{sub 2}O{sub 3} (s) + H{sub 2} (g). In this reaction, the released hydrogen induces cleavage fracture of the material to form small particles. Second, the Al{sub 65}Cu{sub 15}Co{sub 20} quasicrystalline phase is transformed on heating to liquid + Al (Cu, Co) cubicmore » phase through a peritectic reaction at 1050 °C. The Al-rich liquid then reacts with water vapor, forming Al{sub 2}O{sub 3} nanowires. X-ray diffraction (XRD) analysis shows that the formed nanowires have a hexagonal structure, and infrared analysis further confirms the presence of α-Al{sub 2}O{sub 3} phase in the final products. Transmission electron microscopy observations show that nanoparticles are present at the end of nanowires, suggesting the VLS growth mechanism. Elemental analysis by energy dispersive spectroscopy (EDS) indicates that the particles at the tip of the nanowires are mainly formed by Co and Cu alloying elements and small amounts of Al. Electron microscopy observations showed nanowires with diameters ranging from 20 to 70 nm; the average diameter was 37 nm and the nanowire lengths were up to several micrometers. - Highlights: • Hexagonal alumina nanowires are grown at 1050 °C through the VLS process. • Alumina nanowires are obtained by the decomposition of decagonal quasicrystalline phase. • The decagonal phase decomposition follows a peritectic reaction at 1030 °C. • Nanoparticles are obtained by hydrogen embrittlement mechanism. • The nanoparticles catalyze the water decomposition to form wires.« less

Formation and characterization of mullite fibers produced by inviscid melt-spinning

NASA Astrophysics Data System (ADS)

Xiao, Zhijun

IMS is a technique used to form fibers from low viscosity melts by means of stream stabilization in a reactant gas, in this case propane. Mullite (3Alsb2Osb3*2SiOsb2) was selected as the material to be fiberized. A stable mullite melt was obtained at 2000sp°C. Some short fibers and shot were formed in the fiber forming experiments. Crucible material selection is a prerequisite for proper application of the IMS technique. The effect of two crucible materials-graphite and boron nitride were studied. A carbothermal reaction occurred between the mullite melt and the graphite crucible. Boron nitride was selected as the crucible material because a relatively stable melt could be obtained. Operating environment is another factor that affects IMS mullite fiber formation. The effects of vacuum, nitrogen and argon on mullite melting behavior were studied. Argon gas was selected as the operating environment. A 2sp3 factorial design was developed to study the effect of such variables as temperature, holding time at the temperature, and heating rate on mullite melting behavior. The effects of the variables and interactions were calculated. Temperature has the biggest positive effect, holding time is the second, heating rate just has a very small negative effect. A detailed investigation of the mullite decomposition mechanism and kinetics was conducted in this work. A solid reaction mechanism was proposed. The kinetic results and IR analysis support the proposed mechanism. The carbon source inside the furnace led to the decomposition of mullite. A feasible experimental technique was developed to prevent the decomposition of mullite. The experiments with this design completely controlled the mullite decomposition. The short fibers, shot and some side products formed in the fiber forming experiments were characterized using XRD, XRF and SEM-EDS. The composition of the short fiber and shot was in the range of mullite composition. XRD showed that the diffraction pattern of shot is that of mullite.

Synthesis of porous sheet-like Co{sub 3}O{sub 4} microstructure by precipitation method and its potential applications in the thermal decomposition of ammonium perchlorate

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lu Shanshan; Jing Xiaoyan; Liu Jingyuan

2013-01-15

Porous sheet-like cobalt oxide (Co{sub 3}O{sub 4}) were successfully synthesized by precipitation method combined with calcination of cobalt hydroxide precursors. The structure, morphology and porosity properties of the products were characterized by X-ray powder diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and nitrogen adsorption-desorption measurement. The as-prepared sheet-like microstructures were approximately 2-3 {mu}m in average diameter, and the morphology of the cobalt hydroxide precursors was retained after the calcination process. However, it appeared a large number of uniform pores in the sheets after calcination. In order to calculate the potential catalytic activity, the thermal decomposition of ammoniummore » perchlorate (AP) has been analyzed, in which cobalt oxide played a role of an additive and the porous sheet-like Co{sub 3}O{sub 4} microstructures exhibited high catalytic performance and considerable decrease in the thermal decomposition temperature of AP. Moreover, a formation mechanism for the sheet-like microstructures has been discussed. - Graphical abstract: Porous sheet-like Co{sub 3}O{sub 4} were synthesized by facile precipitation method combined with calcination of {beta}-Co(OH){sub 2} precursors. Thermogravimetric-differential scanning calorimetric analysis indicates potential catalytic activity in the thermal decomposition of ammonium perchlorate. Highlights: Black-Right-Pointing-Pointer Synthesis of sheet-like {beta}-Co(OH){sub 2} precursors by precipitation method. Black-Right-Pointing-Pointer Porous sheet-like Co{sub 3}O{sub 4} were obtained by calcining {beta}-Co(OH){sub 2} precursors. Black-Right-Pointing-Pointer The possible formation mechanism of porous sheet-like Co{sub 3}O{sub 4} has been discussed. Black-Right-Pointing-Pointer Porous sheet-like Co{sub 3}O{sub 4} decrease the thermal decomposition temperature of ammonium perchlorate.« less

Micro-kinetic simulations of the catalytic decomposition of hydrazine on the Cu(111) surface.

PubMed

Tafreshi, Saeedeh S; Roldan, Alberto; de Leeuw, Nora H

2017-04-28

Hydrazine (N 2 H 4 ) is produced at industrial scale from the partial oxidation of ammonia or urea. The hydrogen content (12.5 wt%) and price of hydrazine make it a good source of hydrogen fuel, which is also easily transportable in the hydrate form, thus enabling the production of H 2 in situ. N 2 H 4 is currently used as a monopropellant thruster to control and adjust the orbits and altitudes of spacecrafts and satellites; with similar procedures applicable in new carbon-free technologies for power generators, e.g. proton-exchange membrane fuel cells. The N 2 H 4 decomposition is usually catalysed by the expensive Ir/Al 2 O 3 material, but a more affordable catalyst is needed to scale-up the process whilst retaining reaction control. Using a complementary range of computational tools, including newly developed micro-kinetic simulations, we have derived and analysed the N 2 H 4 decomposition mechanism on the Cu(111) surface, where the energetic terms of all states have been corrected by entropic terms. The simulated temperature-programmed reactions have shown how the pre-adsorbed N 2 H 4 coverage and heating rate affect the evolution of products, including NH 3 , N 2 and H 2 . The batch reactor simulations have revealed that for the scenario of an ideal Cu terrace, a slow but constant production of H 2 occurs, 5.4% at a temperature of 350 K, while the discharged NH 3 can be recycled into N 2 H 4 . These results show that Cu(111) is not suitable for hydrogen production from hydrazine. However, real catalysts are multi-faceted and present defects, where previous work has shown a more favourable N 2 H 4 decomposition mechanism, and, perhaps, the decomposition of NH 3 improves the production of hydrogen. As such, further investigation is needed to develop a general picture.

Cross Directorate Proposal: Nanostructured Materials for Munitions and Propellants-Production, Modeling, and Characterization

DTIC Science & Technology

2016-07-15

towards hydration and decomposition along with probing their hydration mechanisms, we are now exploring processing and deposition effects for this...oxidizer films and tested for their reactivity. Hydration Mechanism for HI3O8 → HIO3 Previous efforts by our group investigating the hydration ...mechanism of I2O5 → HI3O8 reflected that the hydration mechanism proceeded through a nucleation and growth process followed by a diffusion limited

Neurons the decision makers, Part I: The firing function of a single neuron.

PubMed

Saaty, Thomas

2017-02-01

This paper is concerned with understanding synthesis of electric signals in the neural system based on making pairwise comparisons. Fundamentally, every person and every animal are born with the talent to compare stimuli from things that share properties in space or over time. Comparisons always need experience to distinguish among things. Pairwise comparisons are numerically reciprocal. If a value is assigned to the larger of two elements that have a given property when compared with the smaller one, then the smaller has the reciprocal of that value when compared with the larger. Because making comparisons requires the reciprocal property, we need mathematics that can cope with division. There are four division algebras that would allow us to use our reciprocals arising from comparisons: The real numbers, the complex numbers, the non-commutative quaternions and the non-associative octonions. Rather than inferring function as from electric flow in a network, in this paper we infer the flow from function. Neurons fire in response to stimuli and their firings vary relative to the intensities of the stimuli. We believe neurons use some kind of pairwise comparison mechanism to determine when to fire based on the stimuli they receive. The ideas we develop here about flows are used to deduce how a system based on this kind of firing determination works and can be described. Furthermore the firing of neurons requires continuous comparisons. To develop a formula describing the output of these pairwise comparisons requires solving Fredholm's equation of the second kind which is satisfied if and only if a simple functional equation has solutions. The Fourier transform of the real solution of this equation leads to inverse square laws like those that are common in physics. The Fourier transform applied to a complex valued solution leads to Dirac type of firings. Such firings are dense in the very general fields of functions known as Sobolev spaces and thus can be used to represent the very diverse phenomena in and around us. The non-commutative solution in quaternions can be interpreted as rotations in space. The also non-commutative and non-associative solution in octonions has yet to be adequately interpreted outside physics. Copyright © 2016 Elsevier Ltd. All rights reserved.

Mutagenesis: Interactions with a parallel universe.

PubMed

Miller, Jeffrey H

Unexpected observations in mutagenesis research have led to a new perspective in this personal reflection based on years of studying mutagenesis. Many mutagens have been thought to operate via a single principal mechanism, with secondary effects usually resulting in only minor changes in the observed mutation frequencies and spectra. For example, we conceive of base analogs as resulting in direct mispairing as their main mechanism of mutagenesis. Recent studies now show that in fact even these simple mutagens can cause very large and unanticipated effects both in mutation frequencies and in the mutational spectra when used in certain pair-wise combinations. Here we characterize this leap in mutation frequencies as a transport to an alternate universe of mutagenesis. Copyright © 2018 Elsevier B.V. All rights reserved.

Characterization and Thermal Decomposition of Nanometer 2,2', 4,4', 6,6'-Hexanitro-Stilbene and 1,3,5-Triamino-2,4,6-Trinitrobenzene Fabricated by a Mechanical Milling Method

NASA Astrophysics Data System (ADS)

Song, Xiaolan; Wang, Yi; Zhao, Shanshan; An, Chongwei; Wang, Jingyu; Zhang, Jinglin

2018-04-01

Nanometer 2,2', 4,4', 6,6'-hexanitro-stilbene (HNS) and 1,3,5-triamino-2,4,6-trinitrobenzene (TATB) were fabricated on a high-energy ball mill. The particle sizes of nano-HNS and nano-TATB were 98.4 and 57.8 nm, respectively. An SEM analysis was employed to image the micron morphology of nano-explosives. The particle size distribution was calculated by measuring the size of 300 particles in SEM images. XRD, IR, and XPS analyses were used to confirm whether the crystal phase, molecule structure, and surface elements were changed by the milling process. Thermal decomposition of nano-HNS and nano-TATB was investigated by differential scanning calorimetry (DSC) and thermal-infrared spectrometry online (DSC-IR) analyses. Using DSC traces collected from different heating rates, the kinetic and thermodynamic parameters of thermolysis of raw and nano-explosives were calculated (activation energy (EK), pre-exponential factor (lnAK), rate constant (k), activation heat (ΔH≠), activation free energy (ΔG≠), activation entropy (ΔS≠), critical temperature of thermal explosion (Tb), and critical heating rate of thermal explosion (dT/dt)Tb). The results indicated that nano-explosives were of different kinetic and thermodynamic properties from starting explosives. In addition, the gas products for thermal decomposition of nano-HNS and nano-TATB were detected. Although HNS and TATB are both nitro explosives, the decomposition products of the two were different. A mechanism to explain the difference is proposed.

Additive effect on reductive decomposition and binding of carbonate-based solvent toward solid electrolyte interphase formation in lithium-ion battery.

PubMed

Ushirogata, Keisuke; Sodeyama, Keitaro; Okuno, Yukihiro; Tateyama, Yoshitaka

2013-08-14

The solid-electrolyte interphase (SEI) formed through the reductive decomposition of solvent molecules plays a crucial role in the stability and capability of a lithium-ion battery (LIB). Here we investigated the effects of adding vinylene carbonate (VC) to ethylene carbonate (EC) solvent, a typical electrolyte in LIBs, on the reductive decomposition. We focused on both thermodynamics and kinetics of the possible processes and used density functional theory-based molecular dynamics with explicit solvent and Blue-moon ensemble technique for the free energy change. We considered Li(+) in only EC solvent (EC system) and in EC solvent with a VC additive (EC/VC system) to elucidate the additive effects. In addition to clarifying the equilibrium properties, we evaluated the free energy changes along several EC or VC decomposition pathways under one-electron (1e) reduction condition. Two-electron (2e) reduction and attacks of anion radicals to intact molecules were also examined. The present results completely reproduce the gaseous products observed in the experiments. We also found a new mechanism involving the VC additive: the VC additive preferentially reacts with the EC anion radical to suppress the 2e reduction of EC and enhance the initial SEI formation, contrary to the conventional scenario in which VC additive is sacrificially reduced and its radical oligomerization becomes the source of SEI. Because our mechanism needs only 1e reduction, the irreversible capacity at the SEI formation will decrease, which is also consistent with the experimental observations. These results reveal the primary role of VC additive in the EC solvent.

Multiscale Fiber Kinking: Computational Micromechanics and a Mesoscale Continuum Damage Mechanics Models

NASA Technical Reports Server (NTRS)

Herraez, Miguel; Bergan, Andrew C.; Gonzalez, Carlos; Lopes, Claudio S.

2017-01-01

In this work, the fiber kinking phenomenon, which is known as the failure mechanism that takes place when a fiber reinforced polymer is loaded under longitudinal compression, is studied. A computational micromechanics model is employed to interrogate the assumptions of a recently developed mesoscale continuum damage mechanics (CDM) model for fiber kinking based on the deformation gradient decomposition (DGD) and the LaRC04 failure criteria.

Spark-integrated propellant injector head with flashback barrier

NASA Technical Reports Server (NTRS)

Mungas, Gregory Stuart (Inventor); Fisher, David James (Inventor); Mungas, Christopher (Inventor)

2012-01-01

High performance propellants flow through specialized mechanical hardware that allows for effective and safe thermal decomposition and/or combustion of the propellants. By integrating a sintered metal component between a propellant feed source and the combustion chamber, an effective and reliable fuel injector head may be implemented. Additionally the fuel injector head design integrates a spark ignition mechanism that withstands extremely hot running conditions without noticeable spark mechanism degradation.

Validation of Heat Transfer Thermal Decomposition and Container Pressurization of Polyurethane Foam.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Scott, Sarah Nicole; Dodd, Amanda B.; Larsen, Marvin E.

Polymer foam encapsulants provide mechanical, electrical, and thermal isolation in engineered systems. In fire environments, gas pressure from thermal decomposition of polymers can cause mechanical failure of sealed systems. In this work, a detailed uncertainty quantification study of PMDI-based polyurethane foam is presented to assess the validity of the computational model. Both experimental measurement uncertainty and model prediction uncertainty are examined and compared. Both the mean value method and Latin hypercube sampling approach are used to propagate the uncertainty through the model. In addition to comparing computational and experimental results, the importance of each input parameter on the simulation resultmore » is also investigated. These results show that further development in the physics model of the foam and appropriate associated material testing are necessary to improve model accuracy.« less

Reaction mechanisms in the organometallic vapor phase epitaxial growth of GaAs

NASA Technical Reports Server (NTRS)

Larsen, C. A.; Buchan, N. I.; Stringfellow, G. B.

1988-01-01

The decomposition mechanisms of AsH3, trimethylgallium (TMGa), and mixtures of the two have been studied in an atmospheric-pressure flow system with the use of D2 to label the reaction products which are analyzed in a time-of-flight mass spectrometer. AsH3 decomposes entirely heterogeneously to give H2. TMGa decomposes by a series of gas-phase steps, involving methyl radicals and D atoms to produce CH3D, CH4, C2H6, and HD. TMGa decomposition is accelerated by the presence of AsH3. When the two are mixed, as in the organometallic vapor phase epitaxial growth of GaAs, both compounds decompose in concert to produce only CH4. A likely model is that of a Lewis acid-base adduct that forms and subsequently eliminates CH4.

Reaction mechanisms in the organometallic vapor phase epitaxial growth of GaAs

NASA Astrophysics Data System (ADS)

Larsen, C. A.; Buchan, N. I.; Stringfellow, G. B.

1988-02-01

The decomposition mechanisms of AsH3, trimethylgallium (TMGa), and mixtures of the two have been studied in an atmospheric-pressure flow system with the use of D2 to label the reaction products which are analyzed in a time-of-flight mass spectrometer. AsH3 decomposes entirely heterogeneously to give H2. TMGa decomposes by a series of gas-phase steps, involving methyl radicals and D atoms to produce CH3D, CH4, C2H6, and HD. TMGa decomposition is accelerated by the presence of AsH3. When the two are mixed, as in the organometallic vapor phase epitaxial growth of GaAs, both compounds decompose in concert to produce only CH4. A likely model is that of a Lewis acid-base adduct that forms and subsequently eliminates CH4.

Formation of Aldehydic Phosphatidylcholines during the Anaerobic Decomposition of a Phosphatidylcholine Bearing the 9-Hydroperoxide of Linoleic Acid

PubMed Central

2016-01-01

Lipid oxidation-derived carbonyl compounds are associated with the development of various physiological disorders. Formation of most of these products has recently been suggested to require further reactions of oxygen with lipid hydroperoxides. However, in rat and human tissues, the formation of 4-hydroxy-2-nonenal is greatly elevated during hypoxic/ischemic conditions. Furthermore, a previous study found an unexpected result that the decomposition of a phosphatidylcholine (PC) bearing the 13-hydroperoxide of linoleic acid under a nitrogen atmosphere afforded 9-oxononanoyl-PC rather than 13-oxo-9,11-tridecadienoyl-PC as the main aldehydic PC. In the present study, products of the anaerobic decomposition of a PC bearing the 9-hydroperoxide of linoleic acid were analysed by electrospray ionization mass spectrometry. 9-Oxononanoyl-PC (ONA-PC) and several well-known bioactive aldehydes including 12-oxo-9-hydroperoxy-(or oxo or hydroxy)-10-dodecenoyl-PCs were detected. Hydrolysis of the oxidized PC products, methylation of the acids obtained thereby, and subsequent gas chromatography-mass spectroscopy with electron impact ionization further confirmed structures of some of the key aldehydic PCs. Novel, hydroxyl radical-dependent mechanisms of formation of ONA-PC and peroxyl-radical dependent mechanisms of formation of the rest of the aldehydes are proposed. The latter mechanisms will mainly be relevant to tissue injury under hypoxic/anoxic conditions, while the former are relevant under both normoxia and hypoxia/anoxia. PMID:27366754

A comparative evaluation of explosion hazards in chemical and mechanical pulp bleaching systems

Treesearch

P.W. Hart; Alan Rudie

2010-01-01

Three pulp mills in North America using 50% hydrogen peroxide have suffered explosions of pumps, mixers, and tanks. In two instances, alkali-catalyzed decomposition of peroxide is implicated in the explosion. Although many mechanical pulping facilities use hydrogen peroxide to bleach pulp, no &-catalyzed explosions have been reported. This research uses a kinetic...

Generation of Synthetic Spike Trains with Defined Pairwise Correlations

PubMed Central

Niebur, Ernst

2008-01-01

Recent technological advances as well as progress in theoretical understanding of neural systems have created a need for synthetic spike trains with controlled mean rate and pairwise cross-correlation. This report introduces and analyzes a novel algorithm for the generation of discretized spike trains with arbitrary mean rates and controlled cross correlation. Pairs of spike trains with any pairwise correlation can be generated, and higher-order correlations are compatible with common synaptic input. Relations between allowable mean rates and correlations within a population are discussed. The algorithm is highly efficient, its complexity increasing linearly with the number of spike trains generated and therefore inversely with the number of cross-correlated pairs. PMID:17521277

Prospects for inferring pairwise relationships with single nucleotide polymorphisms

Treesearch

Jeffery C. Glaubitz; O. Eugene, Jr. Rhodes; J. Andrew DeWoody

2003-01-01

An extraordinarily large number of single nucleotide polymorphisms (SNPs) are now available in humans as well as in other model organisms. Technological advancements may soon make it feasible to assay hundreds of SNPs in virtually any organism of interest. One potential application of SNPs is the determination of pairwise genetic relationships in populations without...

Hierarchical semi-numeric method for pairwise fuzzy group decision making.

PubMed

Marimin, M; Umano, M; Hatono, I; Tamura, H

2002-01-01

Gradual improvements to a single-level semi-numeric method, i.e., linguistic labels preference representation by fuzzy sets computation for pairwise fuzzy group decision making are summarized. The method is extended to solve multiple criteria hierarchical structure pairwise fuzzy group decision-making problems. The problems are hierarchically structured into focus, criteria, and alternatives. Decision makers express their evaluations of criteria and alternatives based on each criterion by using linguistic labels. The labels are converted into and processed in triangular fuzzy numbers (TFNs). Evaluations of criteria yield relative criteria weights. Evaluations of the alternatives, based on each criterion, yield a degree of preference for each alternative or a degree of satisfaction for each preference value. By using a neat ordered weighted average (OWA) or a fuzzy weighted average operator, solutions obtained based on each criterion are aggregated into final solutions. The hierarchical semi-numeric method is suitable for solving a larger and more complex pairwise fuzzy group decision-making problem. The proposed method has been verified and applied to solve some real cases and is compared to Saaty's (1996) analytic hierarchy process (AHP) method.

A new method of content based medical image retrieval and its applications to CT imaging sign retrieval.

PubMed

Ma, Ling; Liu, Xiabi; Gao, Yan; Zhao, Yanfeng; Zhao, Xinming; Zhou, Chunwu

2017-02-01

This paper proposes a new method of content based medical image retrieval through considering fused, context-sensitive similarity. Firstly, we fuse the semantic and visual similarities between the query image and each image in the database as their pairwise similarities. Then, we construct a weighted graph whose nodes represent the images and edges measure their pairwise similarities. By using the shortest path algorithm over the weighted graph, we obtain a new similarity measure, context-sensitive similarity measure, between the query image and each database image to complete the retrieval process. Actually, we use the fused pairwise similarity to narrow down the semantic gap for obtaining a more accurate pairwise similarity measure, and spread it on the intrinsic data manifold to achieve the context-sensitive similarity for a better retrieval performance. The proposed method has been evaluated on the retrieval of the Common CT Imaging Signs of Lung Diseases (CISLs) and achieved not only better retrieval results but also the satisfactory computation efficiency. Copyright © 2017 Elsevier Inc. All rights reserved.

SVM-dependent pairwise HMM: an application to protein pairwise alignments.

PubMed

Orlando, Gabriele; Raimondi, Daniele; Khan, Taushif; Lenaerts, Tom; Vranken, Wim F

2017-12-15

Methods able to provide reliable protein alignments are crucial for many bioinformatics applications. In the last years many different algorithms have been developed and various kinds of information, from sequence conservation to secondary structure, have been used to improve the alignment performances. This is especially relevant for proteins with highly divergent sequences. However, recent works suggest that different features may have different importance in diverse protein classes and it would be an advantage to have more customizable approaches, capable to deal with different alignment definitions. Here we present Rigapollo, a highly flexible pairwise alignment method based on a pairwise HMM-SVM that can use any type of information to build alignments. Rigapollo lets the user decide the optimal features to align their protein class of interest. It outperforms current state of the art methods on two well-known benchmark datasets when aligning highly divergent sequences. A Python implementation of the algorithm is available at http://ibsquare.be/rigapollo. wim.vranken@vub.be. Supplementary data are available at Bioinformatics online. © The Author (2017). Published by Oxford University Press. All rights reserved. For Permissions, please email: journals.permissions@oup.com

Frequency-Dependent Selection: The High Potential for Permanent Genetic Variation in the Diallelic, Pairwise Interaction Model

PubMed Central

Asmussen, M. A.; Basnayake, E.

1990-01-01

A detailed analytic and numerical study is made of the potential for permanent genetic variation in frequency-dependent models based on pairwise interactions among genotypes at a single diallelic locus. The full equilibrium structure and qualitative gene-frequency dynamics are derived analytically for a symmetric model, in which pairwise fitnesses are chiefly determined by the genetic similarity of the individuals involved. This is supplemented by an extensive numerical investigation of the general model, the symmetric model, and nine other special cases. Together the results show that there is a high potential for permanent genetic diversity in the pairwise interaction model, and provide insight into the extent to which various forms of genotypic interactions enhance or reduce this potential. Technically, although two stable polymorphic equilibria are possible, the increased likelihood of maintaining both alleles, and the poor performance of protected polymorphism conditions as a measure of this likelihood, are primarily due to a greater variety and frequency of equilibrium patterns with one stable polymorphic equilibrium, in conjunction with a disproportionately large domain of attraction for stable internal equilibria. PMID:2341034

Thermal decomposition of ammonium perchlorate in the presence of Al(OH)(3)·Cr(OH)(3) nanoparticles.

PubMed

Zhang, WenJing; Li, Ping; Xu, HongBin; Sun, Randi; Qing, Penghui; Zhang, Yi

2014-03-15

An Al(OH)(3)·Cr(OH)(3) nanoparticle preparation procedure and its catalytic effect and mechanism on thermal decomposition of ammonium perchlorate (AP) were investigated using transmission electron microscopy (TEM), X-ray diffraction (XRD), thermogravimetric analysis and differential scanning calorimetry (TG-DSC), X-ray photoelectron spectroscopy (XPS), and thermogravimetric analysis and mass spectroscopy (TG-MS). In the preparation procedure, TEM, SAED, and FT-IR showed that the Al(OH)(3)·Cr(OH)(3) particles were amorphous particles with dimensions in the nanometer size regime containing a large amount of surface hydroxyl under the controllable preparation conditions. When the Al(OH)(3)·Cr(OH)(3) nanoparticles were used as additives for the thermal decomposition of AP, the TG-DSC results showed that the addition of Al(OH)(3)·Cr(OH)(3) nanoparticles to AP remarkably decreased the onset temperature of AP decomposition from approximately 450°C to 245°C. The FT-IR, RS and XPS results confirmed that the surface hydroxyl content of the Al(OH)(3)·Cr(OH)(3) nanoparticles decreased from 67.94% to 63.65%, and Al(OH)3·Cr(OH)3 nanoparticles were limitedly transformed from amorphous to crystalline after used as additives for the thermal decomposition of AP. Such behavior of Al(OH)(3)·Cr(OH)(3) nanoparticles promoted the oxidation of NH3 of AP to decompose to N2O first, as indicated by the TG-MS results, accelerating the AP thermal decomposition. Copyright © 2014 Elsevier B.V. All rights reserved.

Marginal semi-supervised sub-manifold projections with informative constraints for dimensionality reduction and recognition.

PubMed

Zhang, Zhao; Zhao, Mingbo; Chow, Tommy W S

2012-12-01

In this work, sub-manifold projections based semi-supervised dimensionality reduction (DR) problem learning from partial constrained data is discussed. Two semi-supervised DR algorithms termed Marginal Semi-Supervised Sub-Manifold Projections (MS³MP) and orthogonal MS³MP (OMS³MP) are proposed. MS³MP in the singular case is also discussed. We also present the weighted least squares view of MS³MP. Based on specifying the types of neighborhoods with pairwise constraints (PC) and the defined manifold scatters, our methods can preserve the local properties of all points and discriminant structures embedded in the localized PC. The sub-manifolds of different classes can also be separated. In PC guided methods, exploring and selecting the informative constraints is challenging and random constraint subsets significantly affect the performance of algorithms. This paper also introduces an effective technique to select the informative constraints for DR with consistent constraints. The analytic form of the projection axes can be obtained by eigen-decomposition. The connections between this work and other related work are also elaborated. The validity of the proposed constraint selection approach and DR algorithms are evaluated by benchmark problems. Extensive simulations show that our algorithms can deliver promising results over some widely used state-of-the-art semi-supervised DR techniques. Copyright © 2012 Elsevier Ltd. All rights reserved.

Deciphering life history transcriptomes in different environments

PubMed Central

Etges, William J.; Trotter, Meredith V.; de Oliveira, Cássia C.; Rajpurohit, Subhash; Gibbs, Allen G.; Tuljapurkar, Shripad

2014-01-01

We compared whole transcriptome variation in six preadult stages and seven adult female ages in two populations of cactophilic Drosophila mojavensis reared on two host plants in order to understand how differences in gene expression influence standing life history variation. We used Singular Value Decomposition (SVD) to identify dominant trajectories of life cycle gene expression variation, performed pair-wise comparisons of stage and age differences in gene expression across the life cycle, identified when genes exhibited maximum levels of life cycle gene expression, and assessed population and host cactus effects on gene expression. Life cycle SVD analysis returned four significant components of transcriptional variation, revealing functional enrichment of genes responsible for growth, metabolic function, sensory perception, neural function, translation and aging. Host cactus effects on female gene expression revealed population and stage specific differences, including significant host plant effects on larval metabolism and development, as well as adult neurotransmitter binding and courtship behavior gene expression levels. In 3 - 6 day old virgin females, significant up-regulation of genes associated with meiosis and oogenesis was accompanied by down-regulation of genes associated with somatic maintenance, evidence for a life history tradeoff. The transcriptome of D. mojavensis reared in natural environments throughout its life cycle revealed core developmental transitions and genome wide influences on life history variation in natural populations. PMID:25442828

Goal-Function Tree Modeling for Systems Engineering and Fault Management

NASA Technical Reports Server (NTRS)

Johnson, Stephen B.; Breckenridge, Jonathan T.

2013-01-01

This paper describes a new representation that enables rigorous definition and decomposition of both nominal and off-nominal system goals and functions: the Goal-Function Tree (GFT). GFTs extend the concept and process of functional decomposition, utilizing state variables as a key mechanism to ensure physical and logical consistency and completeness of the decomposition of goals (requirements) and functions, and enabling full and complete traceabilitiy to the design. The GFT also provides for means to define and represent off-nominal goals and functions that are activated when the system's nominal goals are not met. The physical accuracy of the GFT, and its ability to represent both nominal and off-nominal goals enable the GFT to be used for various analyses of the system, including assessments of the completeness and traceability of system goals and functions, the coverage of fault management failure detections, and definition of system failure scenarios.

Study on the mechanism of copper-ammonia complex decomposition in struvite formation process and enhanced ammonia and copper removal.

PubMed

Peng, Cong; Chai, Liyuan; Tang, Chongjian; Min, Xiaobo; Song, Yuxia; Duan, Chengshan; Yu, Cheng

2017-01-01

Heavy metals and ammonia are difficult to remove from wastewater, as they easily combine into refractory complexes. The struvite formation method (SFM) was applied for the complex decomposition and simultaneous removal of heavy metal and ammonia. The results indicated that ammonia deprivation by SFM was the key factor leading to the decomposition of the copper-ammonia complex ion. Ammonia was separated from solution as crystalline struvite, and the copper mainly co-precipitated as copper hydroxide together with struvite. Hydrogen bonding and electrostatic attraction were considered to be the main surface interactions between struvite and copper hydroxide. Hydrogen bonding was concluded to be the key factor leading to the co-precipitation. In addition, incorporation of copper ions into the struvite crystal also occurred during the treatment process. Copyright © 2016. Published by Elsevier B.V.

Resonant electron capture by aspartame and aspartic acid molecules.

PubMed

Muftakhov, M V; Shchukin, P V

2016-12-30

The processes for dissociative electron capture are the key mechanisms for decomposition of biomolecules, proteins in particular, under interaction with low-energy electrons. Molecules of aspartic acid and aspartame, i.e. modified dipeptides, were studied herein to define the impact of the side functional groups on peptide chain decomposition in resonant electron-molecular reactions. The processes of formation and decomposition of negative ions of both aspartame and aspartic acid were studied by mass spectrometry of negative ions under resonant electron capture. The obtained mass spectra were interpreted under thermochemical analysis by quantum chemical calculations. Main channels of negative molecular ions fragmentation were found and characteristic fragment ions were identified. The СООН fragment of the side chain in aspartic acid is shown to play a key role like the carboxyl group in amino acids and aliphatic oligopeptides. Copyright © 2016 John Wiley & Sons, Ltd. Copyright © 2016 John Wiley & Sons, Ltd.

Consistency-based rectification of nonrigid registrations

PubMed Central

Gass, Tobias; Székely, Gábor; Goksel, Orcun

2015-01-01

Abstract. We present a technique to rectify nonrigid registrations by improving their group-wise consistency, which is a widely used unsupervised measure to assess pair-wise registration quality. While pair-wise registration methods cannot guarantee any group-wise consistency, group-wise approaches typically enforce perfect consistency by registering all images to a common reference. However, errors in individual registrations to the reference then propagate, distorting the mean and accumulating in the pair-wise registrations inferred via the reference. Furthermore, the assumption that perfect correspondences exist is not always true, e.g., for interpatient registration. The proposed consistency-based registration rectification (CBRR) method addresses these issues by minimizing the group-wise inconsistency of all pair-wise registrations using a regularized least-squares algorithm. The regularization controls the adherence to the original registration, which is additionally weighted by the local postregistration similarity. This allows CBRR to adaptively improve consistency while locally preserving accurate pair-wise registrations. We show that the resulting registrations are not only more consistent, but also have lower average transformation error when compared to known transformations in simulated data. On clinical data, we show improvements of up to 50% target registration error in breathing motion estimation from four-dimensional MRI and improvements in atlas-based segmentation quality of up to 65% in terms of mean surface distance in three-dimensional (3-D) CT. Such improvement was observed consistently using different registration algorithms, dimensionality (two-dimensional/3-D), and modalities (MRI/CT). PMID:26158083

Towards a paradigm shift in the modeling of soil organic carbon decomposition for earth system models

NASA Astrophysics Data System (ADS)

He, Yujie

Soils are the largest terrestrial carbon pools and contain approximately 2200 Pg of carbon. Thus, the dynamics of soil carbon plays an important role in the global carbon cycle and climate system. Earth System Models are used to project future interactions between terrestrial ecosystem carbon dynamics and climate. However, these models often predict a wide range of soil carbon responses and their formulations have lagged behind recent soil science advances, omitting key biogeochemical mechanisms. In contrast, recent mechanistically-based biogeochemical models that explicitly account for microbial biomass pools and enzyme kinetics that catalyze soil carbon decomposition produce notably different results and provide a closer match to recent observations. However, a systematic evaluation of the advantages and disadvantages of the microbial models and how they differ from empirical, first-order formulations in soil decomposition models for soil organic carbon is still needed. This dissertation consists of a series of model sensitivity and uncertainty analyses and identifies dominant decomposition processes in determining soil organic carbon dynamics. Poorly constrained processes or parameters that require more experimental data integration are also identified. This dissertation also demonstrates the critical role of microbial life-history traits (e.g. microbial dormancy) in the modeling of microbial activity in soil organic matter decomposition models. Finally, this study surveys and synthesizes a number of recently published microbial models and provides suggestions for future microbial model developments.

Leaf litter traits of invasive species slow down decomposition compared to Spanish natives: a broad phylogenetic comparison.

PubMed

Godoy, Oscar; Castro-Díez, Pilar; Van Logtestijn, Richard S P; Cornelissen, Johannes H C; Valladares, Fernando

2010-03-01

Leaf traits related to the performance of invasive alien species can influence nutrient cycling through litter decomposition. However, there is no consensus yet about whether there are consistent differences in functional leaf traits between invasive and native species that also manifest themselves through their "after life" effects on litter decomposition. When addressing this question it is important to avoid confounding effects of other plant traits related to early phylogenetic divergences and to understand the mechanism underlying the observed results to predict which invasive species will exert larger effects on nutrient cycling. We compared initial leaf litter traits, and their effect on decomposability as tested in standardized incubations, in 19 invasive-native pairs of co-familial species from Spain. They included 12 woody and seven herbaceous alien species representative of the Spanish invasive flora. The predictive power of leaf litter decomposition rates followed the order: growth form > family > status (invasive vs. native) > leaf type. Within species pairs litter decomposition tended to be slower and more dependent on N and P in invaders than in natives. This difference was likely driven by the higher lignin content of invader leaves. Although our study has the limitation of not representing the natural conditions from each invaded community, it suggests a potential slowing down of the nutrient cycle at ecosystem scale upon invasion.

Effects of dissolved organic matter leaching from macrophyte litter on black water events in shallow lakes.

PubMed

He, Yuhong; Song, Na; Jiang, He-Long

2018-04-01

In recent years, the black water phenomenon has become an environmental event in eutrophic shallow lakes in China, leading to deterioration of lake ecosystems and potable water crises. Decomposition of macrophyte debris has been verified as a key inducement for black water events. In this study, the effects of the decomposition of dissolved organic matter (Kottelat et al., WASP 187:343-351, 2008) derived from macrophyte leachate on the occurrence of black water events are investigated to clarify the detailed mechanisms involved. Results show that dissolved organic matter (DOM) is composed of a trace of chromophoric DOM and mostly non-chromophoric dissolved organic matter (CDOM). DOM decomposition is accompanied by varied concentration of CDOM components, generation of organic particles, and increased microbial concentrations. These processes increase water chroma only during initial 48 h, so the intensified water color cannot be maintained by DOM decomposition alone. During DOM decomposition, microorganisms first consume non-CDOM, increasing the relative CDOM concentration and turning the water color to black (or brown). Simultaneously, tryptophan and aromatic proteins, which are major ingredients of CDOM, enhance UV light absorption, further aggravating the macroscopic phenomenon of black color. Our results show that DOM leached from decayed macrophytes promotes or even triggers the occurrence of black water events and should be taken more seriously in the future.

Application of vacuum stability test to determine thermal decomposition kinetics of nitramines bonded by polyurethane matrix

NASA Astrophysics Data System (ADS)

Elbeih, Ahmed; Abd-Elghany, Mohamed; Elshenawy, Tamer

2017-03-01

Vacuum stability test (VST) is mainly used to study compatibility and stability of energetic materials. In this work, VST has been investigated to study thermal decomposition kinetics of four cyclic nitramines, 1,3,5-trinitro-1,3,5-triazinane (RDX) and 1,3,5,7-tetranitro-1,3,5,7-tetrazocane (HMX), cis-1,3,4,6-tetranitrooctahydroimidazo-[4,5-d]imidazole (BCHMX), 2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane (ε-HNIW, CL-20), bonded by polyurethane matrix based on hydroxyl terminated polybutadiene (HTPB). Model fitting and model free (isoconversional) methods have been applied to determine the decomposition kinetics from VST results. For comparison, the decomposition kinetics were determined isothermally by ignition delay technique and non-isothermally by Advanced Kinetics and Technology Solution (AKTS) software. The activation energies for thermolysis obtained by isoconversional method based on VST technique of RDX/HTPB, HMX/HTPB, BCHMX/HTPB and CL20/HTPB were 157.1, 203.1, 190.0 and 176.8 kJ mol-1 respectively. Model fitting method proved that the mechanism of thermal decomposition of BCHMX/HTPB is controlled by the nucleation model while all the other studied PBXs are controlled by the diffusion models. A linear relationship between the ignition temperatures and the activation energies was observed. BCHMX/HTPB is interesting new PBX in the research stage.

A study of photothermal laser ablation of various polymers on microsecond time scales.

PubMed

Kappes, Ralf S; Schönfeld, Friedhelm; Li, Chen; Golriz, Ali A; Nagel, Matthias; Lippert, Thomas; Butt, Hans-Jürgen; Gutmann, Jochen S

2014-01-01

To analyze the photothermal ablation of polymers, we designed a temperature measurement setup based on spectral pyrometry. The setup allows to acquire 2D temperature distributions with 1 μm size and 1 μs time resolution and therefore the determination of the center temperature of a laser heating process. Finite element simulations were used to verify and understand the heat conversion and heat flow in the process. With this setup, the photothermal ablation of polystyrene, poly(α-methylstyrene), a polyimide and a triazene polymer was investigated. The thermal stability, the glass transition temperature Tg and the viscosity above Tg were governing the ablation process. Thermal decomposition for the applied laser pulse of about 10 μs started at temperatures similar to the start of decomposition in thermogravimetry. Furthermore, for polystyrene and poly(α-methylstyrene), both with a Tg in the range between room and decomposition temperature, ablation already occurred at temperatures well below the decomposition temperature, only at 30-40 K above Tg. The mechanism was photomechanical, i.e. a stress due to the thermal expansion of the polymer was responsible for ablation. Low molecular weight polymers showed differences in photomechanical ablation, corresponding to their lower Tg and lower viscosity above the glass transition. However, the difference in ablated volume was only significant at higher temperatures in the temperature regime for thermal decomposition at quasi-equilibrium time scales.

NOx formation in apokamp-type atmospheric pressure plasma jets in air initiated by a pulse-repetitive discharge

NASA Astrophysics Data System (ADS)

Sosnin, Eduard A.; Didenko, Maria V.; Panarin, Victor A.; Skakun, Victor S.; Tarasenko, Victor F.; Liu, Dongping P.; Song, Ying

2018-04-01

The decomposition products of atmospheric pressure plasma of repetitive pulsed discharge in apokamp and corona modes were determined by optical and chemical methods. It is shown, that the decomposition products contain mainly nitrogen oxides NOx. A brief review of the plasma- and thermochemical reactions in the pulsed discharges was made. The review and experimental data allow us to explain the reactive oxygen species formation mechanisms in a potential discharge channel with apokamp. The possible applications of this plasma source for treatment of seeds of agricultural crops are discussed.

Partial information decomposition as a spatiotemporal filter.

PubMed

Flecker, Benjamin; Alford, Wesley; Beggs, John M; Williams, Paul L; Beer, Randall D

2011-09-01

Understanding the mechanisms of distributed computation in cellular automata requires techniques for characterizing the emergent structures that underlie information processing in such systems. Recently, techniques from information theory have been brought to bear on this problem. Building on this work, we utilize the new technique of partial information decomposition to show that previous information-theoretic measures can confound distinct sources of information. We then propose a new set of filters and demonstrate that they more cleanly separate out the background domains, particles, and collisions that are typically associated with information storage, transfer, and modification in cellular automata.

Chevron Behavior and Isostable Enthalpic Barriers in Protein Folding: Successes and Limitations of Simple Gō-like Modeling

PubMed Central

Kaya, Hüseyin; Liu, Zhirong; Chan, Hue Sun

2005-01-01

It has been demonstrated that a “near-Levinthal” cooperative mechanism, whereby the common Gō interaction scheme is augmented by an extra favorability for the native state as a whole, can lead to apparent two-state folding/unfolding kinetics over a broad range of native stabilities in lattice models of proteins. Here such a mechanism is shown to be generalizable to a simplified continuum (off-lattice) Langevin dynamics model with a Cα protein chain representation, with the resulting chevron plots exhibiting an extended quasilinear regime reminiscent of that of apparent two-state real proteins. Similarly high degrees of cooperativity are possible in Gō-like continuum models with rudimentary pairwise desolvation barriers as well. In these models, cooperativity increases with increasing desolvation barrier height, suggesting strongly that two-state-like folding/unfolding kinetics would be achievable when the pairwise desolvation barrier becomes sufficiently high. Besides cooperativity, another generic folding property of interest that has emerged from published experiments on several apparent two-state proteins is that their folding relaxation under constant native stability (isostability) conditions is essentially Arrhenius, entailing high intrinsic enthalpic folding barriers of ∼17–30 kcal/mol. Based on a new analysis of published data on barnase, here we propose that a similar property should also apply to a certain class of non-two-state proteins that fold with chevron rollovers. However, several continuum Gō-like constructs considered here fail to predict any significant intrinsic enthalpic folding barrier under isostability conditions; thus the physical origin of such barriers in real proteins remains to be elucidated. PMID:15863486

Intrinsic Decomposition of The Stretch Tensor for Fibrous Media

NASA Astrophysics Data System (ADS)

Kellermann, David C.

2010-05-01

This paper presents a novel mechanism for the description of fibre reorientation based on the decomposition of the stretch tensor according to a given material's intrinsic constitutive properties. This approach avoids the necessity for fibre directors, structural tensors or specialised model such as the ideal fibre reinforced model, which are commonly applied to the analysis of fibre kinematics in the finite deformation of fibrous media for biomechanical problems. The proposed approach uses Intrinsic-Field Tensors (IFTs) that build upon the linear orthotropic theory presented in a previous paper entitled Strongly orthotropic continuum mechanics and finite element treatment. The intrinsic decomposition of the stretch tensor therein provides superior capacity to represent the intermediary kinematics driven by finite orthotropic ratios, where the benefits are predominantly expressed in cases of large deformation as is typical in the biomechanical studies. Satisfaction of requirements such as Material Frame-Indifference (MFI) and Euclidean objectivity are demonstrated here—these factors being necessary for the proposed IFTs to be valid tensorial quantities. The resultant tensors, initially for the simplest case of linear elasticity, are able to describe the same fibre reorientation as would the contemporary approaches such as with use of structural tensors and the like, while additionally being capable of showing results intermediary to classical isotropy and the infinitely orthotropic representations. This intermediary case is previously unreported.

Study of the laser-induced decomposition of energetic materials at static high-pressure by time-resolved absorption spectroscopy

NASA Astrophysics Data System (ADS)

Hebert, Philippe; Saint-Amans, Charles

2013-06-01

A detailed description of the reaction rates and mechanisms occurring in shock-induced decomposition of condensed explosives is very important to improve the predictive capabilities of shock-to-detonation transition models. However, direct measurements of such experimental data are difficult to perform during detonation experiments. By coupling pulsed laser ignition of an explosive in a diamond anvil cell (DAC) with time-resolved streak camera recording of transmitted light, it is possible to make direct observations of deflagration phenomena at detonation pressure. We have developed an experimental set-up that allows combustion front propagation rates and time-resolved absorption spectroscopy measurements. The decomposition reactions are initiated using a nanosecond YAG laser and their kinetics is followed by time-resolved absorption spectroscopy. The results obtained for two explosives, nitromethane (NM) and HMX are presented in this paper. For NM, a change in reactivity is clearly seen around 25 GPa. Below this pressure, the reaction products are essentially carbon residues whereas at higher pressure, a transient absorption feature is first observed and is followed by the formation of a white amorphous product. For HMX, the evolution of the absorption as a function of time indicates a multi-step reaction mechanism which is found to depend on both the initial pressure and the laser fluence.

Orlistat interaction with sibutramine and carnitine. A physicochemical and theoretical study

NASA Astrophysics Data System (ADS)

Nicolás-Vázquez, Inés; Hinojosa Torres, Jaime; Cruz Borbolla, Julián; Miranda Ruvalcaba, René; Aceves-Hernández, Juan Manuel

2014-03-01

Chemical degradation of orlistat, (ORT) after melting and reaction of decomposition byproducts with sibutramine, SIB was studied. Interactions between the active pharmaceutical ingredients by using thermal analysis, TA, methods and other experimental techniques such as PXRD, IR and UV-vis spectroscopies were carried out to investigate chemical reactions between components. It was found that orlistat melts with decomposition and byproducts quickly affect sibutramine molecule and then reacting also with carnitine, CRN when the three active pharmaceutical ingredients (API's) are mixed. However ORT byproducts do not react when ORT is mixed only with carnitine. It was found that compounds containing chlorine atoms react easily with orlistat when the temperature increases up to its melting point. Some reaction mechanisms of orlistat decomposition are proposed, the fragments in the mechanisms were found in the corresponding mass spectra. Results obtained indicate that special studies should be carried out in the formulation stage before the final composition of a poly-pill could be established. Similar results are commonly found for compounds very prone to react in presence of water, light and/or temperature. In order to explain the reactivity of orlistat with sibutramine and carnitine, theoretical calculations were carried out and the results are in agreement with the experimental results.

The generalized Hill model: A kinematic approach towards active muscle contraction

NASA Astrophysics Data System (ADS)

Göktepe, Serdar; Menzel, Andreas; Kuhl, Ellen

2014-12-01

Excitation-contraction coupling is the physiological process of converting an electrical stimulus into a mechanical response. In muscle, the electrical stimulus is an action potential and the mechanical response is active contraction. The classical Hill model characterizes muscle contraction though one contractile element, activated by electrical excitation, and two non-linear springs, one in series and one in parallel. This rheology translates into an additive decomposition of the total stress into a passive and an active part. Here we supplement this additive decomposition of the stress by a multiplicative decomposition of the deformation gradient into a passive and an active part. We generalize the one-dimensional Hill model to the three-dimensional setting and constitutively define the passive stress as a function of the total deformation gradient and the active stress as a function of both the total deformation gradient and its active part. We show that this novel approach combines the features of both the classical stress-based Hill model and the recent active-strain models. While the notion of active stress is rather phenomenological in nature, active strain is micro-structurally motivated, physically measurable, and straightforward to calibrate. We demonstrate that our model is capable of simulating excitation-contraction coupling in cardiac muscle with its characteristic features of wall thickening, apical lift, and ventricular torsion.

Document Level Assessment of Document Retrieval Systems in a Pairwise System Evaluation

ERIC Educational Resources Information Center

Rajagopal, Prabha; Ravana, Sri Devi

2017-01-01

Introduction: The use of averaged topic-level scores can result in the loss of valuable data and can cause misinterpretation of the effectiveness of system performance. This study aims to use the scores of each document to evaluate document retrieval systems in a pairwise system evaluation. Method: The chosen evaluation metrics are document-level…

Pairwise Multiple Comparisons in Single Group Repeated Measures Analysis.

ERIC Educational Resources Information Center

Barcikowski, Robert S.; Elliott, Ronald S.

Research was conducted to provide educational researchers with a choice of pairwise multiple comparison procedures (P-MCPs) to use with single group repeated measures designs. The following were studied through two Monte Carlo (MC) simulations: (1) The T procedure of J. W. Tukey (1953); (2) a modification of Tukey's T (G. Keppel, 1973); (3) the…

Impaired Discrimination Learning in Mice Lacking the NMDA Receptor NR2A Subunit

ERIC Educational Resources Information Center

Brigman, Jonathan L.; Feyder, Michael; Saksida, Lisa M.; Bussey, Timothy J.; Mishina, Masayoshi; Holmes, Andrew

2008-01-01

N-Methyl-D-aspartate receptors (NMDARs) mediate certain forms of synaptic plasticity and learning. We used a touchscreen system to assess NR2A subunit knockout mice (KO) for (1) pairwise visual discrimination and reversal learning and (2) acquisition and extinction of an instrumental response requiring no pairwise discrimination. NR2A KO mice…

The effect of liquid-liquid phase separation of glass on the properties and crystallization behavior

NASA Technical Reports Server (NTRS)

Li, J. Z.

1985-01-01

A theoretical discussion is given of the phase separation mechanism of amorphous materials. This includes nucleus growth, spinoidal decomposition, and nuclei agglomeration and coarsening. Various types of glass are analyzed.

Reconciling Mechanistic Hypotheses About Rhizosphere Priming

NASA Astrophysics Data System (ADS)

Cheng, W.

2016-12-01

Rhizosphere priming on soil organic matter decomposition has emerged as a key mechanism regulating biogeochemnical cycling of carbon, nitrogen and other elements from local to global scales. The level of the rhizosphere priming effect on decomposition rates can be comparable to the levels of controls from soil temperature and moisture conditions. However, our understanding on mechanisms responsible for rhizosphere priming remains rudimentary and controversial. The following individual hypotheses have been postulated in the published literature: (1) microbial activation, (2) microbial community succession, (3) aggregate turnover, (4) nitrogen mining, (5) nutrient competition, (6) preferential substrate utilization, and (7) drying-rewetting. Meshing these hypotheses with existing empirical evidence tends to support a general conclusion: each of these 7 hypotheses represents an aspect of the overall rhizosphere priming complex while the relative contribution by each individual aspect varies depending on the actual plant-soil conditions across time and space.

Priming alters soil carbon dynamics during forest succession

NASA Astrophysics Data System (ADS)

Qiao, Na; Xu, Xingliang; Wang, Juan; Kuzyakov, Yakov

2017-04-01

The mechanisms underlying soil carbon (C) dynamics during forest succession remain challenged. We examined priming of soil organic matter (SOM) decomposition along a vegetation succession: grassland, young and old-growth forests. Soil C was primed much more strongly in young secondary forest than in grassland or old-growth forest. Priming resulted in large C losses (negative net C balance) in young-forest soil, whereas C stocks increased in grassland and old-growth forest. Microbial composition assessed by phospholipid fatty acids (PLFA) and utilization of easily available organics (13C-PLFA) indicate that fungi were responsible for priming in young-forest soils. Consequently, labile C inputs released by litter decomposition and root exudation determine microbial functional groups that decompose SOM during forest succession. These findings provide novel insights into connections between SOM dynamics and stabilization with microbial functioning during forest succession and show that priming is an important mechanism for contrasting soil C dynamics in young and old-growth forests.

Simulations of Fluid Nitromethane Under Extreme Conditions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Fried, L E; Reed, E J; Manaa, M R

2003-07-15

We report density functional molecular dynamics simulations to determine the early chemical events of hot (T = 3000 K) and dense (1.97 g/cm{sup 3}, V/V{sub 0} = 0.68) nitromethane (CH{sub 3}NO{sub 2}). The first step in the decomposition process is an intermolecular proton abstraction mechanism that leads to the formation of CH{sub 3}NO{sub 2}H and the aci ion H{sub 2}CNO{sub 2}{sup -}, in support of evidence from static high-pressure and shock experiments. An intramolecular hydrogen transfer that transforms nitromethane into the aci acid form, CH{sub 2}NO{sub 2}H, accompanies this event. This is the first confirmation of chemical reactivity with bondmore » selectivity for an energetic material near the condition of fully reacted specimen. We also report the decomposition mechanism followed up to the formation of H{sub 2}O as the first stable product.« less

A Continuum Damage Mechanics Model to Predict Kink-Band Propagation Using Deformation Gradient Tensor Decomposition

NASA Technical Reports Server (NTRS)

Bergan, Andrew C.; Leone, Frank A., Jr.

2016-01-01

A new model is proposed that represents the kinematics of kink-band formation and propagation within the framework of a mesoscale continuum damage mechanics (CDM) model. The model uses the recently proposed deformation gradient decomposition approach to represent a kink band as a displacement jump via a cohesive interface that is embedded in an elastic bulk material. The model is capable of representing the combination of matrix failure in the frame of a misaligned fiber and instability due to shear nonlinearity. In contrast to conventional linear or bilinear strain softening laws used in most mesoscale CDM models for longitudinal compression, the constitutive response of the proposed model includes features predicted by detailed micromechanical models. These features include: 1) the rotational kinematics of the kink band, 2) an instability when the peak load is reached, and 3) a nonzero plateau stress under large strains.

Ectomycorrhizal fungi decompose soil organic matter using oxidative mechanisms adapted from saprotrophic ancestors.

PubMed

Shah, Firoz; Nicolás, César; Bentzer, Johan; Ellström, Magnus; Smits, Mark; Rineau, Francois; Canbäck, Björn; Floudas, Dimitrios; Carleer, Robert; Lackner, Gerald; Braesel, Jana; Hoffmeister, Dirk; Henrissat, Bernard; Ahrén, Dag; Johansson, Tomas; Hibbett, David S; Martin, Francis; Persson, Per; Tunlid, Anders

2016-03-01

Ectomycorrhizal fungi are thought to have a key role in mobilizing organic nitrogen that is trapped in soil organic matter (SOM). However, the extent to which ectomycorrhizal fungi decompose SOM and the mechanism by which they do so remain unclear, considering that they have lost many genes encoding lignocellulose-degrading enzymes that are present in their saprotrophic ancestors. Spectroscopic analyses and transcriptome profiling were used to examine the mechanisms by which five species of ectomycorrhizal fungi, representing at least four origins of symbiosis, decompose SOM extracted from forest soils. In the presence of glucose and when acquiring nitrogen, all species converted the organic matter in the SOM extract using oxidative mechanisms. The transcriptome expressed during oxidative decomposition has diverged over evolutionary time. Each species expressed a different set of transcripts encoding proteins associated with oxidation of lignocellulose by saprotrophic fungi. The decomposition 'toolbox' has diverged through differences in the regulation of orthologous genes, the formation of new genes by gene duplications, and the recruitment of genes from diverse but functionally similar enzyme families. The capacity to oxidize SOM appears to be common among ectomycorrhizal fungi. We propose that the ancestral decay mechanisms used primarily to obtain carbon have been adapted in symbiosis to scavenge nutrients instead. © 2015 The Authors. New Phytologist © 2015 New Phytologist Trust.

Origin of Outstanding Stability in the Lithium Solid Electrolyte Materials: Insights from Thermodynamic Analyses Based on First-Principles Calculations

DOE PAGES

Zhu, Yizhou; He, Xingfeng; Mo, Yifei

2015-10-06

First-principles calculations were performed to investigate the electrochemical stability of lithium solid electrolyte materials in all-solid-state Li-ion batteries. The common solid electrolytes were found to have a limited electrochemical window. Our results suggest that the outstanding stability of the solid electrolyte materials is not thermodynamically intrinsic but is originated from kinetic stabilizations. The sluggish kinetics of the decomposition reactions cause a high overpotential leading to a nominally wide electrochemical window observed in many experiments. The decomposition products, similar to the solid-electrolyte-interphases, mitigate the extreme chemical potential from the electrodes and protect the solid electrolyte from further decompositions. With the aidmore » of the first-principles calculations, we revealed the passivation mechanism of these decomposition interphases and quantified the extensions of the electrochemical window from the interphases. We also found that the artificial coating layers applied at the solid electrolyte and electrode interfaces have a similar effect of passivating the solid electrolyte. Our newly gained understanding provided general principles for developing solid electrolyte materials with enhanced stability and for engineering interfaces in all-solid-state Li-ion batteries.« less

Boron Nitride-supported Sub-nanometer Pd 6 Clusters for Formic Acid Decomposition: A DFT Study

DOE Office of Scientific and Technical Information (OSTI.GOV)

Schimmenti, Roberto; Cortese, Remedios; Duca, Dario

A periodic, self-consistent planewave DFT study was carried out to explore the potential use of Pd 6 clusters supported on a boron nitride sheet as a catalyst for the selective decomposition of formic acid (HCOOH) to CO 2 and H 2. The competition between formate (HCOO) and carboxyl (COOH) paths on catalytic sites, with different proximities to the support, was studied. Based on energetics alone, the reaction may mainly follow the HCOO route. Slightly lower activation energies were found at the lateral sites of the cluster as compared to top face sites. This is particularly true for the bidentate tomore » monodentate HCOO conversion. Through comparison of results with similar studies on HCOOH decomposition on extended Pd surfaces, it was demonstrated that the existence of undercoordinated sites in the sub-nanometer cluster could play a key role in preferentially stabilizing HCOO over COOH, which is a common CO precursor in this reaction. A hydrogen spillover mechanism was also investigated; migration toward the boron nitride support is not favorable, at least in the early stages of the reaction. However, hydrogen diffusion on the cluster has low barriers compared to those involved in formic acid decomposition.« less

Boron Nitride-supported Sub-nanometer Pd 6 Clusters for Formic Acid Decomposition: A DFT Study

DOE PAGES

Schimmenti, Roberto; Cortese, Remedios; Duca, Dario; ...

2017-04-25

A periodic, self-consistent planewave DFT study was carried out to explore the potential use of Pd 6 clusters supported on a boron nitride sheet as a catalyst for the selective decomposition of formic acid (HCOOH) to CO 2 and H 2. The competition between formate (HCOO) and carboxyl (COOH) paths on catalytic sites, with different proximities to the support, was studied. Based on energetics alone, the reaction may mainly follow the HCOO route. Slightly lower activation energies were found at the lateral sites of the cluster as compared to top face sites. This is particularly true for the bidentate tomore » monodentate HCOO conversion. Through comparison of results with similar studies on HCOOH decomposition on extended Pd surfaces, it was demonstrated that the existence of undercoordinated sites in the sub-nanometer cluster could play a key role in preferentially stabilizing HCOO over COOH, which is a common CO precursor in this reaction. A hydrogen spillover mechanism was also investigated; migration toward the boron nitride support is not favorable, at least in the early stages of the reaction. However, hydrogen diffusion on the cluster has low barriers compared to those involved in formic acid decomposition.« less

Pressure-induced metallization of condensed phase β-HMX under shock loadings via molecular dynamics simulations in conjunction with multi-scale shock technique.

PubMed

Ge, Ni-Na; Wei, Yong-Kai; Zhao, Feng; Chen, Xiang-Rong; Ji, Guang-Fu

2014-07-01

The electronic structure and initial decomposition in high explosive HMX under conditions of shock loading are examined. The simulation is performed using quantum molecular dynamics in conjunction with multi-scale shock technique (MSST). A self-consistent charge density-functional tight-binding (SCC-DFTB) method is adapted. The results show that the N-N-C angle has a drastic change under shock wave compression along lattice vector b at shock velocity 11 km/s, which is the main reason that leads to an insulator-to-metal transition for the HMX system. The metallization pressure (about 130 GPa) of condensed-phase HMX is predicted firstly. We also detect the formation of several key products of condensed-phase HMX decomposition, such as NO2, NO, N2, N2O, H2O, CO, and CO2, and all of them have been observed in previous experimental studies. Moreover, the initial decomposition products include H2 due to the C-H bond breaking as a primary reaction pathway at extreme condition, which presents a new insight into the initial decomposition mechanism of HMX under shock loading at the atomistic level.

Decomposition of hydroxy amino acids in foraminiferal tests; kinetics, mechanism and geochronological implications

USGS Publications Warehouse

Bada, J.L.; Shou, M.-Y.; Man, E.H.; Schroeder, R.A.

1978-01-01

The diagenesis of the hydroxy amino acids serine and threonine in foraminiferal tests has been investigated. The decomposition pathways of these amino acids are complex; the principal reactions appear to be dehydration, aldol cleavage and decarboxylation. Stereochemical studies indicate that the ??-amino-n-butyric acid (ABA) detected in foraminiferal tests is the end product of threonine dehydration pathway. Decomposition of serine and threonine in foraminiferal tests from two well-dated Caribbean deep-sea cores, P6304-8 and -9, has been found to follow irreversible first-order kinetics. Three empirical equations were derived for the disappearance of serine and threonine and the appearance of ABA. These equations can be used as a new geochronological method for dating foraminiferal tests from other deep-sea sediments. Preliminary results suggest that ages deduced from the ABA kinetics equation are most reliable because "species effect" and contamination problems are not important for this nonbiological amino acid. Because of the variable serine and threonine contents of modern foraminiferal species, it is likely that the accurate age estimates can be obtained from the serine and threonine decomposition equations only if a homogeneous species assemblage or single species sample isolated from mixed natural assemblages is used. ?? 1978.

Succession change of microorganisms on plant waste decomposition in simulation modelling field experiment

NASA Astrophysics Data System (ADS)

Vinogradova, Julia; Perminova, Evgenia; Khabibullina, Fluza; Kovaleva, Vera; Lapteva, Elena

2016-04-01

Plant waste decomposition processes are closely associated with living activity of soil microbiota in aboveground ecosystems. Functional activity of microorganisms and soil invertebrates determines plant material transformation rate whereby changes in plant material chemical composition during destruction - succession change of soil biota. The purpose of the work was revealing the mechanism of microorganisms succession change during plant waste decomposition in middle-taiga green-moss spruce forests and coniferous-deciduous secondary stands formed after earlier cut bilberry spruce forests. The study materials were undisturbed bilberry spruce forest (Sample Plot 1 - SP1) and coniferous-deciduous secondary stands which were formed after tree cutting activities of 2001-2002 (SP2) and 1969 and 1970 (SP3). Plant material decomposition intensity was determined in microcosms isolated into kapron bags with cell size of 1 mm. At SP1 and SP2, test material was living mosses and at SP3 - fallen birch and aspen leaves. Every test material was exposed for 2 years. Destruction rate was calculated as a weight loss for a particular time period. Composition of micromycetes which participated in plant material decomposition was assessed by the method of inoculation of soil extract to Getchinson's medium and acidified Czapek's medium (pH=4.5). Microbe number and biomass was analyzed by the method of luminescent microscopy. Chemical analysis of plant material was done in the certified Ecoanalytical Laboratory of the Institute of Biology Komi SC UrD RAS. Finally, plant material destruction intensity was similar for study plots and comprised 40-44 % weight loss for 2 years. The strongest differences in plant material decomposition rate between undisturbed spruce forests and secondary after-cut stands were observed at first stages of destruction process. In the first exposition year, mineralizing processes were most active in undisturbed spruce forest. Decomposition rate in cuts at that period was less by a factor of 1.7-2.3. The highest diversity of moss-decomposing micromycetes (30 species of microscopic fungi of 13 genera) was found for undisturbed spruce forest (SP1). At cuts, the figures were 17 and 23 species of micromycetes, correspondingly. Succession change in composition of micromycetes was best pronounced in undisturbed spruce forest. At cuts, there was no clear mechanism of micromycetes species diversity change during plant waste decomposition. This could serve an anthropogenic disturbance marker of taiga ecosystems. Generally, microscopic moss- and leaf-decomposing fungi at all plots were very species specific. Total biomass of microorganisms in microcosms at cuts was less than that at undisturbed spruce forest by 1.4-1.6 time. Its structure was dominated by mycelium and fungal spores (98-99 % total biomass). On leaf waste decomposition (SP3), microbe biomass got more bacteria. By the obtained data, undisturbed middle-taiga spruce forests have better conditions for living activity of plant waste-decomposing microscopic fungi. This is evidenced by less species diversity of microscopic fungi, shorter length and less biomass of mycelium at cuts as compared with undisturbed spruce forests.

Characterizing Feedback Control Mechanisms in Nonlinear Microbial Models of Soil Organic Matter Decomposition by Stability Analysis

NASA Astrophysics Data System (ADS)

Georgiou, K.; Tang, J.; Riley, W. J.; Torn, M. S.

2014-12-01

Soil organic matter (SOM) decomposition is regulated by biotic and abiotic processes. Feedback interactions between such processes may act to dampen oscillatory responses to perturbations from equilibrium. Indeed, although biological oscillations have been observed in small-scale laboratory incubations, the overlying behavior at the plot-scale exhibits a relatively stable response to disturbances in input rates and temperature. Recent studies have demonstrated the ability of microbial models to capture nonlinear feedbacks in SOM decomposition that linear Century-type models are unable to reproduce, such as soil priming in response to increased carbon input. However, these microbial models often exhibit strong oscillatory behavior that is deemed unrealistic. The inherently nonlinear dynamics of SOM decomposition have important implications for global climate-carbon and carbon-concentration feedbacks. It is therefore imperative to represent these dynamics in Earth System Models (ESMs) by introducing sub-models that accurately represent microbial and abiotic processes. In the present study we explore, both analytically and numerically, four microbe-enabled model structures of varying levels of complexity. The most complex model combines microbial physiology, a non-linear mineral sorption isotherm, and enzyme dynamics. Based on detailed stability analysis of the nonlinear dynamics, we calculate the system modes as functions of model parameters. This dependence provides insight into the source of state oscillations. We find that feedback mechanisms that emerge from careful representation of enzyme and mineral interactions, with parameter values in a prescribed range, are critical for both maintaining system stability and capturing realistic responses to disturbances. Corroborating and expanding upon the results of recent studies, we explain the emergence of oscillatory responses and discuss the appropriate microbe-enabled model structure for inclusion in ESMs.

Elucidating electrolyte decomposition under electron-rich environments at the lithium-metal anode

DOE PAGES

Camacho-Forero, Luis E.; Balbuena, Perla B.

2017-11-07

The lithium metal anode is one of the key components of the lithium–sulfur (Li–S) batteries, which are considered one of the most promising candidates for the next generation of battery systems. However, one of the main challenges that have prevented Li-metal anodes from becoming feasible to be used in commercial batteries is the continuous decomposition of the electrolyte due to its high reactivity, which leads to the formation of solid–electrolyte interphase (SEI) layers. The properties of the SEI can dramatically affect the performance of the batteries. Thus, a rigorous understanding of the electrolyte decomposition is crucial to elucidate improvements inmore » performance of the Li–S technology. Here, in this work, using density functional theory (DFT) and ab initio molecular dynamics simulations (AIMD), we investigate the effect of electron-rich environments on the decomposition mechanism of electrolyte species in pure 1,2-dimethoxyethane (DME) solvent and 1 M lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) and lithium bis(fluorosulfonyl)imide (LiFSI) salt solutions. It is found that systems with pure DME require an average environment of at least ~0.9 |e| per molecule for a DME to decompose into CH 3O - and C 2H 4 2-via a 4-electron transfer. In the case of mixtures, the salts are very prone to react with any excess of electrons. In addition, DME dehydrogenation due to reactions with fragments coming from the salt decompositions was detected. Formation of oligomer anionic species from DME and salt fragments were also identified from the AIMD simulations. Finally, the thermodynamics and kinetics of the most relevant electrolyte decomposition reactions were characterized. DME decomposition reactions predicted from the AIMD simulations were found to be thermodynamically favorable under exposure to Li atoms and/or by reactions with salt fragments. Lastly, in most cases, these reactions were shown to have low to moderate activation barriers.« less

Towards a representation of priming on soil carbon decomposition in the global land biosphere model ORCHIDEE (version 1.9.5.2)

NASA Astrophysics Data System (ADS)

Guenet, Bertrand; Esteban Moyano, Fernando; Peylin, Philippe; Ciais, Philippe; Janssens, Ivan A.

2016-03-01

Priming of soil carbon decomposition encompasses different processes through which the decomposition of native (already present) soil organic matter is amplified through the addition of new organic matter, with new inputs typically being more labile than the native soil organic matter. Evidence for priming comes from laboratory and field experiments, but to date there is no estimate of its impact at global scale and under the current anthropogenic perturbation of the carbon cycle. Current soil carbon decomposition models do not include priming mechanisms, thereby introducing uncertainty when extrapolating short-term local observations to ecosystem and regional to global scale. In this study we present a simple conceptual model of decomposition priming, called PRIM, able to reproduce laboratory (incubation) and field (litter manipulation) priming experiments. Parameters for this model were first optimized against data from 20 soil incubation experiments using a Bayesian framework. The optimized parameter values were evaluated against another set of soil incubation data independent from the ones used for calibration and the PRIM model reproduced the soil incubations data better than the original, CENTURY-type soil decomposition model, whose decomposition equations are based only on first-order kinetics. We then compared the PRIM model and the standard first-order decay model incorporated into the global land biosphere model ORCHIDEE (Organising Carbon and Hydrology In Dynamic Ecosystems). A test of both models was performed at ecosystem scale using litter manipulation experiments from five sites. Although both versions were equally able to reproduce observed decay rates of litter, only ORCHIDEE-PRIM could simulate the observed priming (R2 = 0.54) in cases where litter was added or removed. This result suggests that a conceptually simple and numerically tractable representation of priming adapted to global models is able to capture the sign and magnitude of the priming of litter and soil organic matter.

Towards a representation of priming on soil carbon decomposition in the global land biosphere model ORCHIDEE (version 1.9.5.2)

NASA Astrophysics Data System (ADS)

Guenet, B.; Moyano, F. E.; Peylin, P.; Ciais, P.; Janssens, I. A.

2015-10-01

Priming of soil carbon decomposition encompasses different processes through which the decomposition of native (already present) soil organic matter is amplified through the addition of new organic matter, with new inputs typically being more labile than the native soil organic matter. Evidence for priming comes from laboratory and field experiments, but to date there is no estimate of its impact at global scale and under the current anthropogenic perturbation of the carbon cycle. Current soil carbon decomposition models do not include priming mechanisms, thereby introducing uncertainty when extrapolating short-term local observations to ecosystem and regional to global scale. In this study we present a simple conceptual model of decomposition priming, called PRIM, able to reproduce laboratory (incubation) and field (litter manipulation) priming experiments. Parameters for this model were first optimized against data from 20 soil incubation experiments using a Bayesian framework. The optimized parameter values were evaluated against another set of soil incubation data independent from the ones used for calibration and the PRIM model reproduced the soil incubations data better than the original, CENTURY-type soil decomposition model, whose decomposition equations are based only on first order kinetics. We then compared the PRIM model and the standard first order decay model incorporated into the global land biosphere model ORCHIDEE. A test of both models was performed at ecosystem scale using litter manipulation experiments from 5 sites. Although both versions were equally able to reproduce observed decay rates of litter, only ORCHIDEE-PRIM could simulate the observed priming (R2 = 0.54) in cases where litter was added or removed. This result suggests that a conceptually simple and numerically tractable representation of priming adapted to global models is able to capture the sign and magnitude of the priming of litter and soil organic matter.

Elucidating electrolyte decomposition under electron-rich environments at the lithium-metal anode

DOE Office of Scientific and Technical Information (OSTI.GOV)

Camacho-Forero, Luis E.; Balbuena, Perla B.

The lithium metal anode is one of the key components of the lithium–sulfur (Li–S) batteries, which are considered one of the most promising candidates for the next generation of battery systems. However, one of the main challenges that have prevented Li-metal anodes from becoming feasible to be used in commercial batteries is the continuous decomposition of the electrolyte due to its high reactivity, which leads to the formation of solid–electrolyte interphase (SEI) layers. The properties of the SEI can dramatically affect the performance of the batteries. Thus, a rigorous understanding of the electrolyte decomposition is crucial to elucidate improvements inmore » performance of the Li–S technology. Here, in this work, using density functional theory (DFT) and ab initio molecular dynamics simulations (AIMD), we investigate the effect of electron-rich environments on the decomposition mechanism of electrolyte species in pure 1,2-dimethoxyethane (DME) solvent and 1 M lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) and lithium bis(fluorosulfonyl)imide (LiFSI) salt solutions. It is found that systems with pure DME require an average environment of at least ~0.9 |e| per molecule for a DME to decompose into CH 3O - and C 2H 4 2-via a 4-electron transfer. In the case of mixtures, the salts are very prone to react with any excess of electrons. In addition, DME dehydrogenation due to reactions with fragments coming from the salt decompositions was detected. Formation of oligomer anionic species from DME and salt fragments were also identified from the AIMD simulations. Finally, the thermodynamics and kinetics of the most relevant electrolyte decomposition reactions were characterized. DME decomposition reactions predicted from the AIMD simulations were found to be thermodynamically favorable under exposure to Li atoms and/or by reactions with salt fragments. Lastly, in most cases, these reactions were shown to have low to moderate activation barriers.« less

Elucidating electrolyte decomposition under electron-rich environments at the lithium-metal anode.

PubMed

Camacho-Forero, Luis E; Balbuena, Perla B

2017-11-22

The lithium metal anode is one of the key components of the lithium-sulfur (Li-S) batteries, which are considered one of the most promising candidates for the next generation of battery systems. However, one of the main challenges that have prevented Li-metal anodes from becoming feasible to be used in commercial batteries is the continuous decomposition of the electrolyte due to its high reactivity, which leads to the formation of solid-electrolyte interphase (SEI) layers. The properties of the SEI can dramatically affect the performance of the batteries. Thus, a rigorous understanding of the electrolyte decomposition is crucial to elucidate improvements in performance of the Li-S technology. In this work, using density functional theory (DFT) and ab initio molecular dynamics simulations (AIMD), we investigate the effect of electron-rich environments on the decomposition mechanism of electrolyte species in pure 1,2-dimethoxyethane (DME) solvent and 1 M lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) and lithium bis(fluorosulfonyl)imide (LiFSI) salt solutions. It is found that systems with pure DME require an average environment of at least ∼0.9 |e| per molecule for a DME to decompose into CH 3 O - and C 2 H 4 2- via a 4-electron transfer. In the case of mixtures, the salts are very prone to react with any excess of electrons. In addition, DME dehydrogenation due to reactions with fragments coming from the salt decompositions was detected. Formation of oligomer anionic species from DME and salt fragments were also identified from the AIMD simulations. Finally, the thermodynamics and kinetics of the most relevant electrolyte decomposition reactions were characterized. DME decomposition reactions predicted from the AIMD simulations were found to be thermodynamically favorable under exposure to Li atoms and/or by reactions with salt fragments. In most cases, these reactions were shown to have low to moderate activation barriers.

Early-stage changes in natural (13)C and (15)N abundance and nutrient dynamics during different litter decomposition.

PubMed

Gautam, Mukesh Kumar; Lee, Kwang-Sik; Song, Byeong-Yeol; Lee, Dongho; Bong, Yeon-Sik

2016-05-01

Decomposition, nutrient, and isotopic (δ(13)C and δ(15)N) dynamics during 1 year were studied for leaf and twig litters of Pinus densiflora, Castanea crenata, Erigeron annuus, and Miscanthus sinensis growing on a highly weathered soil with constrained nutrient supply using litterbags in a cool temperate region of South Korea. Decay constant (k/year) ranged from 0.58 to 1.29/year, and mass loss ranged from 22.36 to 58.43 % among litter types. The results demonstrate that mass loss and nutrient dynamics of decomposing litter were influenced by the seasonality of mineralization and immobilization processes. In general, most nutrients exhibited alternate phases of rapid mineralization followed by gradual immobilization, except K, which was released throughout the field incubation. At the end of study, among all the nutrients only N and P showed net immobilization. Mobility of different nutrients from decomposing litter as the percentage of initial litter nutrient concentration was in the order of K > Mg > Ca > N ≈ P. The δ(13)C (0.32-6.70 ‰) and δ(15)N (0.74-3.90 ‰) values of residual litters showed nonlinear increase and decrease, respectively compared to initial isotopic values during decomposition. Litter of different functional types and chemical quality converged toward a conservative nutrient use strategy through mechanisms of slow decomposition and slow nutrient mobilization. Our results indicate that litter quality and season, are the most important regulators of litter decomposition in these forests. The results revealed significant relationships between litter decomposition rates and N, C:N ratio and P, and seasonality (temperature). These results and the convergence of different litters towards conservative nutrient use in these nutrient constrained ecosystems imply optimization of litter management because litter removal can have cascading effects on litter decomposition and nutrient availability in these systems.

Kinetics evaluation and thermal decomposition characteristics of co-pyrolysis of municipal sewage sludge and hazelnut shell.

PubMed

Zhao, Bing; Xu, Xinyang; Li, Haibo; Chen, Xi; Zeng, Fanqiang

2018-01-01

Hazelnut shell, as novel biomass, has lower ash content and abundant hydrocarbon, which can be utilized resourcefully with municipal sewage sludge (MSS) by co-pyrolyisis to decrease total content of pollution. The co-pyrolysis of MSS and hazelnut shell blend was analyzed by a method of multi-heating rates and different blend ratios with TG-DTG-MS under N 2 atmosphere. The apparent activation energy of co-pyrolysis was calculated by three iso-conversional methods. Satava-Sestak method was used to determine mechanism function G(α) of co-pyrolysis, and Lorentzian function was used to simulate multi-peaks curves. The results showed there were four thermal decomposition stages, and the biomass were cracked and evolved at different temperature ranges. The apparent activation energy increased from 123.99 to 608.15kJ/mol. The reaction mechanism of co-pyrolysis is random nucleation and nuclei growth. The apparent activation energy and mechanism function afford a theoretical groundwork for co-pyrolysis technology. Copyright © 2017 Elsevier Ltd. All rights reserved.

A configuration space of homologous proteins conserving mutual information and allowing a phylogeny inference based on pair-wise Z-score probabilities.

PubMed

Bastien, Olivier; Ortet, Philippe; Roy, Sylvaine; Maréchal, Eric

2005-03-10

Popular methods to reconstruct molecular phylogenies are based on multiple sequence alignments, in which addition or removal of data may change the resulting tree topology. We have sought a representation of homologous proteins that would conserve the information of pair-wise sequence alignments, respect probabilistic properties of Z-scores (Monte Carlo methods applied to pair-wise comparisons) and be the basis for a novel method of consistent and stable phylogenetic reconstruction. We have built up a spatial representation of protein sequences using concepts from particle physics (configuration space) and respecting a frame of constraints deduced from pair-wise alignment score properties in information theory. The obtained configuration space of homologous proteins (CSHP) allows the representation of real and shuffled sequences, and thereupon an expression of the TULIP theorem for Z-score probabilities. Based on the CSHP, we propose a phylogeny reconstruction using Z-scores. Deduced trees, called TULIP trees, are consistent with multiple-alignment based trees. Furthermore, the TULIP tree reconstruction method provides a solution for some previously reported incongruent results, such as the apicomplexan enolase phylogeny. The CSHP is a unified model that conserves mutual information between proteins in the way physical models conserve energy. Applications include the reconstruction of evolutionary consistent and robust trees, the topology of which is based on a spatial representation that is not reordered after addition or removal of sequences. The CSHP and its assigned phylogenetic topology, provide a powerful and easily updated representation for massive pair-wise genome comparisons based on Z-score computations.

Simulations of the pairwise kinematic Sunyaev-Zel'dovich signal

DOE PAGES

Flender, Samuel; Bleem, Lindsey; Finkel, Hal; ...

2016-05-26

The pairwise kinematic Sunyaev–Zel'dovich (kSZ) signal from galaxy clusters is a probe of their line of sight momenta, and thus a potentially valuable source of cosmological information. In addition to the momenta, the amplitude of the measured signal depends on the properties of the intracluster gas and observational limitations such as errors in determining cluster centers and redshifts. In this work, we simulate the pairwise kSZ signal of clusters atmore » $$z\\lt 1$$, using the output from a cosmological N-body simulation and including the properties of the intracluster gas via a model that can be varied in post-processing. We find that modifications to the gas profile due to star formation and feedback reduce the pairwise kSZ amplitude of clusters by $$\\sim 50\\%$$, relative to the naive "gas traces mass" assumption. We demonstrate that miscentering can reduce the overall amplitude of the pairwise kSZ signal by up to 10%, while redshift errors can lead to an almost complete suppression of the signal at small separations. We confirm that a high-significance detection is expected from the combination of data from current generation, high-resolution cosmic microwave background experiments, such as the South Pole Telescope, and cluster samples from optical photometric surveys, such as the Dark Energy Survey. As a result, we forecast that future experiments such as Advanced ACTPol in conjunction with data from the Dark Energy Spectroscopic Instrument will yield detection significances of at least $$20\\sigma $$, and up to $$57\\sigma $$ in an optimistic scenario.« less

Study of the solid-phase thermal decomposition of NTO using Simultaneous Thermogravimetric Modulated Beam Mass Spectrometry (STMBMS)

NASA Technical Reports Server (NTRS)

Minier, L.; Behrens, R.; Burkey, T. J.

1997-01-01

The solid phase thermal reaction chemistry of NTO between 190 and 250 C is presently being evaluated by utilizing STMBMS, a technique that enables the authors to measure the vapor pressure of NTO and to explore the reaction mechanisms and chemical kinetics associated with the NTO thermal decomposition process. The vapor pressure of NTO is expressed as Log(sub 10) p(torr) = 12.5137 + 6,296.553(1/t(k)) and the Delta-H(sub subl) = 28.71 +/- 0.07 kcal/mol (120.01 +/- 0.29 kJ/mol). The pyrolysis of NTO results in the formation of gaseous products and a condensed-phase residue. The identity of the major gaseous products and their origin from within the NTO molecules are determined based on the results from pyrolysis of NTO, NTO-3-C-13, NTO-1,2- (15)N2 and NTO-(2)H2. Identification of the products show the major gaseous products to be N2, CO2, NO, HNCO, H2O and some N2O, CO, HCN and NH3. The N2 is mostly derived from the N-1 and N-2 positions with some being from the N-4 and N-1 or N-2 positions. The CO2 is derived from both carbons in the NTO molecule in comparable amounts. The residue has an elemental formula of C(2.1)H(.26)N(2.9)O and FTIR analysis suggests that the residue is polyurea- and polycarbamate- like in nature. The temporal behaviors of the rates of formation of the gaseous products indicate that the overall thermal decomposition of NTO in the temperature range evaluated involves four major processes: (1) NTO sublimation; (2) an apparent solid-solid phase transition between 190 and 195 C; (3) a decomposition regime induced by the presence of exogenous H2O at the onset of decomposition; and (4) a decomposition regime that occurs at the onset of decomposition and continues until the depletion of NTO. Decomposition pathways that are consistent with the data are presented.

Wood decomposition as influenced by invertebrates.

PubMed

Ulyshen, Michael D

2016-02-01

The diversity and habitat requirements of invertebrates associated with dead wood have been the subjects of hundreds of studies in recent years but we still know very little about the ecological or economic importance of these organisms. The purpose of this review is to examine whether, how and to what extent invertebrates affect wood decomposition in terrestrial ecosystems. Three broad conclusions can be reached from the available literature. First, wood decomposition is largely driven by microbial activity but invertebrates also play a significant role in both temperate and tropical environments. Primary mechanisms include enzymatic digestion (involving both endogenous enzymes and those produced by endo- and ectosymbionts), substrate alteration (tunnelling and fragmentation), biotic interactions and nitrogen fertilization (i.e. promoting nitrogen fixation by endosymbiotic and free-living bacteria). Second, the effects of individual invertebrate taxa or functional groups can be accelerative or inhibitory but the cumulative effect of the entire community is generally to accelerate wood decomposition, at least during the early stages of the process (most studies are limited to the first 2-3 years). Although methodological differences and design limitations preclude meta-analysis, studies aimed at quantifying the contributions of invertebrates to wood decomposition commonly attribute 10-20% of wood loss to these organisms. Finally, some taxa appear to be particularly influential with respect to promoting wood decomposition. These include large wood-boring beetles (Coleoptera) and termites (Termitoidae), especially fungus-farming macrotermitines. The presence or absence of these species may be more consequential than species richness and the influence of invertebrates is likely to vary biogeographically. Published 2014. This article is a U.S. Government work and is in the public domain in the USA.

Subcalcic diopsides from kimberlites: Chemistry, exsolution microstructures, and thermal history

USGS Publications Warehouse

McCallister, R.H.; Nord, G.L.

1981-01-01

Twenty-six subcalcic diopside megacrysts (Ca/(Ca+ Mg)) = 0.280-0.349, containing approximately 10 mol% jadeite, from 15 kimberlite bodies in South Africa, Botswana, Tanzania, and Lesotho, have been characterized by electron microprobe analysis, X-ray-precession photography, and transmission electron microscopy. Significant exsolution of pigeonite was observed only in those samples for which Ca/(Ca+Mg)???0.320. The exsolution microstructure consists of coherent (001) lamellae with wavelengths ranging from 20 to 31 nm and compositional differences between the hosts and lamellae ranging from 10 to 30 mol% wollastonite. These observations suggest that the exsolution reaction mechanism was spinodal decomposition and that the megacrysts have been quenched at various stages of completion of the decomposition process. Annealing experiments in evacuated SiO2 glass tubes at 1,150?? C for 128 hours failed to homogenize microstructure, whereas, at 5 kbar and 1,150?? C for only 7.25 hours, the two lattices were homogenized. This "pressure effect" suggests that spinodal decomposition in the kimberlitic subcalcic diopside megacrysts can only occur at depths less than ???15 km; the cause of the effect may be the jadeite component in the pyroxene. "Apparent quench" temperatures for the exsolution process in the megacrysts range from 1,250?? C to 990?? C, suggesting that decomposition must have commenced at temperatures of more than ???1,000?? C. These P-T limits lead to the conclusion that, in those kimberlites where spinodal decomposition has occurred in subcalcic diopside megacrysts, such decomposition occurred at shallow levels (<15 km) and, at the present erosion level, temperatures must have been greater than 1,000?? C. ?? 1981 Springer-Verlag.

The processing of aluminum gasarites via thermal decomposition of interstitial hydrides

NASA Astrophysics Data System (ADS)

Licavoli, Joseph J.

Gasarite structures are a unique type of metallic foam containing tubular pores. The original methods for their production limited them to laboratory study despite appealing foam properties. Thermal decomposition processing of gasarites holds the potential to increase the application of gasarite foams in engineering design by removing several barriers to their industrial scale production. The following study characterized thermal decomposition gasarite processing both experimentally and theoretically. It was found that significant variation was inherent to this process therefore several modifications were necessary to produce gasarites using this method. Conventional means to increase porosity and enhance pore morphology were studied. Pore morphology was determined to be more easily replicated if pores were stabilized by alumina additions and powders were dispersed evenly. In order to better characterize processing, high temperature and high ramp rate thermal decomposition data were gathered. It was found that the high ramp rate thermal decomposition behavior of several hydrides was more rapid than hydride kinetics at low ramp rates. This data was then used to estimate the contribution of several pore formation mechanisms to the development of pore structure. It was found that gas-metal eutectic growth can only be a viable pore formation mode if non-equilibrium conditions persist. Bubble capture cannot be a dominant pore growth mode due to high bubble terminal velocities. Direct gas evolution appears to be the most likely pore formation mode due to high gas evolution rate from the decomposing particulate and microstructural pore growth trends. The overall process was evaluated for its economic viability. It was found that thermal decomposition has potential for industrialization, but further refinements are necessary in order for the process to be viable.

Classification of forest-based ecotourism areas in Pocahontas County of West Virginia using GIS and pairwise comparison method

Treesearch

Ishwar Dhami; Jinyang. Deng

2012-01-01

Many previous studies have examined ecotourism primarily from the perspective of tourists while largely ignoring ecotourism destinations. This study used geographical information system (GIS) and pairwise comparison to identify forest-based ecotourism areas in Pocahontas County, West Virginia. The study adopted the criteria and scores developed by Boyd and Butler (1994...

Learning Factors Transfer Analysis: Using Learning Curve Analysis to Automatically Generate Domain Models

ERIC Educational Resources Information Center

Pavlik, Philip I. Jr.; Cen, Hao; Koedinger, Kenneth R.

2009-01-01

This paper describes a novel method to create a quantitative model of an educational content domain of related practice item-types using learning curves. By using a pairwise test to search for the relationships between learning curves for these item-types, we show how the test results in a set of pairwise transfer relationships that can be…

Macrobenthic assemblages of the Changjiang River estuary (Yangtze River, China) and adjacent continental shelf relative to mild summer hypoxia

NASA Astrophysics Data System (ADS)

Liao, Yibo; Shou, Lu; Tang, Yanbin; Zeng, Jiangning; Gao, Aigen; Chen, Quanzhen; Yan, Xiaojun

2017-05-01

To assess the effects of hypoxia, macrobenthic communities along an estuarine gradient of the Changjiang estuary and adjacent continental shelf were analyzed. This revealed spatial variations in the communities and relationships with environmental variables during periods of reduced dissolved oxygen (DO) concentration in summer. Statistical analyses revealed significant differences in macrobenthic community composition among the three zones: estuarine zone (EZ), mildly hypoxic zone (MHZ) in the continental shelf, and normoxic zone (NZ) in the continental shelf (Global R =0.206, P =0.002). Pairwise tests showed that the macrobenthic community composition of the EZ was significantly different from the MHZ (pairwise test R =0.305, P =0.001) and the NZ (pairwise test R =0.259, P =0.001). There was no significant difference in macrobenthic communities between the MHZ and the NZ (pairwise test R =0.062, P =0.114). The taxa included small and typically opportunistic polychaetes, which made the greatest contribution to the dissimilarity between the zones. The effects of mild hypoxia on the macrobenthic communities are a result not only of reduced DO concentration but also of differences in environmental variables such as temperature, salinity, and nutrient concentrations caused by stratification.

From pairwise to group interactions in games of cyclic dominance.

PubMed

Szolnoki, Attila; Vukov, Jeromos; Perc, Matjaž

2014-06-01

We study the rock-paper-scissors game in structured populations, where the invasion rates determine individual payoffs that govern the process of strategy change. The traditional version of the game is recovered if the payoffs for each potential invasion stem from a single pairwise interaction. However, the transformation of invasion rates to payoffs also allows the usage of larger interaction ranges. In addition to the traditional pairwise interaction, we therefore consider simultaneous interactions with all nearest neighbors, as well as with all nearest and next-nearest neighbors, thus effectively going from single pair to group interactions in games of cyclic dominance. We show that differences in the interaction range affect not only the stationary fractions of strategies but also their relations of dominance. The transition from pairwise to group interactions can thus decelerate and even revert the direction of the invasion between the competing strategies. Like in evolutionary social dilemmas, in games of cyclic dominance, too, the indirect multipoint interactions that are due to group interactions hence play a pivotal role. Our results indicate that, in addition to the invasion rates, the interaction range is at least as important for the maintenance of biodiversity among cyclically competing strategies.

Detection of the kinematic Sunyaev–Zel'dovich effect with DES Year 1 and SPT

DOE Office of Scientific and Technical Information (OSTI.GOV)

Soergel, B.; Flender, S.; Story, K. T.

Here, we detect the kinematic Sunyaev-Zel'dovich (kSZ) effect with a statistical significance ofmore » $$4.2 \\sigma$$ by combining a cluster catalogue derived from the first year data of the Dark Energy Survey (DES) with CMB temperature maps from the South Pole Telescope Sunyaev-Zel'dovich (SPT-SZ) Survey. This measurement is performed with a differential statistic that isolates the pairwise kSZ signal, providing the first detection of the large-scale, pairwise motion of clusters using redshifts derived from photometric data. By fitting the pairwise kSZ signal to a theoretical template we measure the average central optical depth of the cluster sample, $$\\bar{\\tau}_e = (3.75 \\pm 0.89)\\cdot 10^{-3}$$. We compare the extracted signal to realistic simulations and find good agreement with respect to the signal-to-noise, the constraint on $$\\bar{\\tau}_e$$, and the corresponding gas fraction. High-precision measurements of the pairwise kSZ signal with future data will be able to place constraints on the baryonic physics of galaxy clusters, and could be used to probe gravity on scales $$ \\gtrsim 100$$ Mpc.« less

Detection of the kinematic Sunyaev–Zel'dovich effect with DES Year 1 and SPT

DOE PAGES

Soergel, B.; Flender, S.; Story, K. T.; ...

2016-06-17

Here, we detect the kinematic Sunyaev-Zel'dovich (kSZ) effect with a statistical significance ofmore » $$4.2 \\sigma$$ by combining a cluster catalogue derived from the first year data of the Dark Energy Survey (DES) with CMB temperature maps from the South Pole Telescope Sunyaev-Zel'dovich (SPT-SZ) Survey. This measurement is performed with a differential statistic that isolates the pairwise kSZ signal, providing the first detection of the large-scale, pairwise motion of clusters using redshifts derived from photometric data. By fitting the pairwise kSZ signal to a theoretical template we measure the average central optical depth of the cluster sample, $$\\bar{\\tau}_e = (3.75 \\pm 0.89)\\cdot 10^{-3}$$. We compare the extracted signal to realistic simulations and find good agreement with respect to the signal-to-noise, the constraint on $$\\bar{\\tau}_e$$, and the corresponding gas fraction. High-precision measurements of the pairwise kSZ signal with future data will be able to place constraints on the baryonic physics of galaxy clusters, and could be used to probe gravity on scales $$ \\gtrsim 100$$ Mpc.« less

Workshop on Explosive and Propellant Combustion Mechanisms

DTIC Science & Technology

1991-07-01

Trubert, Decomposition and Combustion Measurements 30 R.S. Miller and A.W. Miziolek, High Energy Density Materials Combustion 56 T.B. Brill...arranging this activity came from Dr. R.S. Miller , Chief Scientist, Mechanics Division, ONR, and Dr. Bernard Finck, Head, New Molecules Section, Defense...34. Armstrong, in consultation with R.S. Miller , J. Boileau, and SNPE colleagues, arranged for the participation of U.S. scientists, especially

Radiolysis of lignin: Prospective mechanism of high-temperature decomposition

NASA Astrophysics Data System (ADS)

Ponomarev, A. V.

2017-12-01

The range of the radiation-thermal processes resulting in conversion of lignin into monomeric phenols is considered. Statistically the most probable places of macromolecule ionization are aromatic units. Release of phenolic products from a lignin macromolecule is the multistage process beginning via fragmentation of primary cation-radicals. Reactions of electrons and small radicals with macromolecules, also as degradation of cation-radicals, result in formation of phenoxyl radicals. Macroradicals possess lower heat stability in comparison with macromolecules. Thermal decomposition of macroradicals leads to release of monohydric and dihydric phenols. The probability of benzenediols formation increases in the presence of alkanes. As noted, partial transformation of lignin into charcoal is inevitable.

Hilbert complexes of nonlinear elasticity

NASA Astrophysics Data System (ADS)

Angoshtari, Arzhang; Yavari, Arash

2016-12-01

We introduce some Hilbert complexes involving second-order tensors on flat compact manifolds with boundary that describe the kinematics and the kinetics of motion in nonlinear elasticity. We then use the general framework of Hilbert complexes to write Hodge-type and Helmholtz-type orthogonal decompositions for second-order tensors. As some applications of these decompositions in nonlinear elasticity, we study the strain compatibility equations of linear and nonlinear elasticity in the presence of Dirichlet boundary conditions and the existence of stress functions on non-contractible bodies. As an application of these Hilbert complexes in computational mechanics, we briefly discuss the derivation of a new class of mixed finite element methods for nonlinear elasticity.

Autonomous movement of silica and glass micro-objects based on a catalytic molecular propulsion system.

PubMed

Stock, Christoph; Heureux, Nicolas; Browne, Wesley R; Feringa, Ben L

2008-01-01

A general approach for the easy functionalization of bare silica and glass surfaces with a synthetic manganese catalyst is reported. Decomposition of H(2)O(2) by this dinuclear metallic center into H(2)O and O(2) induced autonomous movement of silica microparticles and glass micro-sized fibers. Although several mechanisms have been proposed to rationalise movement of particles driven by H(2)O(2) decomposition to O(2) and water (recoil from O(2) bubbles, ([36,45]) interfacial tension gradient([37-42]), it is apparent in the present system that ballistic movement is due to the growth of O(2) bubbles.

Decomposition of the Thermal Boundary Resistance across Carbon Nanotube-Graphene Junctions to Different Mechanisms.

PubMed

Shi, Jingjing; Zhong, Yang; Fisher, Timothy S; Ruan, Xiulin

2018-05-02

Three different mechanisms are identified to contribute to thermal resistances across a carbon nanotube-graphene junction: material mismatch, nonplanar junction, and defects. To isolate the contributions of each mechanism, we have designed five types of junctions and performed nonequilibrium molecular dynamics simulations. The results show that the contributions from the three mechanisms are similar, each at around 2.5 × 10 -11 m 2 K/W. The relations between thermal boundary resistance and both defect number and turning angle at the interface are also studied.

Decomposition of heterogeneous organic matterand its long-term stabilization in soils

USGS Publications Warehouse

Sierra, Carlos A.; Harmon, Mark E.; Perakis, Steven S.

2011-01-01

Soil organic matter is a complex mixture of material with heterogeneous biological, physical, and chemical properties. Decomposition models represent this heterogeneity either as a set of discrete pools with different residence times or as a continuum of qualities. It is unclear though, whether these two different approaches yield comparable predictions of organic matter dynamics. Here, we compare predictions from these two different approaches and propose an intermediate approach to study organic matter decomposition based on concepts from continuous models implemented numerically. We found that the disagreement between discrete and continuous approaches can be considerable depending on the degree of nonlinearity of the model and simulation time. The two approaches can diverge substantially for predicting long-term processes in soils. Based on our alternative approach, which is a modification of the continuous quality theory, we explored the temporal patterns that emerge by treating substrate heterogeneity explicitly. The analysis suggests that the pattern of carbon mineralization over time is highly dependent on the degree and form of nonlinearity in the model, mostly expressed as differences in microbial growth and efficiency for different substrates. Moreover, short-term stabilization and destabilization mechanisms operating simultaneously result in long-term accumulation of carbon characterized by low decomposition rates, independent of the characteristics of the incoming litter. We show that representation of heterogeneity in the decomposition process can lead to substantial improvements in our understanding of carbon mineralization and its long-term stability in soils.

Effect of charged and excited states on the decomposition of 1,1-diamino-2,2-dinitroethylene molecules

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kimmel, Anna V.; Sushko, Peter V.; Shluger, Alexander L.

The authors have calculated the electronic structure of individual 1,1-diamino-2,2-dinitroethylene molecules (FOX-7) in the gas phase by means of density functional theory with the hybrid B3LYP functional and 6-31+G(d,p) basis set and considered their dissociation pathways. Positively and negatively charged states as well as the lowest excited states of the molecule were simulated. They found that charging and excitation can not only reduce the activation barriers for decomposition reactions but also change the dominating chemistry from endo- to exothermic type. In particular, they found that there are two competing primary initiation mechanisms of FOX-7 decomposition: C-NO{sub 2} bond fission andmore » C-NO{sub 2} to CONO isomerization. Electronic excitation or charging of FOX-7 disfavors CONO formation and, thus, terminates this channel of decomposition. However, if CONO is formed from the neutral FOX-7 molecule, charge trapping and/or excitation results in spontaneous splitting of an NO group accompanied by the energy release. Intramolecular hydrogen transfer is found to be a rare event in FOX-7 unless free electrons are available in the vicinity of the molecule, in which case HONO formation is a feasible exothermic reaction with a relatively low energy barrier. The effect of charged and excited states on other possible reactions is also studied. Implications of the obtained results to FOX-7 decomposition in condensed state are discussed.« less

N2-fixing red alder indirectly accelerates ecosystem nitrogen cycling

USGS Publications Warehouse

Perakis, Steven S.; Matkins, Joselin J.; Hibbs, David E.

2012-01-01

Symbiotic N2-fixing tree species can accelerate ecosystem N dynamics through decomposition via direct pathways by producing readily decomposed leaf litter and increasing N supply to decomposers, as well as via indirect pathways by increasing tissue and detrital N in non-fixing vegetation. To evaluate the relative importance of these pathways, we compared three-year decomposition and N dynamics of N2-fixing red alder leaf litter (2.34 %N) to both low-N (0.68 %N) and high-N (1.21 %N) litter of non-fixing Douglas-fir, and decomposed each litter source in four forests dominated by either red alder or Douglas-fir. We also used experimental N fertilization of decomposition plots to assess elevated N availability as a potential mechanism of N2-fixer effects on litter mass loss and N dynamics. Direct effects of N2-fixing red alder on decomposition occurred primarily as faster N release from red alder than Douglas-fir litter, but direct increases in N supply to decomposers via fertilization did not stimulate decomposition of any litter. Fixed N indirectly influenced detrital dynamics by increasing Douglas-fir tissue and litter N concentrations, which accelerated litter N release without accelerating mass loss. By increasing soil N, tissue N, and the rate of N release from litter of non-fixers, we conclude that N2-fixing vegetation can indirectly foster plant-soil feedbacks that contribute to the persistence of elevated N availability in terrestrial ecosystems.

An MPI + $X$ implementation of contact global search using Kokkos

DOE PAGES

Hansen, Glen A.; Xavier, Patrick G.; Mish, Sam P.; ...

2015-10-05

This paper describes an approach that seeks to parallelize the spatial search associated with computational contact mechanics. In contact mechanics, the purpose of the spatial search is to find “nearest neighbors,” which is the prelude to an imprinting search that resolves the interactions between the external surfaces of contacting bodies. In particular, we are interested in the contact global search portion of the spatial search associated with this operation on domain-decomposition-based meshes. Specifically, we describe an implementation that combines standard domain-decomposition-based MPI-parallel spatial search with thread-level parallelism (MPI-X) available on advanced computer architectures (those with GPU coprocessors). Our goal ismore » to demonstrate the efficacy of the MPI-X paradigm in the overall contact search. Standard MPI-parallel implementations typically use a domain decomposition of the external surfaces of bodies within the domain in an attempt to efficiently distribute computational work. This decomposition may or may not be the same as the volume decomposition associated with the host physics. The parallel contact global search phase is then employed to find and distribute surface entities (nodes and faces) that are needed to compute contact constraints between entities owned by different MPI ranks without further inter-rank communication. Key steps of the contact global search include computing bounding boxes, building surface entity (node and face) search trees and finding and distributing entities required to complete on-rank (local) spatial searches. To enable source-code portability and performance across a variety of different computer architectures, we implemented the algorithm using the Kokkos hardware abstraction library. While we targeted development towards machines with a GPU accelerator per MPI rank, we also report performance results for OpenMP with a conventional multi-core compute node per rank. Results here demonstrate a 47 % decrease in the time spent within the global search algorithm, comparing the reference ACME algorithm with the GPU implementation, on an 18M face problem using four MPI ranks. As a result, while further work remains to maximize performance on the GPU, this result illustrates the potential of the proposed implementation.« less

Effect of metal oxides on the stabilization of soil organic matter

NASA Astrophysics Data System (ADS)

Stelmach, Wioleta

2017-04-01

Soil organic matter (SOM) is protected from decomposition by three mechanisms: 1) biochemical stabilization through the accumulation of recalcitrant SOM compounds, 2) physical stabilization, i.e. spatial inaccessibility of SOM for microbes, and 3) chemical protection of SOM through intimate interaction with minerals and metal oxides. The latter mechanisms suggest that added organic substances (i.e. post-fermentation sludge) can be stabilized by metal oxides to increase C sequestration in soil. The aim of this study was to determine the effects of Fe2O3 - one of the dominant metal oxides in soil - on the sequestration of post-fermentation sludge C in soil by separately tracing the decomposition of sludge and of SOM to carbon dioxide (CO2). To determine changes in SOM turnover after the addition of post-fermentation sludge without/with Fe2O3, the isotopic signatures of both C sources (SOM and post-fermentation sludge) were used. Using differences in the 13C natural abundance of the soil (C3 originated, δ13C = -26) and the post-fermentation sludge (C4 originated, δ13C = -18), the CO2 fluxes arising from both C sources were tracked. Addition of post-fermentation sludge to the soil increased the CO2 production by 30% compared to soil without sludge. δ13C analysis of the total CO2 efflux revealed that post-fermentation sludge decreased SOM decomposition. Fe2O3 slightly suppressed sludge decomposition, and therefore increased C sequestration in soil. Only 30% of the post-fermentation sludge had been mineralized after one month of incubation in the soil. The collective results of my study reveal that application of post-fermentation sludge suppresses SOM decomposition, suggesting its use as a fertilizer could positively influence long-term soil quality. Finally, the success of the 13C natural abundance microcosm labeling approach in my study supports its use as an effective method of analyzing the effects of various fertilization techniques on soil nutrient retention. Such results were only possible by partitioning of the total CO2.

Living network meta-analysis compared with pairwise meta-analysis in comparative effectiveness research: empirical study.

PubMed

Nikolakopoulou, Adriani; Mavridis, Dimitris; Furukawa, Toshi A; Cipriani, Andrea; Tricco, Andrea C; Straus, Sharon E; Siontis, George C M; Egger, Matthias; Salanti, Georgia

2018-02-28

To examine whether the continuous updating of networks of prospectively planned randomised controlled trials (RCTs) ("living" network meta-analysis) provides strong evidence against the null hypothesis in comparative effectiveness of medical interventions earlier than the updating of conventional, pairwise meta-analysis. Empirical study of the accumulating evidence about the comparative effectiveness of clinical interventions. Database of network meta-analyses of RCTs identified through searches of Medline, Embase, and the Cochrane Database of Systematic Reviews until 14 April 2015. Network meta-analyses published after January 2012 that compared at least five treatments and included at least 20 RCTs. Clinical experts were asked to identify in each network the treatment comparison of greatest clinical interest. Comparisons were excluded for which direct and indirect evidence disagreed, based on side, or node, splitting test (P<0.10). Cumulative pairwise and network meta-analyses were performed for each selected comparison. Monitoring boundaries of statistical significance were constructed and the evidence against the null hypothesis was considered to be strong when the monitoring boundaries were crossed. A significance level was defined as α=5%, power of 90% (β=10%), and an anticipated treatment effect to detect equal to the final estimate from the network meta-analysis. The frequency and time to strong evidence was compared against the null hypothesis between pairwise and network meta-analyses. 49 comparisons of interest from 44 networks were included; most (n=39, 80%) were between active drugs, mainly from the specialties of cardiology, endocrinology, psychiatry, and rheumatology. 29 comparisons were informed by both direct and indirect evidence (59%), 13 by indirect evidence (27%), and 7 by direct evidence (14%). Both network and pairwise meta-analysis provided strong evidence against the null hypothesis for seven comparisons, but for an additional 10 comparisons only network meta-analysis provided strong evidence against the null hypothesis (P=0.002). The median time to strong evidence against the null hypothesis was 19 years with living network meta-analysis and 23 years with living pairwise meta-analysis (hazard ratio 2.78, 95% confidence interval 1.00 to 7.72, P=0.05). Studies directly comparing the treatments of interest continued to be published for eight comparisons after strong evidence had become evident in network meta-analysis. In comparative effectiveness research, prospectively planned living network meta-analyses produced strong evidence against the null hypothesis more often and earlier than conventional, pairwise meta-analyses. Published by the BMJ Publishing Group Limited. For permission to use (where not already granted under a licence) please go to http://group.bmj.com/group/rights-licensing/permissions.

Living network meta-analysis compared with pairwise meta-analysis in comparative effectiveness research: empirical study

PubMed Central

Nikolakopoulou, Adriani; Mavridis, Dimitris; Furukawa, Toshi A; Cipriani, Andrea; Tricco, Andrea C; Straus, Sharon E; Siontis, George C M; Egger, Matthias

2018-01-01

Abstract Objective To examine whether the continuous updating of networks of prospectively planned randomised controlled trials (RCTs) (“living” network meta-analysis) provides strong evidence against the null hypothesis in comparative effectiveness of medical interventions earlier than the updating of conventional, pairwise meta-analysis. Design Empirical study of the accumulating evidence about the comparative effectiveness of clinical interventions. Data sources Database of network meta-analyses of RCTs identified through searches of Medline, Embase, and the Cochrane Database of Systematic Reviews until 14 April 2015. Eligibility criteria for study selection Network meta-analyses published after January 2012 that compared at least five treatments and included at least 20 RCTs. Clinical experts were asked to identify in each network the treatment comparison of greatest clinical interest. Comparisons were excluded for which direct and indirect evidence disagreed, based on side, or node, splitting test (P<0.10). Outcomes and analysis Cumulative pairwise and network meta-analyses were performed for each selected comparison. Monitoring boundaries of statistical significance were constructed and the evidence against the null hypothesis was considered to be strong when the monitoring boundaries were crossed. A significance level was defined as α=5%, power of 90% (β=10%), and an anticipated treatment effect to detect equal to the final estimate from the network meta-analysis. The frequency and time to strong evidence was compared against the null hypothesis between pairwise and network meta-analyses. Results 49 comparisons of interest from 44 networks were included; most (n=39, 80%) were between active drugs, mainly from the specialties of cardiology, endocrinology, psychiatry, and rheumatology. 29 comparisons were informed by both direct and indirect evidence (59%), 13 by indirect evidence (27%), and 7 by direct evidence (14%). Both network and pairwise meta-analysis provided strong evidence against the null hypothesis for seven comparisons, but for an additional 10 comparisons only network meta-analysis provided strong evidence against the null hypothesis (P=0.002). The median time to strong evidence against the null hypothesis was 19 years with living network meta-analysis and 23 years with living pairwise meta-analysis (hazard ratio 2.78, 95% confidence interval 1.00 to 7.72, P=0.05). Studies directly comparing the treatments of interest continued to be published for eight comparisons after strong evidence had become evident in network meta-analysis. Conclusions In comparative effectiveness research, prospectively planned living network meta-analyses produced strong evidence against the null hypothesis more often and earlier than conventional, pairwise meta-analyses. PMID:29490922

A counterexample and a modification to the adiabatic approximation theorem in quantum mechanics

NASA Technical Reports Server (NTRS)

Gingold, H.

1991-01-01

A counterexample to the adiabatic approximation theorem is given when degeneracies are present. A formulation of an alternative version is proposed. A complete asymptotic decomposition for n dimensional self-adjoint Hamiltonian systems is restated and used.

High-Fidelity, Computational Modeling of Non-Equilibrium Discharges for Combustion Applications

DTIC Science & Technology

2013-10-01

gradient reconstruction)  4th order RK time integration  Domain decomposition parallel enabled Plasma chemistry mechanism 22  Methane-air... plasma chemistry mechanism  Species and pathways relevant to plasma time scale (~10’s ns)  26 Species : E, O, N2 , O2 , H , N2+ , O2+ , N4+ , O4...Photoionization (3-term Helmholtz equation model) 0.0067 0.0447 0.0346 0.1121 0.3059 0.5994 Plasma chemistry mechanism used in studies 81

Representing Matrix Cracks Through Decomposition of the Deformation Gradient Tensor in Continuum Damage Mechanics Methods

NASA Technical Reports Server (NTRS)

Leone, Frank A., Jr.

2015-01-01

A method is presented to represent the large-deformation kinematics of intraply matrix cracks and delaminations in continuum damage mechanics (CDM) constitutive material models. The method involves the additive decomposition of the deformation gradient tensor into 'crack' and 'bulk material' components. The response of the intact bulk material is represented by a reduced deformation gradient tensor, and the opening of an embedded cohesive interface is represented by a normalized cohesive displacement-jump vector. The rotation of the embedded interface is tracked as the material deforms and as the crack opens. The distribution of the total local deformation between the bulk material and the cohesive interface components is determined by minimizing the difference between the cohesive stress and the bulk material stress projected onto the cohesive interface. The improvements to the accuracy of CDM models that incorporate the presented method over existing approaches are demonstrated for a single element subjected to simple shear deformation and for a finite element model of a unidirectional open-hole tension specimen. The material model is implemented as a VUMAT user subroutine for the Abaqus/Explicit finite element software. The presented deformation gradient decomposition method reduces the artificial load transfer across matrix cracks subjected to large shearing deformations, and avoids the spurious secondary failure modes that often occur in analyses based on conventional progressive damage models.

Photocatalytic ozonation of terephthalic acid: a by-product-oriented decomposition study.

PubMed

Fuentes, Iliana; Rodríguez, Julia L; Poznyak, Tatyana; Chairez, Isaac

2014-11-01

Terephthalic acid (TA) is considered as a refractory model compound. For this reason, the TA degradation usually requires a prolonged reaction time to achieve mineralization. In this study, vanadium oxide (VxOy) supported on titanium oxide (TiO2) served as a photocatalyst in the ozonation of the TA with light-emitting diodes (LEDs), having a bandwidth centered at 452 nm. The modified catalyst (VxOy/TiO2) in combination with ozone and LEDs improved the TA degradation and its by-products. The results obtained by this system were compared with photolysis, single ozonation, catalytic ozonation, and photocatalytic ozonation of VxOy/TiO2 with UV lamp. The LED-based photocatalytic ozonation showed almost the same decomposition efficiency of the TA, but it was better in comparison with the use of UV lamp. The oxalic acid accumulation, as the final product of the TA decomposition, was directly influenced by either the presence of VxOy or/and the LED irradiation. Several by-products formed during the TA degradation, such as muconic, fumaric, and oxalic acids, were identified. Besides, two unidentified by-products were completely removed during the observed time (60 min). It was proposed that the TA elimination in the presence of VxOy/TiO2 as catalyst was carried out by the combination of different mechanisms: molecular ozone reaction, indirect mechanism conducted by ·OH, and the surface complex formation.

Intraspecific traits change biodiversity effects on ecosystem functioning under metal stress.

PubMed

Fernandes, Isabel; Pascoal, Cláudia; Cássio, Fernanda

2011-08-01

Studies investigating the impacts of biodiversity loss on ecosystem processes have often reached different conclusions, probably because insufficient attention has been paid to some aspects including (1) which biodiversity measure (e.g., species number, species identity or trait) better explains ecosystem functioning, (2) the mechanisms underpinning biodiversity effects, and (3) how can environmental context modulates biodiversity effects. Here, we investigated how species number (one to three species) and traits of aquatic fungal decomposers (by replacement of a functional type from an unpolluted site by another from a metal-polluted site) affect fungal production (biomass accumulation) and plant litter decomposition in the presence and absence of metal stress. To examine the putative mechanisms that explain biodiversity effects, we determined the contribution of each fungal species to the total biomass produced in multicultures by real-time PCR. In the absence of metal, positive diversity effects were observed for fungal production and leaf decomposition as a result of species complementarity. Metal stress decreased diversity effects on leaf decomposition in assemblages containing the functional type from the unpolluted site, probably due to competitive interactions between fungi. However, dominance effect maintained positive diversity effects under metal stress in assemblages containing the functional type from the metal-polluted site. These findings emphasize the importance of intraspecific diversity in modulating diversity effects under metal stress, providing evidence that trait-based diversity measures should be incorporated when examining biodiversity effects.

Influence of CNTs decomposition during reactive friction-stir processing of an Al-Mg alloy on the correlation between microstructural characteristics and microtextural components.

PubMed

Khodabakhshi, F; Nosko, M; Gerlich, A P

2018-05-03

Multipass friction-stir processing was employed to uniformly disperse multiwalled carbon nanotubes (MW-CNTs) within an Al-Mg alloy metal matrix. Decomposition of MW-CNTs occurs in situ as a result of solid-state chemical reactions, forming fullerene (C60) and aluminium carbide (Al 4 C 3 ) phases during reactive high temperature severe plastic processing. The effects of this decomposition on the microstructural features, dynamic restoration mechanisms and crystallographic microtextural developments are studied for the first time by using electron backscatter diffraction (EBSD) and transmission electron microscopy (TEM) analysis. The formation of an equiaxed grain structure with an average size of ∼1.5 μm occurs within the stirred zone (SZ) under the influence of inclusions which hinder grain boundary migration via Zener-Smith pinning mechanisms during the discontinuous dynamic recrystallisation (DDRX). Formation of two strong Cubic and Brass microtextural components in the heat affected zone (HAZ) and thermomechanical affected zone (TMAZ) was noted as compared to the completely random and Cube components found in the base and SZ regions, respectively. The microstructural modification led to hardening and tensile strength improvement for the processed nanocomposite by ∼55% and 110%, respectively with respect to the annealed Al-Mg base alloy. © 2018 The Authors Journal of Microscopy © 2018 Royal Microscopical Society.

Root surface temperature variation during mechanical removal of root canal filling material. An in vitro study.

PubMed

García-Cuerva, Martín; Horvath, Lucía; Pinasco, Laura; Ciparelli, Verónica; Gualtieri, Ariel; Casadoumecq, Ana C; Rodríguez, Pablo; Gonzalez-Zanotto, Carlos

2017-04-01

The aim of this study was to analyze in vitro temperature changes on the outer surface of the dental root during mechanical filling removal procedures. Thirty recently extracted single-rooted lower premolars were cut transversally at 16 mm from the apex in order to standardize sample length. Endodontic treatment was performed on them. The filling material was subsequently removed using Gates Glidden (G1, G2, G3); Peeso (P1, P2, P3) and PostecPlus FRC (FRC) reamers while temperatures were measured on the outer surface using a digital device with thermocouple at 0, 2, 4, 6, 8, 10 and 15 seconds. Temperatures were compared using repeated measures ANOVA followed by pairwise comparison with Tukey's test. All reamers caused significant temperature variation between different times (p<0.05). Pairwise comparisons indicated that temperature increased with time for all reamers (p<0.05). Significant differences in temperature were found between different reamers after 0, 2, 4, 6, 8,10 and 15 seconds (p<0.05). Temperature at the root surface increased considerably. Values higher than 50°C were recorded, the greatest increase from baseline being 16°C. Accordingly, if the procedure were begun at 37°C (physiological temperature), the temperature in the surrounding tissues - cementum, periodontium and bone - would rise to 53°C. An increase in 10°C above body temperature at the root surface may cause lesions in surrounding tissues. While removing filling material, it is essential to cool, control action time and use instruments in perfect condition, all of which may contribute to reducing the heat generated and transmitted to the outer root surface. Sociedad Argentina de Pediatría.

Influence of high-pressure torsion on formation/destruction of nano-sized spinodal structures

NASA Astrophysics Data System (ADS)

Alhamidi, Ali; Edalati, Kaveh; Horita, Zenji

2018-04-01

The microstructures and hardness of Al - 30 mol.% Zn are investigated after processing by high-pressure torsion (HPT) for different numbers of revolutions, N = 1, 3, 10 or 25, as well as after post-HPT annealing at different temperatures, T = 373 K, 473 K, 573 K and 673 K. It was found that a work softening occurs by decreasing the grain size to the submicrometer level and increasing the fraction of high-angle boundaries. As a result of HPT processing, a complete decomposition of supersaturated solid solution of Zn in Al occurs and the spinodal structure is destroyed. This suggests that softening of the Al-Zn alloys after HPT is due to the decomposition of the supersaturated solid solution and destruction of spinodal decomposition. After post-HPT annealing, ultrafine-grained Al-Zn alloys show an unusual mechanical properties and its hardness increased to 187 HV. Microstructural analysis showed that the high hardness after post-HPT annealing is due to the formation of spinodal structures.

Preparation, characterization and catalytic property of CuO nano/microspheres via thermal decomposition of cathode-plasma generating Cu2(OH)3NO3 nano/microspheres.

PubMed

Zhang, Zhi-Kun; Guo, Deng-Zhu; Zhang, Geng-Min

2011-05-01

CuO nano/microspheres with a wide diametric distribution were prepared by thermal decomposition of Cu(2)(OH)(3)NO(3) nano/microspheres formed in a simple asymmetric-electrode based cathodic-plasma electrolysis. The morphological, componential, and structural information about the two kinds of spheres were characterized in detail by SEM, TEM, EDX, XPS and XRD, and the results revealed that the morphology of the spheres were well kept after the componential and structural transformation from Cu(2)(OH)(3)NO(3) into CuO. The TGA/DSC study showed that the CuO nano/microspheres could be explored to be a promising additive for accelerating the thermal decomposition of ammonium perchlorate (AP). Combining with the current curve and emission spectrum measured in the plasma electrolysis, formation mechanism of the Cu(2)(OH)(3)NO(3) spheres was also discussed. Copyright © 2011 Elsevier Inc. All rights reserved.

Synthesis and characterization of an energetic compound Cu(Mtta)2(NO3)2 and effect on thermal decomposition of ammonium perchlorate.

PubMed

Yang, Qi; Chen, Sanping; Xie, Gang; Gao, Shengli

2011-12-15

An energetic coordination compound Cu(Mtta)(2)(NO(3))(2) has been synthesized by using 1-methyltetrazole (Mtta) as ligand and its structure has been characterized by X-ray single crystal diffraction. The central copper (II) cation was coordinated by four O atoms from two Mtta ligands and two N atoms from two NO(3)(-) anions to form a six-coordinated and distorted octahedral structure. 2D superamolecular layer structure was formed by the extensive intermolecular hydrogen bonds between Mtta ligands and NO(3)(-) anions. Thermal decomposition process of the compound was predicted based on DSC and TG-DTG analyses results. The kinetic parameters of the first exothermic process of the compound were studied by the Kissinger's and Ozawa-Doyle's methods. Sensitivity tests revealed that the compound was insensitive to mechanical stimuli. In addition, compound was explored as additive to promote the thermal decomposition of ammonium perchlorate (AP) by differential scanning calorimetry. Copyright © 2011 Elsevier B.V. All rights reserved.

ZnO twin-cones: synthesis, photoluminescence, and catalytic decomposition of ammonium perchlorate.

PubMed

Sun, Xuefei; Qiu, Xiaoqing; Li, Liping; Li, Guangshe

2008-05-19

ZnO twin-cones, a new member to the ZnO family, were prepared directly by a solvothermal method using a mixed solution of zinc nitrate and ethanol. The reaction and growth mechanisms of ZnO twin-cones were investigated by X-ray diffraction, UV-visible spectra, infrared and ion trap mass spectra, and transmission electron microscopy. All as-prepared ZnO cones consisted of tiny single crystals with lengths of several micrometers. With prolonging of the reaction time from 1.5 h to 7 days, the twin-cone shape did not change at all, while the lattice parameters increased slightly and the emission peak of photoluminescence shifted from the green region to the near orange region. ZnO twin-cones are also explored as an additive to promote the thermal decomposition of ammonium perchlorate. The variations of photoluminescence spectra and catalytic roles in ammonium perchlorate decomposition were discussed in terms of the defect structure of ZnO twin-cones.

Molecular Theory of Detonation Initiation: Insight from First Principles Modeling of the Decomposition Mechanisms of Organic Nitro Energetic Materials.

PubMed

Tsyshevsky, Roman V; Sharia, Onise; Kuklja, Maija M

2016-02-19

This review presents a concept, which assumes that thermal decomposition processes play a major role in defining the sensitivity of organic energetic materials to detonation initiation. As a science and engineering community we are still far away from having a comprehensive molecular detonation initiation theory in a widely agreed upon form. However, recent advances in experimental and theoretical methods allow for a constructive and rigorous approach to design and test the theory or at least some of its fundamental building blocks. In this review, we analyzed a set of select experimental and theoretical articles, which were augmented by our own first principles modeling and simulations, to reveal new trends in energetic materials and to refine known existing correlations between their structures, properties, and functions. Our consideration is intentionally limited to the processes of thermally stimulated chemical reactions at the earliest stage of decomposition of molecules and materials containing defects.

Detecting decompositions of sulfur hexafluoride using reduced graphene oxide decorated with Pt nanoparticles

NASA Astrophysics Data System (ADS)

Chen, Dachang; Tang, Ju; Zhang, Xiaoxing; Fang, Jiani; Li, Yi; Zhuo, Ran

2018-05-01

The resistance-typed gas sensing material of Pt nanoparticles (PtNPs) decorated reduced graphene oxide (RGO) synthesized by one-step chemical reduction for the detection of four types of SF6 decompositions was explored. The PtNPs disperse uniformly on RGO with particle size near 2–4 nm and a small number of particles are larger than 10 nm. Gas sensing tests suggest that the introduction of PtNPs increases the response to SO2, SOF2 and H2S compared to pure RGO and PtNPs-RGO experiences resistance reducing in SO2 and SOF2 while presenting the opposite case in H2S. Elevating the temperature enhances the recovery properties to SO2 and H2S but lowers the sensitivity. The sensing mechanism for Pt-RGO in low oxygen and water environment depends mainly on the charge transfer between gas and adsorbent and the solvent on material surface. The work provides experimental investigation of Pt-RGO to detect SF6 decompositions.

Molecular Theory of Detonation Initiation: Insight from First Principles Modeling of the Decomposition Mechanisms of Organic Nitro Energetic Materials

DOE PAGES

Tsyshevsky, Roman; Sharia, Onise; Kuklja, Maija

2016-02-19

Our review presents a concept, which assumes that thermal decomposition processes play a major role in defining the sensitivity of organic energetic materials to detonation initiation. As a science and engineering community we are still far away from having a comprehensive molecular detonation initiation theory in a widely agreed upon form. However, recent advances in experimental and theoretical methods allow for a constructive and rigorous approach to design and test the theory or at least some of its fundamental building blocks. In this review, we analyzed a set of select experimental and theoretical articles, which were augmented by our ownmore » first principles modeling and simulations, to reveal new trends in energetic materials and to refine known existing correlations between their structures, properties, and functions. Lastly, our consideration is intentionally limited to the processes of thermally stimulated chemical reactions at the earliest stage of decomposition of molecules and materials containing defects.« less

Oxidative decomposition of aromatic hydrocarbons by electron beam irradiation

NASA Astrophysics Data System (ADS)

Han, Do-Hung; Stuchinskaya, Tatiana; Won, Yang-Soo; Park, Wan-Sik; Lim, Jae-Kyong

2003-05-01

Decomposition of aromatic volatile organic compounds (VOCs) under electron beam irradiation was studied in order to examine the kinetics of the process, to characterize the reaction product distribution and to develop a process of waste gas control technology. Toluene, ethylbenzene, o-, m-, p-xylenes and chlorobenzene were used as target materials. The experiments were carried out at doses ranging from 0.5 to 10 kGy, using a flow reactor utilized under electron beam irradiation. Maximum degrees of decomposition carried out at 10 kGy in air environment were 55-65% for “non-chlorinated” aromatic VOC and 85% for chlorobenzene. It was found that a combination of aromatic pollutants with chlorobenzene would considerably increase the degradation value up to nearly 50% compared to the same compounds in the absence of chlorine groups. Based on our experimental observation, the degradation mechanism of the aromatic compounds combined with chloro-compound suggests that a chlorine radical, formed from EB irradiation, induces a chain reaction, resulting in an accelerating oxidative destruction of aromatic VOCs.

1,3,5-trinitro-1,3,5-triazine decomposition and chemisorption on Al(111) surface: first-principles molecular dynamics study.

PubMed

Umezawa, Naoto; Kalia, Rajiv K; Nakano, Aiichiro; Vashista, Priya; Shimojo, Fuyuki

2007-06-21

We have investigated the decomposition and chemisorption of a 1,3,5-trinitro-1,3,5-triazine (RDX) molecule on Al(111) surface using molecular dynamics simulations, in which interatomic forces are computed quantum mechanically in the framework of the density functional theory (DFT). The real-space DFT calculations are based on higher-order finite difference and norm-conserving pseudopotential methods. Strong attractive forces between oxygen and aluminum atoms break N-O and N-N bonds in the RDX and, subsequently, the dissociated oxygen atoms and NO molecules oxidize the Al surface. In addition to these Al surface-assisted decompositions, ring cleavage of the RDX molecule is also observed. These reactions occur spontaneously without potential barriers and result in the attachment of the rest of the RDX molecule to the surface. This opens up the possibility of coating Al nanoparticles with RDX molecules to avoid the detrimental effect of oxidation in high energy density material applications.

Experimental study of trimethyl aluminum decomposition

NASA Astrophysics Data System (ADS)

Zhang, Zhi; Pan, Yang; Yang, Jiuzhong; Jiang, Zhiming; Fang, Haisheng

2017-09-01

Trimethyl aluminum (TMA) is an important precursor used for metal-organic chemical vapor deposition (MOCVD) of most Al-containing structures, in particular of nitride structures. The reaction mechanism of TMA with ammonia is neither clear nor certain due to its complexity. Pyrolysis of trimethyl metal is the start of series of reactions, thus significantly affecting the growth. Experimental study of TMA pyrolysis, however, has not yet been conducted in detail. In this paper, a reflectron time-of-flight mass spectrometer is adopted to measure the TMA decomposition from room temperature to 800 °C in a special pyrolysis furnace, activated by soft X-ray from the synchrotron radiation. The results show that generation of methyl, ethane and monomethyl aluminum (MMA) indicates the start of the pyrolysis process. In the low temperature range from 25 °C to 700 °C, the main product is dimethyl aluminum (DMA) from decomposition of TMA. For temperatures larger than 700 °C, the main products are MMA, DMA, methyl and ethane.

Decomposition of Potassium Ferrate(VI) (K2FeO4) and Potassium Ferrate(III) (KFeO2): In-situ Mössbauer Spectroscopy Approach

NASA Astrophysics Data System (ADS)

Machala, Libor; Zboril, Radek; Sharma, Virender K.; Homonnay, Zoltan

2008-10-01

Mössbauer spectroscopy was shown to be very useful technique studying the mechanism of thermal decomposition or aging processes of the most known ferrate(VI), K2FeO4. In-situ Mössbauer spectroscopy approach was used to monitor the phase composition during the studied processes. The experimental set-up was designed to perform in-situ measurements at high temperatures and at different air humid conditions at room temperature. The potassium ferrate(III), KFeO2 was demonstrated to be the primary product of thermal decomposition of K2FeO4. The KFeO2 was unstable in a humid air at room temperature and reacted with components of air, H2O and CO2 to give Fe2O3 nanoparticles and KHCO3. The aging kinetics of K2FeO4 and KFeO2 under humid air were significantly dependent on the relative air humidity.

CombAlign: a code for generating a one-to-many sequence alignment from a set of pairwise structure-based sequence alignments.

PubMed

Zhou, Carol L Ecale

2015-01-01

In order to better define regions of similarity among related protein structures, it is useful to identify the residue-residue correspondences among proteins. Few codes exist for constructing a one-to-many multiple sequence alignment derived from a set of structure or sequence alignments, and a need was evident for creating such a tool for combining pairwise structure alignments that would allow for insertion of gaps in the reference structure. This report describes a new Python code, CombAlign, which takes as input a set of pairwise sequence alignments (which may be structure based) and generates a one-to-many, gapped, multiple structure- or sequence-based sequence alignment (MSSA). The use and utility of CombAlign was demonstrated by generating gapped MSSAs using sets of pairwise structure-based sequence alignments between structure models of the matrix protein (VP40) and pre-small/secreted glycoprotein (sGP) of Reston Ebolavirus and the corresponding proteins of several other filoviruses. The gapped MSSAs revealed structure-based residue-residue correspondences, which enabled identification of structurally similar versus differing regions in the Reston proteins compared to each of the other corresponding proteins. CombAlign is a new Python code that generates a one-to-many, gapped, multiple structure- or sequence-based sequence alignment (MSSA) given a set of pairwise sequence alignments (which may be structure based). CombAlign has utility in assisting the user in distinguishing structurally conserved versus divergent regions on a reference protein structure relative to other closely related proteins. CombAlign was developed in Python 2.6, and the source code is available for download from the GitHub code repository.

Improving prediction of heterodimeric protein complexes using combination with pairwise kernel.

PubMed

Ruan, Peiying; Hayashida, Morihiro; Akutsu, Tatsuya; Vert, Jean-Philippe

2018-02-19

Since many proteins become functional only after they interact with their partner proteins and form protein complexes, it is essential to identify the sets of proteins that form complexes. Therefore, several computational methods have been proposed to predict complexes from the topology and structure of experimental protein-protein interaction (PPI) network. These methods work well to predict complexes involving at least three proteins, but generally fail at identifying complexes involving only two different proteins, called heterodimeric complexes or heterodimers. There is however an urgent need for efficient methods to predict heterodimers, since the majority of known protein complexes are precisely heterodimers. In this paper, we use three promising kernel functions, Min kernel and two pairwise kernels, which are Metric Learning Pairwise Kernel (MLPK) and Tensor Product Pairwise Kernel (TPPK). We also consider the normalization forms of Min kernel. Then, we combine Min kernel or its normalization form and one of the pairwise kernels by plugging. We applied kernels based on PPI, domain, phylogenetic profile, and subcellular localization properties to predicting heterodimers. Then, we evaluate our method by employing C-Support Vector Classification (C-SVC), carrying out 10-fold cross-validation, and calculating the average F-measures. The results suggest that the combination of normalized-Min-kernel and MLPK leads to the best F-measure and improved the performance of our previous work, which had been the best existing method so far. We propose new methods to predict heterodimers, using a machine learning-based approach. We train a support vector machine (SVM) to discriminate interacting vs non-interacting protein pairs, based on informations extracted from PPI, domain, phylogenetic profiles and subcellular localization. We evaluate in detail new kernel functions to encode these data, and report prediction performance that outperforms the state-of-the-art.

Mössbauer study of iron in high oxidation states in the K Fe O system

NASA Astrophysics Data System (ADS)

Dedushenko, Sergey K.; Perfiliev, Yurii D.; Saprykin, Aleksandr A.

2008-07-01

Oxidation of metallic iron by potassium superoxide leads to the formation of ferrate(V). Under room temperature this compound is unstable and instantly decomposes by disproportionation mechanism. Grinding the substance into powder accelerates the decomposition process.

APOLLO: a quality assessment service for single and multiple protein models.

PubMed

Wang, Zheng; Eickholt, Jesse; Cheng, Jianlin

2011-06-15

We built a web server named APOLLO, which can evaluate the absolute global and local qualities of a single protein model using machine learning methods or the global and local qualities of a pool of models using a pair-wise comparison approach. Based on our evaluations on 107 CASP9 (Critical Assessment of Techniques for Protein Structure Prediction) targets, the predicted quality scores generated from our machine learning and pair-wise methods have an average per-target correlation of 0.671 and 0.917, respectively, with the true model quality scores. Based on our test on 92 CASP9 targets, our predicted absolute local qualities have an average difference of 2.60 Å with the actual distances to native structure. http://sysbio.rnet.missouri.edu/apollo/. Single and pair-wise global quality assessment software is also available at the site.

Kinetic study of the thermal decomposition of uranium metaphosphate, U(PO3)4, into uranium pyrophosphate, UP2O7

NASA Astrophysics Data System (ADS)

Yang, Hee-Chul; Kim, Hyung-Ju; Lee, Si-Young; Yang, In-Hwan; Chung, Dong-Yong

2017-06-01

The thermochemical properties of uranium compounds have attracted much interest in relation to thermochemical treatments and the safe disposal of radioactive waste bearing uranium compounds. The characteristics of the thermal decomposition of uranium metaphosphate, U(PO3)4, into uranium pyrophosphate, UP2O7, have been studied from the view point of reaction kinetics and acting mechanisms. A mixture of U(PO3)4 and UP2O7 was prepared from the pyrolysis residue of uranium-bearing spent TBP. A kinetic analysis of the reaction of U(PO3)4 into UP2O7 was conducted using an isoconversional method and a master plot method on the basis of data from a non-isothermal thermogravimetric analysis. The thermal decomposition of U(PO3)4 into UP2O7 followed a single-step reaction with an activation energy of 175.29 ± 1.58 kJ mol-1. The most probable kinetic model was determined as a type of nucleation and nuclei-growth models, the Avrami-Erofeev model (A3), which describes that there are certain restrictions on nuclei growth of UP2O7 during the solid-state decomposition of U(PO3)4.

Effect of gamma-irradiation on thermal decomposition kinetics, X-ray diffraction pattern and spectral properties of tris(1,2-diaminoethane)nickel(II)sulphate

NASA Astrophysics Data System (ADS)

Jayashri, T. A.; Krishnan, G.; Rema Rani, N.

2014-12-01

Tris(1,2-diaminoethane)nickel(II)sulphate was prepared, and characterised by various chemical and spectral techniques. The sample was irradiated with 60Co gamma rays for varying doses. Sulphite ion and ammonia were detected and estimated in the irradiated samples. Non-isothermal decomposition kinetics, X-ray diffraction pattern, Fourier transform infrared spectroscopy, electronic, fast atom bombardment mass spectra, and surface morphology of the complex were studied before and after irradiation. Kinetic parameters were evaluated by integral, differential, and approximation methods. Irradiation enhanced thermal decomposition, lowering thermal and kinetic parameters. The mechanism of decomposition is controlled by R3 function. From X-ray diffraction studies, change in lattice parameters and subsequent changes in unit cell volume and average crystallite size were observed. Both unirradiated and irradiated samples of the complex belong to trigonal crystal system. Decrease in the intensity of the peaks was observed in the infrared spectra of irradiated samples. Electronic spectral studies revealed that the M-L interaction is unaffected by irradiation. Mass spectral studies showed that the fragmentation patterns of the unirradiated and irradiated samples are similar. The additional fragment with m/z 256 found in the irradiated sample is attributed to S8+. Surface morphology of the complex changed upon irradiation.

Synthesis, characterization and non-isothermal decomposition kinetic of a new galactochloralose based polymer.

PubMed

Kök, Gökhan; Ay, Kadir; Ay, Emriye; Doğan, Fatih; Kaya, Ismet

2014-01-30

A glycopolymer, poly(3-O-methacroyl-5,6-O-isopropylidene-1,2-O-(S)-trichloroethylidene-α-d-galactofuranose) (PMIPTEG) was synthesized from the sugar-carrying methacrylate monomer, 3-O-methacroyl-5,6-O-isopropylidene-1,2-O-(S)-trichloroethylidene-α-d-galactofuranose (MIPTEG) via conventional free radical polymerization with AIBN in 1,4-dioxane. The structures of glycomonomer and their polymers were confirmed by UV-vis, FT-IR, (1)H NMR, (13)C NMR, GPC, TG/DTG-DTA, DSC, and SEM techniques. SEM images showed that PMIPTEG had a straight-chain length structure. On the other hand, the thermal decomposition kinetics of polymer were investigated by means of thermogravimetric analysis in dynamic nitrogen atmosphere at different heating rates. The apparent activation energies for thermal decomposition of the PMIPTEG were calculated using the Kissinger, Kim-Park, Tang, Flynn-Wall-Ozawa (FWO), Kissinger-Akahira-Sunose (KAS) and Friedman methods and were found to be 100.15, 104.40, 102.0, 102.2, 103.2 and 99.6 kJ/mol, respectively. The most likely process mechanism related to the thermal decomposition stage of PMIPTEG was determined to be a Dn deceleration type in terms of master plots results. Copyright © 2013 Elsevier Ltd. All rights reserved.

Shock wave and modeling study of the thermal decomposition reactions of pentafluoroethane and 2-H-heptafluoropropane.

PubMed

Cobos, C J; Sölter, L; Tellbach, E; Troe, J

2014-06-07

The thermal decomposition reactions of CF3CF2H and CF3CFHCF3 have been studied in shock waves by monitoring the appearance of CF2 radicals. Temperatures in the range 1400-2000 K and Ar bath gas concentrations in the range (2-10) × 10(-5) mol cm(-3) were employed. It is shown that the reactions are initiated by C-C bond fission and not by HF elimination. Differing conclusions in the literature about the primary decomposition products, such as deduced from experiments at very low pressures, are attributed to unimolecular falloff effects. By increasing the initial reactant concentrations in Ar from 60 to 1000 ppm, a retardation of CF2 formation was observed while the final CF2 yields remained close to two CF2 per C2F5H or three CF2 per C3F7H decomposed. This is explained by secondary bimolecular reactions which lead to comparably stable transient species like CF3H, releasing CF2 at a slower rate. Quantum-chemical calculations and kinetic modeling help to identify the reaction pathways and provide estimates of rate constants for a series of primary and secondary reactions in the decomposition mechanism.

Scattering property based contextual PolSAR speckle filter

NASA Astrophysics Data System (ADS)

Mullissa, Adugna G.; Tolpekin, Valentyn; Stein, Alfred

2017-12-01

Reliability of the scattering model based polarimetric SAR (PolSAR) speckle filter depends upon the accurate decomposition and classification of the scattering mechanisms. This paper presents an improved scattering property based contextual speckle filter based upon an iterative classification of the scattering mechanisms. It applies a Cloude-Pottier eigenvalue-eigenvector decomposition and a fuzzy H/α classification to determine the scattering mechanisms on a pre-estimate of the coherency matrix. The H/α classification identifies pixels with homogeneous scattering properties. A coarse pixel selection rule groups pixels that are either single bounce, double bounce or volume scatterers. A fine pixel selection rule is applied to pixels within each canonical scattering mechanism. We filter the PolSAR data and depending on the type of image scene (urban or rural) use either the coarse or fine pixel selection rule. Iterative refinement of the Wishart H/α classification reduces the speckle in the PolSAR data. Effectiveness of this new filter is demonstrated by using both simulated and real PolSAR data. It is compared with the refined Lee filter, the scattering model based filter and the non-local means filter. The study concludes that the proposed filter compares favorably with other polarimetric speckle filters in preserving polarimetric information, point scatterers and subtle features in PolSAR data.

Study of thermal, flammability and mechanical properties of intumescent flame retardant PP/kenaf nanocomposites

NASA Astrophysics Data System (ADS)

Subasinghe; Das; Bhattacharyya

2016-07-01

Detrimental physical and mechanical properties are common problems for composites when their flame retardancy is improved through filler additions. An increased interest of the synergistic nanoparticle addition to improve the flame retardancy of natural fiber composites is the aim of this work. The paper investigates the synergistic effect of two different nanoparticles (halloysite nanotubes (HNTs) and montmorillonite (MMT) nanoclay) on the flame and mechanical properties in an intumescent ammonium polyphosphate (APP)-based polypropylene (PP)/kenaf composite system. First, the nature of nanoparticle dispersion in PP through X-ray diffraction (XRD) and transmission electron microscopy (TEM) reveals that under twin screw compounding process, the partial exfoliation and intercalation have taken place within the nanocomposites. An increase in the decomposition temperature was observed under thermogravimetric analysis (TGA), with the presence of HNT. However, MMT tends to lower the maximum decomposition temperature under inert atmosphere. The flammability analysis in an intumescent flame retardant (IFR) system shows that the suitable amount of high aspect ratio nanoparticles with their exfoliation characteristics effectively helps to reduce the sustained combustion. Even though, improved stiffness properties can be observed with the presence of increased filler content, particle agglomeration tends to reduce the mechanical strengths of these composites due to low compatibilization and crack propagation.

Kinetic and Thermodynamics studies for Castor Oil Extraction Using Subcritical Water Technology.

PubMed

Abdelmoez, Wael; Ashour, Eman; Naguib, Shahenaz M; Hilal, Amr; Al Mahdy, Dalia A; Mahrous, Engy A; Abdel-Sattar, Essam

2016-06-01

In this work both kinetic and thermodynamics of castor oil extraction from its seeds using subcritical water technique were studied. It was found that the extraction process followed two consecutive steps. In these steps, the oil was firstly extracted from inside the powder by diffusion mechanism. Then the extracted oil, due to extending the extraction time under high temperature and pressure, was subjected to a decomposition reaction following first order mechanism. The experimental data correlated well with the irreversible consecutive unimolecular-type first order mechanism. The values of both oil extraction rate constants and decomposition rate constants were calculated through non-linear fitting using DataFit software. The extraction rate constants were found to be 0.0019, 0.024, 0.098, 0.1 and 0.117 min(-1), while the decomposition rate constants were 0.057, 0.059, 0.014, 0.019 and 0.17 min(-1) at extraction temperatures of 240, 250, 260, 270 and 280°C, respectively. The thermodynamic properties of the oil extraction process were investigated using Arrhenius equation. The values of the activation energy, Ea, and the frequency factor, A, were 73 kJ mol(-1) and 946, 002 min(-1), respectively. The physicochemical properties of the extracted castor oil including the specific gravity, viscosity, acid value, pH value and calorific value were found to be 0.947, 7.487, 1.094 mg KOH/g, 6.1, and 41.5 MJ/Kg, respectively. Gas chromatography analysis showed that ricinoleic acid (83.6%) appears as the predominant fatty acid in the extracted oil followed by oleic acid (5.5%) and linoleic acid (2.3%).

Decomposition and reactivity of tellurium alkyls in the liquid and gas phases; dihex-5-enyltellurium and dipent-4-enyltellurium as mechanistic probes

NASA Astrophysics Data System (ADS)

Bell, William; McQueen, A. Ewan D.; Walton, John C.; Foster, Douglas F.; Cole-Hamilton, David J.; Hails, Janet E.

1992-02-01

The new tellurium alkyls, dihex-5-enyltellurium and dipent-4-enyltellurium have been prepared and pyrolysed in the gas and liquid phases. in the liquid phase, at 200°C some decomposition occurs but the main isolated products are the tellurium alkyls, bis(cyclopentylmethyl)tellurium and 2-methyltelluracyclopentane respectively. A further product, cyclopentylmethylhex-5-enyltellurium is observed as an intermediate in the rearrangement of dihex-5-enyltellurium, whilst (2-telluracyclopentylmethyl)pent-4-enyltellurium together with pent-1-ene and 1,4-pentadiene is obtained from dipent-4-enyltellurium. These products are interpreted as providing direct evidence for initial homolytic cleavage of the Te-C bonds followed by cyclisation of some of the formed radicals and radical chain reactions. In the gas phase, at 500°C similar products to those obtained in the liquid phase are formed from dipent-4-enyltellurium, although not compounds containing more than one Te atom. Dihex-5-enyltellurium, however, decomposes completely in the gas phase at 700°C to give a mixture of hydrocarbons. Substantial quantities of methylcyclopentane and methylenecyclopentane again confirm that a free radical pathway makes a major contribution to the mechanism. The origin of the other products, especially cyclohexene (the major C 6 product) and cyclohexane is also interpreted in terms of a free radical mechanism leading to the 6-tellurahex-1-enyl radical which cyclises to give the 3-telluracycloheptylradical. This radical rearranges to cyclohexyl Te· which in turn acts as the source of cyclohexene and cyclohexane by H· abstraction or addition. There is little evidence that mechanisms other than free radical operate for decomposition of these metal alkyls.

HNO and NO release from a primary amine-based diazeniumdiolate as a function of pH

PubMed Central

Salmon, Debra J.; Torres de Holding, Claudia L.; Thomas, Lynta; Peterson, Kyle V.; Goodman, Gens P.; Saavedra, Joseph E.; Srinivasan, Aloka; Davies, Keith M.; Keefer, Larry K.; Miranda, Katrina M.

2011-01-01

The growing evidence that nitroxyl (HNO) has a rich pharmacological potential that differs from that of nitric oxide (NO) has intensified interest in HNO donors. Recently, the diazeniumdiolate (NONOate) based on isopropylamine (IPA/NO; Na[(CH3)2CHNH(N(O)NO)]) was demonstrated to function under physiological conditions as an organic analogue to the commonly used HNO donor Angeli’s salt (Na2N2O3). The decomposition mechanism of Angeli’s salt is dependent on pH, with transition from an HNO to an NO donor occurring abruptly near pH 3. Here, pH is shown to also affect product formation from IPA/NO. Chemical analysis of HNO and NO production led to refinement of an earlier, quantum mechanically based prediction of the pH-dependent decomposition mechanisms of primary amine NONOates such as IPA/NO. Under basic conditions, the amine proton of IPA/NO is able to initiate decomposition to HNO by tautomerization to the nitroso nitrogen (N2). At lower pH, protonation activates a competing pathway to NO production. At pH 8, the donor properties of IPA/NO and Angeli’s salt are demonstrated to be comparable, suggesting that at or above this pH, IPA/NO is primarily an HNO donor. Below pH 5, NO is the major product, while IPA/NO functions as a dual donor of HNO and NO at intermediate pH. This pH-dependent variability in product formation may prove useful in examination of the chemistry of NO and HNO. Furthermore, primary amine NONOates may serve as a tunable class of nitrogen oxide donor. PMID:21405089

The issue of gauge choice in the Landau problem and the physics of canonical and mechanical orbital angular momenta

NASA Astrophysics Data System (ADS)

Wakamatsu, M.; Kitadono, Y.; Zhang, P.-M.

2018-05-01

One intriguing issue in the nucleon spin decomposition problem is the existence of two types of decompositions, which are representably characterized by two different orbital angular momenta (OAMs) of quarks. The one is the mechanical OAM, while the other is the so-called gauge-invariant canonical (g.i.c.) OAM, the concept of which was introduced by Chen et al. An especially delicate quantity is the g.i.c. OAM, which must be distinguished from the ordinary (gauge-variant) canonical OAM. We find that, owing to its analytically solvable nature, the famous Landau problem offers an ideal tool to understand the difference and the physical meaning of the above three OAMs, i.e. the standard canonical OAM, g.i.c. OAM, and the mechanical OAM. We analyze these three OAMs in two different formulations of the Landau problem, first in the standard (gauge-fixed) formulation and second in the gauge-invariant (but path-dependent) formulation of DeWitt. Especially interesting is the latter formalism. It is shown that the choice of path has an intimate connection with the choice of gauge, but they are not necessarily equivalent. Then, we answer the question about what is the consequence of a particular choice of path in DeWitt's formalism. This analysis also clarifies the implication of the gauge symmetry hidden in the concept of g.i.c. OAM. Finally, we show that the finding above offers a clear understanding about the uniqueness or non-uniqueness problem of the nucleon spin decomposition, which arises from the arbitrariness in the definition of the so-called physical component of the gauge field.

Alphasatellitidae: a new family with two subfamilies for the classification of geminivirus- and nanovirus-associated alphasatellites.

PubMed

Briddon, Rob W; Martin, Darren P; Roumagnac, Philippe; Navas-Castillo, Jesús; Fiallo-Olivé, Elvira; Moriones, Enrique; Lett, Jean-Michel; Zerbini, F Murilo; Varsani, Arvind

2018-05-09

Nanoviruses and geminiviruses are circular, single stranded DNA viruses that infect many plant species around the world. Nanoviruses and certain geminiviruses that belong to the Begomovirus and Mastrevirus genera are associated with additional circular, single stranded DNA molecules (~ 1-1.4 kb) that encode a replication-associated protein (Rep). These Rep-encoding satellite molecules are commonly referred to as alphasatellites and here we communicate the establishment of the family Alphasatellitidae to which these have been assigned. Within the Alphasatellitidae family two subfamilies, Geminialphasatellitinae and Nanoalphasatellitinae, have been established to respectively accommodate the geminivirus- and nanovirus-associated alphasatellites. Whereas the pairwise nucleotide sequence identity distribution of all the known geminialphasatellites (n = 628) displayed a troughs at ~ 70% and 88% pairwise identity, that of the known nanoalphasatellites (n = 54) had a troughs at ~ 67% and ~ 80% pairwise identity. We use these pairwise identity values as thresholds together with phylogenetic analyses to establish four genera and 43 species of geminialphasatellites and seven genera and 19 species of nanoalphasatellites. Furthermore, a divergent alphasatellite associated with coconut foliar decay disease is assigned to a species but not a subfamily as it likely represents a new alphasatellite subfamily that could be established once other closely related molecules are discovered.

Estimating Seven Coefficients of Pairwise Relatedness Using Population-Genomic Data

PubMed Central

Ackerman, Matthew S.; Johri, Parul; Spitze, Ken; Xu, Sen; Doak, Thomas G.; Young, Kimberly; Lynch, Michael

2017-01-01

Population structure can be described by genotypic-correlation coefficients between groups of individuals, the most basic of which are the pairwise relatedness coefficients between any two individuals. There are nine pairwise relatedness coefficients in the most general model, and we show that these can be reduced to seven coefficients for biallelic loci. Although all nine coefficients can be estimated from pedigrees, six coefficients have been beyond empirical reach. We provide a numerical optimization procedure that estimates all seven reduced coefficients from population-genomic data. Simulations show that the procedure is nearly unbiased, even at 3× coverage, and errors in five of the seven coefficients are statistically uncorrelated. The remaining two coefficients have a negative correlation of errors, but their sum provides an unbiased assessment of the overall correlation of heterozygosity between two individuals. Application of these new methods to four populations of the freshwater crustacean Daphnia pulex reveal the occurrence of half siblings in our samples, as well as a number of identical individuals that are likely obligately asexual clone mates. Statistically significant negative estimates of these pairwise relatedness coefficients, including inbreeding coefficients that were typically negative, underscore the difficulties that arise when interpreting genotypic correlations as estimations of the probability that alleles are identical by descent. PMID:28341647

Ensemble survival tree models to reveal pairwise interactions of variables with time-to-events outcomes in low-dimensional setting

PubMed Central

Dazard, Jean-Eudes; Ishwaran, Hemant; Mehlotra, Rajeev; Weinberg, Aaron; Zimmerman, Peter

2018-01-01

Unraveling interactions among variables such as genetic, clinical, demographic and environmental factors is essential to understand the development of common and complex diseases. To increase the power to detect such variables interactions associated with clinical time-to-events outcomes, we borrowed established concepts from random survival forest (RSF) models. We introduce a novel RSF-based pairwise interaction estimator and derive a randomization method with bootstrap confidence intervals for inferring interaction significance. Using various linear and nonlinear time-to-events survival models in simulation studies, we first show the efficiency of our approach: true pairwise interaction-effects between variables are uncovered, while they may not be accompanied with their corresponding main-effects, and may not be detected by standard semi-parametric regression modeling and test statistics used in survival analysis. Moreover, using a RSF-based cross-validation scheme for generating prediction estimators, we show that informative predictors may be inferred. We applied our approach to an HIV cohort study recording key host gene polymorphisms and their association with HIV change of tropism or AIDS progression. Altogether, this shows how linear or nonlinear pairwise statistical interactions of variables may be efficiently detected with a predictive value in observational studies with time-to-event outcomes. PMID:29453930

Detection of the pairwise kinematic Sunyaev-Zel'dovich effect with BOSS DR11 and the Atacama Cosmology Telescope

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bernardis, F. De; Aiola, S.; Vavagiakis, E. M.

Here, we present a new measurement of the kinematic Sunyaev-Zel'dovich effect using data from the Atacama Cosmology Telescope (ACT) and the Baryon Oscillation Spectroscopic Survey (BOSS). Using 600 square degrees of overlapping sky area, we evaluate the mean pairwise baryon momentum associated with the positions of 50,000 bright galaxies in the BOSS DR11 Large Scale Structure catalog. A non-zero signal arises from the large-scale motions of halos containing the sample galaxies. The data fits an analytical signal model well, with the optical depth to microwave photon scattering as a free parameter determining the overall signal amplitude. We estimate the covariancemore » matrix of the mean pairwise momentum as a function of galaxy separation, using microwave sky simulations, jackknife evaluation, and bootstrap estimates. The most conservative simulation-based errors give signal-to-noise estimates between 3.6 and 4.1 for varying galaxy luminosity cuts. We discuss how the other error determinations can lead to higher signal-to-noise values, and consider the impact of several possible systematic errors. Estimates of the optical depth from the average thermal Sunyaev-Zel'dovich signal at the sample galaxy positions are broadly consistent with those obtained from the mean pairwise momentum signal.« less

Detection of the pairwise kinematic Sunyaev-Zel'dovich effect with BOSS DR11 and the Atacama Cosmology Telescope

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bernardis, F. De; Vavagiakis, E.M.; Niemack, M.D.

We present a new measurement of the kinematic Sunyaev-Zel'dovich effect using data from the Atacama Cosmology Telescope (ACT) and the Baryon Oscillation Spectroscopic Survey (BOSS). Using 600 square degrees of overlapping sky area, we evaluate the mean pairwise baryon momentum associated with the positions of 50,000 bright galaxies in the BOSS DR11 Large Scale Structure catalog. A non-zero signal arises from the large-scale motions of halos containing the sample galaxies. The data fits an analytical signal model well, with the optical depth to microwave photon scattering as a free parameter determining the overall signal amplitude. We estimate the covariance matrixmore » of the mean pairwise momentum as a function of galaxy separation, using microwave sky simulations, jackknife evaluation, and bootstrap estimates. The most conservative simulation-based errors give signal-to-noise estimates between 3.6 and 4.1 for varying galaxy luminosity cuts. We discuss how the other error determinations can lead to higher signal-to-noise values, and consider the impact of several possible systematic errors. Estimates of the optical depth from the average thermal Sunyaev-Zel'dovich signal at the sample galaxy positions are broadly consistent with those obtained from the mean pairwise momentum signal.« less

Detection of the Pairwise Kinematic Sunyaev-Zel'dovich Effect with BOSS DR11 and the Atacama Cosmology Telescope

NASA Technical Reports Server (NTRS)

De Bernardis, F.; Aiola, S.; Vavagiakis, E. M.; Battaglia, N.; Niemack, M. D.; Beall, J.; Becker, D. T.; Bond, J. R.; Calabrese, E.; Cho, H.;

Detection of the pairwise kinematic Sunyaev-Zel'dovich effect with BOSS DR11 and the Atacama Cosmology Telescope

NASA Astrophysics Data System (ADS)

De Bernardis, F.; Aiola, S.; Vavagiakis, E. M.; Battaglia, N.; Niemack, M. D.; Beall, J.; Becker, D. T.; Bond, J. R.; Calabrese, E.; Cho, H.; Coughlin, K.; Datta, R.; Devlin, M.; Dunkley, J.; Dunner, R.; Ferraro, S.; Fox, A.; Gallardo, P. A.; Halpern, M.; Hand, N.; Hasselfield, M.; Henderson, S. W.; Hill, J. C.; Hilton, G. C.; Hilton, M.; Hincks, A. D.; Hlozek, R.; Hubmayr, J.; Huffenberger, K.; Hughes, J. P.; Irwin, K. D.; Koopman, B. J.; Kosowsky, A.; Li, D.; Louis, T.; Lungu, M.; Madhavacheril, M. S.; Maurin, L.; McMahon, J.; Moodley, K.; Naess, S.; Nati, F.; Newburgh, L.; Nibarger, J. P.; Page, L. A.; Partridge, B.; Schaan, E.; Schmitt, B. L.; Sehgal, N.; Sievers, J.; Simon, S. M.; Spergel, D. N.; Staggs, S. T.; Stevens, J. R.; Thornton, R. J.; van Engelen, A.; Van Lanen, J.; Wollack, E. J.

2017-03-01

We present a new measurement of the kinematic Sunyaev-Zel'dovich effect using data from the Atacama Cosmology Telescope (ACT) and the Baryon Oscillation Spectroscopic Survey (BOSS). Using 600 square degrees of overlapping sky area, we evaluate the mean pairwise baryon momentum associated with the positions of 50,000 bright galaxies in the BOSS DR11 Large Scale Structure catalog. A non-zero signal arises from the large-scale motions of halos containing the sample galaxies. The data fits an analytical signal model well, with the optical depth to microwave photon scattering as a free parameter determining the overall signal amplitude. We estimate the covariance matrix of the mean pairwise momentum as a function of galaxy separation, using microwave sky simulations, jackknife evaluation, and bootstrap estimates. The most conservative simulation-based errors give signal-to-noise estimates between 3.6 and 4.1 for varying galaxy luminosity cuts. We discuss how the other error determinations can lead to higher signal-to-noise values, and consider the impact of several possible systematic errors. Estimates of the optical depth from the average thermal Sunyaev-Zel'dovich signal at the sample galaxy positions are broadly consistent with those obtained from the mean pairwise momentum signal.

Ensemble survival tree models to reveal pairwise interactions of variables with time-to-events outcomes in low-dimensional setting.

PubMed

Dazard, Jean-Eudes; Ishwaran, Hemant; Mehlotra, Rajeev; Weinberg, Aaron; Zimmerman, Peter

2018-02-17

Unraveling interactions among variables such as genetic, clinical, demographic and environmental factors is essential to understand the development of common and complex diseases. To increase the power to detect such variables interactions associated with clinical time-to-events outcomes, we borrowed established concepts from random survival forest (RSF) models. We introduce a novel RSF-based pairwise interaction estimator and derive a randomization method with bootstrap confidence intervals for inferring interaction significance. Using various linear and nonlinear time-to-events survival models in simulation studies, we first show the efficiency of our approach: true pairwise interaction-effects between variables are uncovered, while they may not be accompanied with their corresponding main-effects, and may not be detected by standard semi-parametric regression modeling and test statistics used in survival analysis. Moreover, using a RSF-based cross-validation scheme for generating prediction estimators, we show that informative predictors may be inferred. We applied our approach to an HIV cohort study recording key host gene polymorphisms and their association with HIV change of tropism or AIDS progression. Altogether, this shows how linear or nonlinear pairwise statistical interactions of variables may be efficiently detected with a predictive value in observational studies with time-to-event outcomes.

Detection of the pairwise kinematic Sunyaev-Zel'dovich effect with BOSS DR11 and the Atacama Cosmology Telescope

DOE PAGES

Bernardis, F. De; Aiola, S.; Vavagiakis, E. M.; ...

2017-03-07

Here, we present a new measurement of the kinematic Sunyaev-Zel'dovich effect using data from the Atacama Cosmology Telescope (ACT) and the Baryon Oscillation Spectroscopic Survey (BOSS). Using 600 square degrees of overlapping sky area, we evaluate the mean pairwise baryon momentum associated with the positions of 50,000 bright galaxies in the BOSS DR11 Large Scale Structure catalog. A non-zero signal arises from the large-scale motions of halos containing the sample galaxies. The data fits an analytical signal model well, with the optical depth to microwave photon scattering as a free parameter determining the overall signal amplitude. We estimate the covariancemore » matrix of the mean pairwise momentum as a function of galaxy separation, using microwave sky simulations, jackknife evaluation, and bootstrap estimates. The most conservative simulation-based errors give signal-to-noise estimates between 3.6 and 4.1 for varying galaxy luminosity cuts. We discuss how the other error determinations can lead to higher signal-to-noise values, and consider the impact of several possible systematic errors. Estimates of the optical depth from the average thermal Sunyaev-Zel'dovich signal at the sample galaxy positions are broadly consistent with those obtained from the mean pairwise momentum signal.« less

Reduced Order Model Basis Vector Generation: Generates Basis Vectors fro ROMs

DOE Office of Scientific and Technical Information (OSTI.GOV)

Arrighi, Bill

2016-03-03

libROM is a library that implements order reduction via singular value decomposition (SVD) of sampled state vectors. It implements 2 parallel, incremental SVD algorithms and one serial, non-incremental algorithm. It also provides a mechanism for adaptive sampling of basis vectors.

PCB Congener Sorption To Carbonaceous Sediment Components: Macroscopic Comparison And Characterization Of Sorption Kinetics And Mechanism

EPA Science Inventory

Sorption of polychlorinated biphenyls (PCBs) to sediment is a key process in determining their mobility, bioavailability, and chemical decomposition in aquatic environments. In order to examine the validity of currently used interpretation approaches for PCBs sorption, comparati...

Electron attachment to trinitrotoluene (TNT) embedded in He droplets: complete freezing of dissociation intermediates in an extended range of electron energies.

PubMed

Mauracher, Andreas; Schöbel, Harald; Ferreira da Silva, Filipe; Edtbauer, Achim; Mitterdorfer, Christian; Denifl, Stephan; Märk, Tilmann D; Illenberger, Eugen; Scheier, Paul

2009-10-01

Electron attachment to the explosive trinitrotoluene (TNT) embedded in Helium droplets (TNT@He) generates the non-decomposed complexes (TNT)(n)(-), but no fragment ions in the entire energy range 0-12 eV. This strongly contrasts the behavior of single TNT molecules in the gas phase at ambient temperatures, where electron capture leads to a variety of different fragmentation products via different dissociative electron attachment (DEA) reactions. Single TNT molecules decompose by attachment of an electron at virtually no extra energy reflecting the explosive nature of the compound. The complete freezing of dissociation intermediates in TNT embedded in the droplet is explained by the particular mechanisms of DEA in nitrobenzenes, which is characterized by complex rearrangement processes in the transient negative ion (TNI) prior to decomposition. These mechanisms provide the condition for effective energy withdrawal from the TNI into the dissipative environment thereby completely suppressing its decomposition.

Atomistic simulation of orientation dependence in shock-induced initiation of pentaerythritol tetranitrate.

PubMed

Shan, Tzu-Ray; Wixom, Ryan R; Mattsson, Ann E; Thompson, Aidan P

2013-01-24

The dependence of the reaction initiation mechanism of pentaerythritol tetranitrate (PETN) on shock orientation and shock strength is investigated with molecular dynamics simulations using a reactive force field and the multiscale shock technique. In the simulations, a single crystal of PETN is shocked along the [110], [001], and [100] orientations with shock velocities in the range 3-10 km/s. Reactions occur with shock velocities of 6 km/s or stronger, and reactions initiate through the dissociation of nitro and nitrate groups from the PETN molecules. The most sensitive orientation is [110], while [100] is the most insensitive. For the [001] orientation, PETN decomposition via nitro group dissociation is the dominant reaction initiation mechanism, while for the [110] and [100] orientations the decomposition is via mixed nitro and nitrate group dissociation. For shock along the [001] orientation, we find that CO-NO(2) bonds initially acquire more kinetic energy, facilitating nitro dissociation. For the other two orientations, C-ONO(2) bonds acquire more kinetic energy, facilitating nitrate group dissociation.

Efficient solution of the Wigner-Liouville equation using a spectral decomposition of the force field

NASA Astrophysics Data System (ADS)

Van de Put, Maarten L.; Sorée, Bart; Magnus, Wim

2017-12-01

The Wigner-Liouville equation is reformulated using a spectral decomposition of the classical force field instead of the potential energy. The latter is shown to simplify the Wigner-Liouville kernel both conceptually and numerically as the spectral force Wigner-Liouville equation avoids the numerical evaluation of the highly oscillatory Wigner kernel which is nonlocal in both position and momentum. The quantum mechanical evolution is instead governed by a term local in space and non-local in momentum, where the non-locality in momentum has only a limited range. An interpretation of the time evolution in terms of two processes is presented; a classical evolution under the influence of the averaged driving field, and a probability-preserving quantum-mechanical generation and annihilation term. Using the inherent stability and reduced complexity, a direct deterministic numerical implementation using Chebyshev and Fourier pseudo-spectral methods is detailed. For the purpose of illustration, we present results for the time-evolution of a one-dimensional resonant tunneling diode driven out of equilibrium.

Reactions of Criegee Intermediates with Non-Water Greenhouse Gases: Implications for Metal Free Chemical Fixation of Carbon Dioxide.

PubMed

Kumar, Manoj; Francisco, Joseph S

2017-09-07

High-level theoretical calculations suggest that a Criegee intermediate preferably interacts with carbon dioxide compared to two other greenhouse gases, nitrous oxide and methane. The results also suggest that the interaction between Criegee intermediates and carbon dioxide involves a cycloaddition reaction, which results in the formation of a cyclic carbonate-type adduct with a barrier of 6.0-14.0 kcal/mol. These results are in contrast to a previous assumption that the reaction occurs barrierlessly. The subsequent decomposition of the cyclic adduct into formic acid and carbon dioxide follows both concerted and stepwise mechanisms. The latter mechanism has been overlooked previously. Under formic acid catalysis, the concerted decomposition of the cyclic carbonate may be favored under tropospheric conditions. Considering that there is a strong nexus between carbon dioxide levels in the atmosphere and global warming, the high reactivity of Criegee intermediates could be utilized for designing efficient carbon capture technologies.

Modified reaction mechanism of aerated n-dodecane liquid flowing over heated metal tubes

NASA Technical Reports Server (NTRS)

Reddy, K. T.; Cernansky, N. P.; Cohen, R. S.

1988-01-01

The degradation mechanism of the n-dodecane was studied using a modified jet fuel thermal oxidation tester containing a sample withdrawal system as a reaction vessel. The reaction products were identified using gas chromatography and mass spectorometry. The soluble products were found to consist mainly of C5-C10 n-alkanes and 1-alkenes, C7-C10 aldehydes, tetrahydrofuran derivatives, dodecanol and dodecanone isomers, dodecyl hydroperoxide (ROOH) decomposition products, and C24 alkane isomers. The data from the experiments agreed with those of Hazlett et al. (1977). It was found that alkyl peroxide radical reactions dominate in the autooxidation temperature regime (at T not above 300 C); the dominant path is for the alkyl peroxyl radical to react bimolecularly with fuel to yield primarily alkyl hydroperoxides. The alkyl peroxide radical also undergoes self-termination and unimolecular isomerization and decomposition reactions, to yield smaller amounts of C12 alcohol plus ketone products and tetrahydrofuran derivatives, respectively.